::r ::] ~••••~·--- - -Order of Contents
Committees
Sponsors and Exhibitors
General Information
Program Timetable
Advertizing Section
Maps
Abstracts
Plenary Lectures

PL 1-6Microsymposia

MS 01-15

Poster Sessions

PO 001-209

Author Index

Committees
Asian Crystallographic Association
President:

Prof. Yu WANG
National Taiwan University, Taiwan

Vice-President:

Prof. M. VIJAYAN
Indian Institute of Science, India

Secreta ry/T reas urer:

Dr. Brian W. SKELTON
University of Western Australia, Australia

International Program Committee for AsCA'04
ChairmanProf. Makoto SAKATA

Nagoya University, Japan

Prof. Kunio MIKI

Kyoto University, Japan

Dr. Chris HOWARDANSTO, Australia

Prof. Mitchell GUSS

University of Sydney, Australia

Prof. S.L.CHANG

National Tsing Hua University, Taiwan

Prof. Jing Tai ZHAO

Chinese Academy of Sciences, China

Prof. Y.J. PARK

Sook Myung Womens University, Korea

Prof. Nguyen VAN TRI

Hanoi University of Technology, Vietnam

Prof. M. VIJAYAN

Indian Institute of Science, India

International Organizing Committee for AsCA'04
ChairmanProf. lan D. WILLIAMSHKUST, Hong Kong

Prof. Thomas C-W. MAK

The Chinese University of Hong Kong

Prof. Wing Tak WONG

University of Hong Kong, Hong Kong

Dr. Raymond W-Y. WONG

Hong Kong Baptist University, Hong Kong

Prof. Wa Hung LEUNG

HKUST, Hong Kong

Prof. Zhen Yang LIN

HKUST, Hong Kong

Prof. Yu Fong YEN

HKUST, Hong Kong

Prof. Ji Wen CAl

Sun Yat-Sen (Zhongshan) University, China

Prof. Zhong Yuan ZHOU

Hong Kong Polytechnic University

AsCA04 Secretariat:
Mr. Alvin W-H. SIU

HKUST, Hong Kong

Dr. Eiji NISHIBORIU. Nagoya, Japan

IUCr Scientific Freedom Policy Statement
The organizing committee of the AsCA'04 conference observes the basic policyof non-discrimination . We affirm the rights of scientists throughout the world toadhere to, or to associate with , international scientific activity. There will be norestrictions based on nationality, race , color, age , religion , political philosophy,
ethnic origin , citizenship , language or sex , in accordance with the statutes on
the International Council of Scientific Unions. At this meeting no barriers will
exist which would prevent the participation of bona fide scientists.

Scientific Program
Plenary Lectures:Prof Jun AKIMITSU
Department of Physics, Aoyama Gakuin University, Japan
Superconductivity and Magnetism of Borides

Prof Tei . P. SINGH
Department of Biophysics, All India Institute of Medical Sciences , India
Structures of Novel Signaling Proteins Secreted During Involution
and Involved in Apoptosis

Prof Shie Ming PENG
Department of Chemistry , National Taiwan University, Taiwan
From Metal String Complexes to Molecular Metal Wires

Prof lsao TANAKA
Division of Biological Sciences , Hokkaido University Japan
High-throughput Protein Crystallography

Dr Jian Wei MIAO
Stanford Linear Accelerator Center, Stanford University, USA
Crystallography without Crystals

Prof Mike HURSTHOUSE
University of Southampton , UKA Grid-enabled High Throughput Chemical CrystallographyNew Opportunity for Structural Chemistry

Microsymposia
Monday, June 28

10:15-12:15

MS-1

Molecular Recognition and Catalysis

MS-2

Synchrotron-related Science and Applications

MS-3

Structural Chemistry

Monday, June 28

16:00-18:00

MS-4

Macromolecular Assemblies

MS-5

Neutron Scattering Science

MS-6

Supramolecular Chemistry & Crystal Engineering

Tuesday, June 29

10:15-12:15

MS-7

Receptors, Signaling & receptor-drug Interactions

MS-8

Materials Science I

MS-9

Electron Diffraction and Microscopy

Tuesday, June 29

16:00-18:00

MS-1 0

Structural Genomics

MS-11

Structural Nanoscience

MS-12

Sic-informatics and Computational Analysis I

Wednesday, June 30

10:15-12:15

MS-13

Sic-informatics and Computational Analysis II

MS-14

Advanced Applications of Powder Diffraction

MS-15

Materials Science IISponsors and Exhibitors
International Union of Crystallography
Asian Crystallographic Association
Crystallographic Society of Japan
Society of Crystallographers in Australia and New ZealandHong Kong University of Science and Technology
Rigaku Corporation
Bruker Nonius
PANalyticalmarresearch

Oxford Cryosystems
Oxford Diffraction
CCP4
Fluidigm
Universal Analytical - Discovery Partners
Crystal Impact

XenocsRCSB Protein Data Bank
Stoe & CIE
Hitachilshikawajima
Ricoh

Fujifilm
LAS
Ryoka Systems

Gloria-Tourist, Japan
Hong Kong Tourist Association

Evening Social Functions:Sunday June 27
PANalytical Welcome Mixer
A reception and social mixer will be organized for all AscA04 registrants andaccompanying persons in the University Bistro , University Center, HKUST.
Free drinks and light buffet meal will be provided. Time 18:30-21:00. We are
grateful to PANalytical for their sponsorship of this event.

Monday June 28
Bruker Nonius Harbor Cruise and Dinner Buffet
The Hong Kong harbor at night is a spectacular sight not to be missed . Space islimited to 200 persons. Available to all full conference registrants andaccompanying persons. Some space available for students, enquire atconference desk to sign up ! Buses will depart HKUST at 18:45 and return
21:45 . We are grateful to Bruker/Nonius for their sponsorship of this event.

Tuesday June 29
Rigaku Traditional Chinese Seafood Banquet
The Star Seafood Floating restaurant in Shatin is famous for its seafoodbanquet. This event is open to all conference registrants and accompanying
persons. Buses will depart HKUST at 18:45 and return at 21:45. Residents of
Nikko Hotel please contact conference secretariat for arrangements. We are
grateful to Rigaku Corporation for their sponsorship of this event.

Wednesday June30
marresearch Farewell Party
Say good-bye with a farewell party featuring drinks and snack buffet at theconclusion of the final academic session in the afternoon . Open for allparticipants and held in the academic concourse, HKUST. We are grateful tomarresearch for their sponsorship of this event.

General Information:
Meeting Dates and Venue:
The meeting is being held on the campus of the Hong Kong University of
Science and Technology, June 27- 30 2004 . Registration will commence on theafternoon of Sunday June 27 (12 :00 - 21 :00) and may be continued on Monday
June 28 (08:00). In case of early check in on Saturday 26 June or late arrival on
Sunday evening , please call (9777 -4149) , (9276-7717) or (6112-0829) .

Conference Office:The conference office is located in the academic concourse , opposite Lecture
Theatre B. It will be open on Sunday June 27 for registration from 14:00 until
21 :00 . Delegates arriving after this time should register on Monday morning
before 10:00. Messages and communications for delegates may be posted on
notice boards next to the conference desk. During the conference period
FAXes may be sent to +(852)-3106-3446 and clearly marked to the attention of
the delegate in question. For phone contact please call +(852)-2358-7359 , or+(852)-9777-4149 . The time zone for Hong Kong in June is +7 GMT.

Phone, Fax and Post:
If you wish to make an overseas call or FAX please contact the conference
secretariat at the conference desk. In general only local calls can be made fromthe public phones on campus. Local calls within Hong Kong are normally 8digits. For directory enquiries in English dial 1081 . Phone cards with discount
IDD rates may be purchased at the airport or down-town . When phoning
overseas , for example on mobile phones , note that the international dialingcode should be preceded with 001 . Due to the relatively short duration of theconference and variability of post we do not recommend sending regular mail. If
you wish to send mail there is a mailing desk inside the University Souvenir
Shop on the Entrance Plaza near Lift 2.
In case of need speed-post items may be sent to: AsCA Secretariat. c/o Prof.
lan Williams , Department of Chemistry , HKUST, Clear Water Bay, Kowloon
Hong Kong .

E-mail and Internet:
The university has over 20 workstations for free E-mail and internet accessaround the campus and we have arranged computing facilities to be available in
Computer Barn A, Lift 17-18. For further details or assistance please contact
Prof. Zhenyang Lin at the conference help desk.

Banking and Currency Exchange:
Currency in Hong Kong is the Hong Kong dollar, which is pegged at a rate of
7.78 per US$. It is advisable that you change to local currency before you
depart. since exchange rates at the Hong Kong airport may not be favorable .
The campus of HKUST has two bank branches , the Hang Seng Bank (Ph:2198-0441) and the Bank of China (Ph: 2358-2345) located near Lift 1 acrossfrom the sun-dial. Opening hours Mon-Fri 09:00 to 17:00. They can provide
exchange to HK dollars for limited foreign currencies such as US dollars,
Japanese Yen or Ri:mminbi. There are numerous money exchanges in the
tourist areas of Tsim Sha Tsui , Kowloon or Hong Kong Island , but these arelocated far from the university campus.
The most convenient access to local cash may be from four ATM machines on
campus, two at the bank branches and two at the entrance to the academic
concourse. These are open 24 hours and should accept most international
credit cards , or bank cards on the Plus or Cirrus systems.

Name Badges:
Name badges are required for entry to all scientific sessions, lunches andevening functions. Different colors for name badges of participants is as below:
Conference organizers

Red

Exhibitors

Yellow

Full registrants

Green

Students

Blue

Accompanying persons

White

For inquiries when the conference desk is closed , please contact member oforganizing committee or one of the assistants. Students must show proof of acurrent valid student identity upon registration. Accompanying persons areallowed access to all meals and social functions but not the academic sessions

Medical and Emergency Contacts:
The phone number for emergency in Hong Kong is 999. This will connect you to
POLICE . FIRE and AMBULANCE (MEDICAL) services. State your problem andlocation clearly and assistance will be sent as soon as possible. Help should beavailable in English , Cantonese or Mandarin. If you are on the university
campus either dial extension 8999 or 6565 from a campus internal phone(otherwise 2358-8999 or 2358-6565). The 8999 number is the line for all main
emergency services. The campus security center will contact 999 on yourbehalf and send more immediate assistance. For difficulties such as report ofstolen property, locked out of room , please use the 6565 number.

Accommodation:
Many delegates have elected to stay on campus in faculty apartments , visitor
center or student dormitory rooms . An information sheet on guest facilities andprocedures for check-in/out will be provided to you upon registration .
Special conference room rates had been negotiated with the Nikko Hotel , Mody
Road , East Tsim Sha Tsui. Please contact Ms. Pat Chan (Ph : 2313-4508) for
details. A conference bus to the HKUST campus will be provided at 08 :00 on
Monday , Tuesday and Wednesday from outside the lobby of Nikko Hotel.

Meals and Catering Arrangements:
Delegates staying on campus accommodation will be given breakfast vouchers
and all delegates will receive lunch vouchers. Details of time and locations forthese will be given at registration. The campus is relatively remote from theurban area and so there are few off-site restaurants within walking distance. A
list of restaurants , bars and tourist attractions are listed on the pages that follow .
On-campus there are a number of dining choices:
Maxim's Chinese Restaurant: Ground Floor (Lift 14-16)
Chinese food- meals for ca HK$50 (US$7 .50)
Dim sum and Sun Roast Chinese Tea room : Level LG1 (Lift 14-16)
Also operated by the Maxims group, set meals for ca HK$25 (US$3 .00)
Student Canteens and Eateries : Levels LG7 and LG5 (Lift 11 /12)
variety of meals, noodles and rice dishes ca HK$20 (US$2 .50)
there is also a MacDonald's franchise on LG5 if you crave a 'happy meal'
University Bistro: University Center
mostly Western meals for ca HK$50 (US$7 .50) Venue for the welcome mixer.
Coffee Shop: Academic concourse (Lift 25-26)
This has snacks , sandwiches and light meals . Starbuck's coffee in the cart
outside with espresso and cappuccino . Conveniently located near to theconference desk and lecture theatres .

Transport:
Buses will be provided to campus on Sunday 27 June from HK International
airport. Please sign up at conference desk if you need assistance with a return
trip to the airport on Wednesday 30 June or Thursday 1 July. The nearest shops
and restaurants to HKUST campus are in the newly developed Tseung Kwan 0 ,which can be accessed in 10-15 mins . by shuttle mini-bus from outside theuniversity main gate. There are large shopping centers based around the Hang
Hau and Po Lam MTR stations in Tseung Kwan 0.

Transportation to Down Town:
Kowloon:Taxis to the Nikko Hotel or Star Ferry terminal in Tsim Sha Tsui should cost
about HK$100 (US$12) and take 25-30 minutes. Alternatively take public mini
bus to Choi Hung MTR station and then the MTR subway to stations in
Mongkok , Yau Ma Tei , Jordan or Tsim Sha Tsui .
Hong Kong Island:
Taxis to Causeway Bay , Wanchai , Admiralty or Central districts of Hong Kong
Island will cost ca HK$140-160 (about US$20) and take about 30-35 minutes.
Alternatively take a mini-bus to Hang Hau MTR station in Tseung Kwan 0 andthen MTR subway to Hong Kong Island.

Tours and Attractions:
Hong Kong is a world famous travel destination and city. It is a center forinternational commerce and trade . Most visitors are familiar with the high riseskyscrapers of Hong Kong island and the views of Victoria Harbor. The
conference venue is outside of the urban area with a beautiful vista overlooking
Clear Water Bay. However there is relatively easy access to the down-town
areas of Kowloon and Hong Kong Island by variety of public transportation.
A number of attractions are listed on the next few pages. For further details it issuggested that you purchase one of the many guide books available in different
languages. Some information leaflets from the Hong Kong Tourist Association
are available at the conference desk.

Things to Do/See:
Kowloon:Victoria Harbor
The Star ferry terminal is a good place to begin a visit to the down town area .
From near the old KCR clock tower there is an excellent view of the harbor, anda pleasant walk along the water front. Star ferry is also a convenient starting
place for shopping in the nearby Star House (computers) or the Ocean Center
shopping mall. The Star Ferries are the famous green and white boats thattraverse the Hong Kong harbor. They offer a cheap mode of transport (caHK$2) for a crossing between Kowloon (Star Ferry terminal) and Hong Kong
Island (either Central or Wanchai piers) and at least one trip is recommended!
Tsim Sha Tsui (TST)Near to Star Ferry is the main tourist area of Kowloon , called Tsim Sha Tsui.
The main shopping strip is along Nathan Road , which is referred to as theGolden Mile , due to the lights at night-time. Be cautious when buying gold ,jewelry, 'copy' watches and electronic goods. In stores look for HK tourist
association signs in the window. TST also houses many of the museums inHong Kong near the Star Ferry or along Chatham Road.

Jordan, Yau Ma Tei and Mongkok
These areas north of TST along Nathan Road are also served by MTR stations
and offer a glimpse of a more authentic Hong Kong. Highlights in Yau Ma Tei
include the Jade Market open 10:00-15: 30 and the Temple Street night market.
Wong Tai Sin Temple
To get good karma or a glimpse of your future , a visit to Wong Tai Sin temple
and its fortune tellers may be worthwhile . It is open from 07:00 - 17:30 .
Relatively close to HKUST, take MTR from Choi Hung to Wong Tai Sin station.

Hong Kong Island:Victoria Peak via the Peak Tram
The highest overlook of the city and Hong Kong harbor, has lookout withtelescope . Sadly these days pollution has reduced the beauty of this vista
however the weather in late June predominates from the sea so the air is clear,even though hot and humid . The Peak can be accessed via the Peak Tram ,which is a funicular cable railway ride , some sections have steep ascentdescent and are not for the faint hearted!
Hong Kong Island Tram
Hong Kong island is famous for its modern skyscraper landscape, whilst few
older buildings survive one tradition is the Hong Kong island tram , which runs
between North Point and Kennedy Town and costs about HK$2. Though rather
slow a ride provides an interesting and way of sightseeing through the main
business and shopping districts at a leisurely pace.
Ocean Park
In the hot weather of June, some like to cool down with a visit to this water
theme-park , located on Hong Kong island between Stanley and Aberdeen . It is
open daily 10:00-18 :00 , admission ca. HK$150. To get there we suggest take
MTR to Admiralty station and then taxi.
Causeway Bay
One of the busiest parts of downtown Hong Kong , this is an experience forthose who are comfortable with crowds . Causeway Bay is accessible from the
MTR system and has a host of shopping options from expensive to bargain.
There is a large Japanese department store , Sago, and variety of outlets in airconditioned Times Square shopping mall.
StanleyAn alternative to down town bustle is to take a trip to Stanley on the far south
side of Hong Kong island. This has a recently developed water-front withmodern shops and eateries as well as retaining the old tourist bazaar, which isthe place to get presents , silk fashions , chops, tee-shirts , local art andsouvenirs.

Shopping malls can be found based around most of the subway (MTR) stations.
Hong Kong's past reputation for shopping bargains is rather jaded these days ,the city has become one of the most expensive in the world so high overhead
costs mean bargains are usually a thing of the past. Regarding electronic goods
people from the West are often amazed by the range of modern items , but
shoppers from Taiwan or Japan are less likely to be impressed .

Outlying Islands and Beyond :If you have 1 or 2 free days the following may be interesting side trips :Lantau Island
A visit to the world's largest seated golden Buddha statue on Lantau Island (theother side of the airport) is a popular trip . Take MTR/taxi to Central to the Pierfor the Outlying Islands and the ferry (1 hr) to Silver-mine Bay. Bus or taxi to thebuddha then takes about another 30 mins. There are excellent hiking trails on
Lantau , though the weather in late June is hot and humid so take plenty ofwater.
Macau
This former Portugese colony is readily reached from the Hong Kong-Macau
Ferry Terminal , Shum Tak Center, Central district Hong Kong Island. (Sheung
Wan MTR station) The trip takes 1 hr by jetfoil which leave every 30 minutes , ormore frequently at weekends. Macau is a separate Special Administrative
Region within China from Hong Kong , so please check on your entry and visa
requirements beforehand. If you intend to stay overnight you can book a hotel
room at one of the travel agents near to the ferry terminal entrance. The room
rates for Macau in mid-week are quite favorable , since Macau relies heavily on
visitors from Hong Kong at the weekends . Note that July 1 is a public holiday inHong Kong so discount rates may not apply. Macau is famous for its nightlife,
casinos (we advise you not to take too much money with you!) restored colonialbuildings and some excellent Macanese and Portuguese cuisine . Macau has aquite different atmosphere from Hong Kong and despite the higher population
density, it actually can seem less crowded . Sites worth visiting include St.
Paul's Edifice, the Guia Lighthouse and its surrounding park, a casino such as
the famous Hotel Lisboa and the new observation tower, which is one of thetallest in Asia.
Guangzhou, Shenzhen and China
Trips across the border to China can be arranged through most travel agents inHong Kong , or visit an office of the China Travel Service (CTS). Trains leave
Kowloon main railway station to Guangzhou about every hour. For a more
simple trip across the border to the adjacent city of Shenzhen a Special
Economic Zone of China , you can take the KCR railway to the last station (LoWu) and cross over the foot-bridge. Make sure you have appropriate paper
work and visa before you travel. Whilst the economic prosperity of Shenzhen
has dramatically improved , we do advise that you be aware that security ismore of a concern than in Hong Kong and be especially careful with valuables
and cash. That having been said a trip to China can offer much to the first time
visitor and , like Macau , provides an interesting contrast to Hong Kong .

Restaurants and Night-life:
Although we hope to cater for registrants through the course of the conference
Hong Kong has some of the widest range and best food in Asia-Pacific region .
Excellent restaurant information can be the Guide 2004 , published by bemagazine or visit the website www.hongkongrestaurantguide.com .
A variety of restaurants are selected here , naturally there are many more
Chinese than listed , but these are not difficult to find . One suggestion is to visit
the food 'tower' Times Square, Causeway Bay , which has a number of regional
Chinese restaurants including Shanghai and Yunnan .

Chinese:Cantonese
Ph : 2722-0932
Serenade
HK Cultural Center, Tsim Sha Tsui
Fine local cuisine, located near to Star Ferry terminal.
Szechuan
The Red Pepper Ph: 2577-3811
7 Lan Fong Rd. , Causeway Bay
A good choice for those who wish to try fiery Chinese food.
Xinjiang
Ph: 3162-3544
Pasha
G/F Cleveland Mansions, Cleveland St, Causeway Bay
One of the latest trends in Hong Kong is Xinjiang cuisine from the uighur regionof Western China. Lamb shank is recommended .

Asian:
Japanese
Ph: 2506-0009
Wasabisabi
13/F Times Square, Causeway Bay Fashionable Japanese fusion cuisine .
Ph : 2369-1111 ext 3087 Japanese
Unkai
Sheraton Hotel , Tsim Sha Tsui
Popular Japanese restaurant - one of the best in Hong Kong .
Indian Food
Ph : 2376-1001
Gaylord
1F Ashley Center 23-5 Ashley Road Tsim Sha Tsui
Vegetarian Indian
Woodlands Ph : 2369-3718
Rm516 G/F Mirror Tower 61 Mody Road Tsim Sha TsuiLong established south indian vegetarian food, try the thali.
Nepalese
Nepal Restaurant Ph: 2869-6212
SoHo, Central
Pioneer restaurant in SoHo area . Small so reservations recommended.
Vietnamese
lndochine 1929
Ph : 2869-7399
2F California Tower, Lan Kwai Fong
Fine vietnamese dining , hard to beat, try soft shell crabs.

Western:
The Verandah
Ph : 2812-2722
European
109 Repulse Bay Rd, Repulse Bay
Upmarket and expensive for an elegant, romantic candlelight dinner.
Ivan the Kozak
Ph : 2851-1193
Ukrainian/Russian
LG 46-8 Cochrane St, SoHo, Central
Unusual cuisine from eastern europe along with wide selection of vodkas!
The Swiss Chalet Ph: 2191-9197
Swiss
12-14 Hart Avenue Tsim Sha Tsui
Quality european cuisine including veal , fondue , cheese and fine wine.
Le Tire Bouchon Ph : 2523-5459
45 Graham St, SoHo , Central
High quality bistro home style French cuisine.

FrenchDan Ryan's Chicago Grill Ph: 2735-6111
American
Ocean Centre , Tsim Sha Tsui
Popular American restaurant chain , with three outlets. The one in Tsim Sha
Tsui may be the most accessible. Ideal for US steaks, burgers , crab cakes or
try a Philly cheese steak or Reuben - surprisingly authentic.
GermanKing Ludwig Beer Hall Ph : 2899-0122
202 Murray House, Stanley
If you like german beer and wurst (sausages) this is the place , overlooking thesea in Stanley in refurbished Murray House. Recommended stop after shopping
for tourist bargains in Stanley market.

Entertainment:
Hong Kong is a lively city at night with several active centers for night-life. Latenight shopping can also be found in some of the tourist areas like Tsim Sha
Tsui in Kowloon. For restaurants , bars and clubs the main areas include in
Kowloon , Mongkok , Jordan to Tsim Sha Tsui and on Hong Kong island SoHo,
Lan Kwai Fang and Wanchai through to Causeway Bay.
Recommended bars include Dixieland jazz at Ned Kelly's , Ashley Rd , TST. Bit
Point and Schnurrbart, two german bars next door to each other in Lan Kwai
Fang entertainment district offer good draft beer and food. The Dublin Jack,
SoHo off Mid-levels Escalator is an Irish bar with vast selection of whiskies fromaround the world. For the young at heart discos include the upmarket JJ's in
the Grand Hyatt Hotel, North Wanchai and popular Joe Banana's in Wanchai.
For those enjoying karaoke Hong Kong has number of chains with many outlets
around Hong Kong , especially in TST and Causeway Bay.
For any other specific inquiries and assistance with bookings please ask us at
the conferen ce desk.

AsCA'04
June

27

Program Timetable
29

28

30

Opening Cerem ony

Plenary 1 /2

Plenary 3/4

LT B 09:00-09:45

LT B /C 09:00-09:45

LT B I C 09:00-09:45

MS -1 , 2 & 3

MS-7, 8&9

MS -13, 14 & 15

LTB, C&E
10:15-12:15

LT B. C & E
10:15-12:15

LTB, C&E
10:15-12:15

Posters- 1

Posters- 2

Registration(odd numbers)(even numbers)

Concourse

12:00-21 :00

13:30-16:00

Concourse
13:30-16:00

MS - 4, 5 & 6

MS -10, 11 & 12

LT B. C & E
16:00-18:00

LT B. C & E
16:00-18:00

Plenary 5
LT B 13:30 -14:15

Plenary 6
LT B 14:15 -15:00

Academic
Concourse

Notes: Morn ing coffee and Afternoon tea wi ll be served in the concourse during am and pm
sessions . snacks wi ll be provided at 9:45 and 15:30.
The o riginal MS-12 and 13 are now merged under the topic 'Bio-informatics andComputationa l Analysis'.

June 28 Monday
09:00

Welcoming Ceremony

Lecture Theatre B

Morning Microsymposia
MS01: Molecular recognition and catalysis

Lecture Theatre B

Chair/Co-Chair: S. Suh/ K . Miki~:15 MS01-1
IIC/ 10:40,.

\ 11 :05

CRYSTAL STRUCTURE OF A HEMOLYTIC LECTIN CEL-111 FROM MARINE
INVERTEBRATE CUCUMARIA ECHINATA AT 1.7 A RESOLUTION
Tatsuya Uchida , Tomomitsu Hatakeyama , Takayuki Yamasaki , Seiichiro Eto, Hajime
Sugawa ra, Kurisu Genji, Atsushi Nakagawa and Masami Kusunoki

MS01-2CRYSTAL STRUCTURES OF ARTOCARPIN-SUGAR COMPLEXES : VARIATION
IN THE LENGTH OF A LOOP AS A STRATEGY FOR GENERATING LIGAND
SPECIFICITY
M. Vijayan , Anand Srivastav, A. Surolia and A. Arockia JeyaprakashMS01-3

CRYSTAL STRUCTURE OF ZINC CONTAINING MONOFERRIC C-LOBE OF
BOVINE LACTOFERRIN AT 1.9 A RESOLUTION
Sujata Sharma , Talat Jabeen , Jayashankar Jasti, Janesh Kumar, Ashok K. Mohanty
and Tej P. Singh

J 11 :25 MS01-4

STRUCTURAL BASIS OF BACTERIAL LIPOPROTEIN TRANSPORT
Kazuki Takeda , Hideyuki Miyatake, Naoko Yokota, Shin-ichi Matsuyama , Hajime
Tokuda and Kunia Mikil 11 :50

CRYSTAL STRUCTURE OF LEUA, AN ESSENTIAL BIOSYNTHETIC ENZYMEFROM MYCOBACTERIUM TUBERCULOSIS
Edward N. Baker, Nayden Koon and Christopher J. SquireMS01-5

MS02: Synchrotron related science and applications

Lecture Theatre C

Chair/ Co-Chair: S.L.Chang/ S.Sasaki

10:15

MS02-1SYCHROTRON RADIATION AND SAD PHASING IN PROTEIN
CRYSTALLOGRAPHY
Hai-fu Fan and Yuan-xin Gu

10:45

MS02-2

HIGH - RESOLUTION XRD AND IMAGING POLYCRYSTALLINEMICROSTRUCTURES BY MOVING AREA DETECTOR METHOD WITH HIGHENERGY SYNCHROTRON RADIATION
L. Wcislak, H.J. Bunge, H. Klein , U. Garbe and J.R. Schneider

11 :15MS02-3

X-RAY SCATTERING STUDY OF SELF-ASSEMBLED QUANTUM DOTS
C.-H. Hsu , Yuri P. Stetsko, Mau-Tsu Tang , Hsin -Yi Lee , Yung-Wei Hsieh , Chih-Mon
Huang , W. -S Liu , N.T. Yeh , J.-1. Chyi and K.S. Liang

11 :35MS02-4NOVEL TECHNIQUE OF NON-RESONANT X-RAY MAGNETIC SCATTERING
Hiroyuki Ohsumi , Masaki Takata and Hiroyoshi Suematsu

11 :55MS02-5OBSERVATION OF TRANSIENT ROTATOR PHASE OF N-HEXADECANE IN
EMULSIFIED DROPLETS BY SMALL- AND WIDE-ANGLE X-RAY SCATTERING
Y. Shinohara , N. Kawasaki , S. Ueno, I. Kobayashi , M. Nakajima and Y. Amemiya

June 28 Monday
MS03: Structural chemistry

Lecture Theatre E

Chair/Co-Chair: H. U ekusa/0 . E . Hibbs

10:15

MS03-1VERY SHORT OACID-H ·· ·OWATER HYDROGEN BOND STUDY BY VARIABLE
TEMPERATURE NEUTRON DIFFRACTION
Ashwini Nangia, P. Vishweshwar, John A. Cowan , Sax A. Mason , Horst Puschmann ,and Judith A. K. Howard

10:40

MS03-2TOPOLOGY AND SUBMOLECULAR PARTITIONING OF BIOLOGICALLY ACTIVE
MOLECULES BASED ON EXPERIMENTAL CHARGE DENSITYDETERMINATIONS AT 100 K AND AT 20 K
Peter Luger, Marc Messerschmidt, Stephan Scheins and Birger Dittrich

11 :05MS03-3

STUDIES ON THE VARIANT COORDINATION MODES OF ARENESULFONATE
Jiwen Cai and Jin-Sen Zhou

11 :30MS03-4

NTHU-2: A HIGHLY POROUS ORGANO-METALLOPHOSPHATE STRUCTURE
DETERMINED FROM A NON-MEROHEDRAL TWIN
Yueh-Chun Liao , Fen-Ling Liao and Sue-Lein Wang

11 :55MS03-5

REACTION CAVITY GEOMETRY DEPENDENT CONFORMATIONAL
TRANSFORAMTION ON MIXED CRYSTAL FORMATIONChampika Vithana , Hidehiro Uekusa, Akiko Sekine and Yuji Ohashi

Afternoon Microsymposia
MS04: Macromolecular assemblies

Lecture Theatre B

Chair/Co-Chair: K. Fuku yama/ S. H. Eom

16 00

MS04-1CRYSTAL STRUCTURE OF BACTERIAL MULTIDRUG EFFLUX TRANSPORTER
AcrB
Satoshi Murakami , Takashi Matsumoto, Ryosuke Nakashima, Eiki Yamashita andAkihito Yamaguchi

16:25

MS04-2CRYSTAL STRUCTURE OF CYTOCHROME B6 F COMPLEX OF OXYGENICPHOTOSYNTHESISGenj i Ku ri su , Huamin Zhang , Janet L. Smith and William A. Cramer

16:50

MS04-3

THE ATOMIC STRUCTURE OF RICE DWARF VIRUS REVELAS THE SELFASSEMBLY MECHANISM OF COMPONENT PROTEINS
Atsushi Nakagawa, Naoyuki Miyazaki, Junichiro Taka , Hisashi Naitow, Akira Ogawa,Zui Fujimoto , Hiroshi Mizuno, Kyoji Hagiwara , Takahiko Higashi, Yasuo Watanabe ,Toshihiro Omura , R. Holland Cheng and Tomitake Tsukihara

17:10 MS04-4

STRUCTURAL BASIS OF MEMBRANE-INDUCED CARDIOTOXIN A3
OLIGOMERIZATION
C.-D . Hsiao , F. Forouhar, We.N. Huang , J.-H . Liu , K.-Y . Chien , and W-G . Wu

17:35

VESICLE TRANSPORT MACHINERY: X-RAY STRUCTURES OF HUMAN GGAPROTEINS AND THEIR PARTNERS IN THE TRANS GOLGI NETWORK
Soichi Wakatsuki , T. Shiba , T . Nogi , M. Kawasaki, R. Kato , Y. Yamada , M. Inoue, S.
Kametaka , M. Shibata , S Wag uri , Y. Uchiyama, Y. Shiba and K. Nakayama

MS04-5

June 28 Monday

MS05: Neutron scattering science

Lecture Th eatre C

Chair/ Co-Chair : H. A. Robinson/ K. Kakura i

16:00

MS05-1A NEW OPPORTUNITY OF NEUTRON SCIENCE - J-PARC PROJECT IN JAPANYasuh iko Fujii

16:30

MS05-2

ON STRUCTURAL PHASE TRANSITIONS IN PEROVSKITES
Christop her J. Howa rd, Michael A. Ca rp enter, and Kevin S. Knig ht

16:55

MS05-3

STRUCTURAL DISTORTION , CHARGE AND SPIN ORDERINGS IN
Pro.ssCao.2sSro.1 Mn03
W .-H. Li , C. C. Yang , F. C. Tsao , P. J. Huang, J. W. Lynn and H. D. Ya ng

17:20

MS05-4IN SITU NEUTRON DIFFRACTION DURING DEUTERIUM ABSORPTION OF Pd
PARTICLES EMBEDDED IN Zr0 2 MATRIX
Stefa nus Harj o, Takas hi Kamiyama, Toshimitsu Yamazaki , Wataru Higemoto , Aki nori
Hos hikawa , Shin-ichi Ya maura , Hisa michi Kim ura, Akihi sa Inoue and Yosh iaki Arata

17:40

MS05-5

THE NEW QUASI-LAUE DIFFRACTOMETER AT THE REPLACEMENTRESEARCH REACTOR
Wim T. Klooster

MS06: Supramolecu/ar chemistry and crystal engineering

Lecture Theatre E

Chair/ Co-Chair: A. Nangia/ S. R. Batten

16:00

MS06- 1

RECENT ADVANCE IN CONSTRUCTION OF NEW TOPOLOGICALCOORDINATION POLYMER NETS
Xiao-Min g Chen , Ming-Liang Tong, Jie- Peng Zhang and Xiao-Ch un Hua ng

16:25

MS06-2CRYSTAL STRUCTURE OF 2D GRID-LIKE POLYMER BASED ON 3d -4d
MIXED METALSPeng Cheng and Bin Zh ao

16:50

MS06-3

THE ROLE OF DOUB LE C-H .. . N WEAK HYDROGEN BONDING MOTIFS IN NHETEROAROMATIC INCLUSION CHEMISTRY
Roger Bi shop , Solhe F. Alshahateet, Donald C. Cra ig, A. Noman , M.M. Rahman andMarcia L. Scudder

17: 15

MS06-4HYDROGEN-BONDED POL YROTOXANE STRUCTURE CONTAININT CYCLIC(H 20) 4 in [Zn(0Ac),(~ - bpe)]·2H 2 0: X-RAY AND NEUTRON DIFFRACTIONSTUDIES
Jagadese J. Vittal , Ng Meng Tack, Wim T. Kloooster and Ga rry J Mcintyre

17:40

MS06-5FROM HEXANUCLEAR TO DODECANUCLEAR AZAMETALLACROWNS
Shi-Xiong Liu , Shen Lin, Wen-S hi Wu , Chi-Chang Lina and Ji an-Quan Hua ng

June 29 Tuesday
Plenary Lectures

Lecture Theatres B & C

9:00

PL 1

SUPERCONDUCTIVITY OF BORIDE AND CARBIDE SYSTEMS
Jun Ak imitsu

9:00

PL2

STRUCTURES OF NOVEL SIGNALING PROTEINS SECRETED DURING
INVOLUTION AND INVOLVED IN APOPTOSIS
T.P. Si ngh

Morning Micro-symposia
MS07: Receptors, signaling and receptor- drug interactions

Lecture Theatre B

Chair/Co-Chair: P . M . Co lma n/ T. P . Sing h
10: 15MS07- 1

DRUG-RECEPTOR INTERACTIONS : CRYSTAL STRUCTURE OF A COMPLEXFORMED BETWEEN PHOSPHOLIPASE A2 AND ASPIRIN AT 1.9 A RESOLUTION
Rajendra Kumar Si ng h, A S. Ethayathulla, Talat Jabee n, Sujata Sharma , Pun it Kaur,A Srini vasan and Tej P. S ingh

10:45

MS07-2CRYSTAL STRUCTURE OF AN INHIBITORY ANTI-FACTOR IX FAB IN COMPLEX
WITH FACTOR IX GLA DOMAIN
Mingdong Huang, Barba ra Furi e a nd Bruce Furi e

11 :15MS07-3

STRUCTURE OF THE N1 DOMAIN OF XpsE PROTEIN FROM XANTHOMONAS
CAMPESTRIS
Nei-Li Chan , Yeh Chen, Jiun- Li Chang, and Nien-Tai Hu

11 :45MS07 -4

CRYSTAL STRUCTURE OF A SECRETORY ANTIAPOPTOTIC GLYCO-PROTEINFROM SHEEP (SPS -40)
Devend ra B. Sri vastava , Janesh Kumar, K. Sarvana n, Nage ndra S ingh,
Sujata Sha rma , A Srinivasa n and Tej P. Singh

MS-08: Materials Science I

Lecture Theatre C

Chair/ Co-Chair: M . T akata/ B . K e nnedy
10: 15MS08-1

3D POROUS MAGNETS OF M 3 (HC00) 6 (M=Mn and Co)
Zheming Wang, Bin Zhang, Hideki Fujiwa ra, Takeo Otsuka , Hayao Kobayashi andMohamedall y Kurmoo

10:45

MS08-2CUBIC PEROVSKITE-RELATED PHASES IN THE TERNARY SrO-CuO-Nb20 s
SYSTEM
Y. Li u, R. L. Wi the rs, F. Brink, L. Noren andV. Ting

11 :15

MSOB-3NON-AMBIENT X-RAY DIFFRACTION ANALYSIS OF PHARMACEUTICAL SOLIDS
A Stefa novic

11 :45

MSOB-4

CRYSTAL STRUCTURE OF POLY (3-HYDROXYBUTYRATE-C0-3HYDROXYHEXANOATE) CLOSE TO MELTING POINT
Ka tsu hito Mori, Masayuki Nakamura , Harum i Sato, I sao Takahas hi , Hikaru Te rauc hi,
Yukihiro Ozaki, Fuminobu Hirose, Kenichi Senda, and !sao Noda

June 29 Tuesday

MS-09: Electron diffraction and microscopy

Lecture Theatre E

Chair/ Co-Chair: J. Etheridge/ K . Sa itoh

10:15 MS09-1

BLOCH WAVE DEGENERACIES IN NON-SYSTEMATIC CRITICAL VOLTAGE
EFFECT OBSERVED IN ELECTRON DIFFRACTION
Hirfumi Matsuhata and Jon Gj 0nnes

10:45 MS09-2

DIRECT IMAGING OF A LOCAL DEBYE-WALLER FACTOR ANOMALY IN
QUASICRYSTALS THROUGH ADF-STEM OBSERVATIONS
Eiji Abe111 5 MS09-3

STRUCTURAL STUDIES OF THE A2LnNb06 1:1 AND A3CoNb209 1:2 ORDEREDPEROVSKITES (A= Ca 2•, Sr 2•, Ba 2•)
V.Ting, Y. Liu , R. L Withers and L. Noren

11:35

MS09-4

UNUSUAL MAGNETIC BEHAVIOR IN Pr 1.,Sr, Co0 3 : A LORENTZ MICROSCOPE
STUDY
Masaya Uchida, Ramanath an Ma hendiran , Yasuh ide Tom ioka , Yoshinori Tokura andYoshio Matsu i

11:55

MS09-5ICOSAHEDRAL QUASICRYSTAL MISSING ICOSAHEDRAL SYMMETRY
Koh Sa ito h, T ada hiro Yokosawa , Michi yoshi Tanaka and An Pang Tsai

Afternoon Micro-symposia

MS-10: Structural genomics

Lecture Theatre 8

Chair/ Co-Chair: Z. Rao/ 1. T anaka

16:00

MS 10-1

STRUCTURAL GENOMIC$ STUDY OF THE SARS CORONA VIRUS- THE
CRYSTAL STRUCTURES OF SARS VIRUS MAIN PROTEASE (Mpro) AND ITSCOMPLEX WITH AN INHIBITOR
Zihe Rao

16:30

MS 10-2

A HIGH-THROUGHPUT APPROACH TO LINK THE BIOCHEMICAL AND
CELLULAR FUNCTIONS OF MACROPHAGE PROTEINS
Bost jan Kobe , Pawel Listwan, Nathan Cowieson, Anna Aagard , Thomas Hube r,
Ti mothy Ravasi , Christine Well s, David A. Hume and Jennifer L. Martin

17:00

MS 10-3

STRUCTURAL GENOMIC$ OF C. ELEGANS
Ming Luo

17:30

MS10-4AN INTEGRATED APPROACH FOR SYNCHROTRON BASED STRUCTURALPROTEOMICS ON PROTEIN GL YCOSYLATION AND TRANSPORT
Soichi Wa katsuki , M. Kawasaki, R. Kato , M. Hiraki, N. Matsuga ki , N. Iga rashi and
M. Suzuki

June 29 Tuesday

MS-11: Structural nanoscience

Lecture Theatre C

Chair/ Co-Chair: D. Y . Noh/ C. -H . Hsu
16:00

MS11-1MAGNETIC STRUCTURE ANALYSIS OF ANTIFERROMAGNETIC ANDFERROELECTRIC COMPOUND ErMn 20 5 and YMn 20 5
Y. Noda , S . Kobayash i, T. Osawa , Y. Fu kuda , H. Kimura, I. Kagomiya and K. Kahn

16:25

MS 11-2

RESONANT X-RAY SCATTERING FROM Fe 30 4 SINGLE CRYSTAL : A SCENARIO
OF ELECTRONIC PHASE SEPARATION BELOW THE VERWEY TRANSITION
Hsueh-Hsing Hung

16:50

MS11-3

CORRELATIONSHIP BETWEEN CRYSTAL STRUCTURE AND
PIEZOELECTRICITY IN LANGASITE WITH FOUR CATIONS
H. Ohsato, T. lwataki, N. Araki, H. Morikoshi and K. Kakimoto

17:15

MS 11-4

CRYSTAL STRUCTURES AND PHASE TRANSITIONS IN THE SYSTEM SrTiO, La 213Ti03
Christopher J. Howard, A. Gregory R. Lum pki n, Ronald I. Smith and Zhaom ing Zhang

17:40

MS 11-5

ANTIPHASE DOMAINS AND B-SITE ORDERING IN Pb(Mg 113 Nb 213 . 6 )0 3/SrTiO, THIN
FILMS
Sean Hee Seo , Suraj Yadav, Do Young Noh and Kiyotaka Wasa

MS-12&13: Bioinformatics and Computational Analysis I

Lecture Theatre E

Chair/ Co-Chair: S. Hall/ M. Bansa l
16:00

MS 12&13-1

MULTIPLE OPEN READING FRAMES , CODON BIOS AND AMINO ACID USE AND
THE EVOLUTION OF THE GENETIC CODE .
W . L. Duax , R. Huether, L. Habegger, S. Conna re, V. Pletnev and J. Sc habe r

1630

MS 12& 13-2

STRUCTURE BASED 'PUNCTUTATION MARKS ' IN GENOMIC DNA
Manj u Bansal and Aditi Kan here

17:00 MS 12& 13-3

BIOINFORMATICS IN STRUCTURAL GENOMICS OF C. ELEGANS
Jun Tsao , David H. Johnson and Mike Ca rson

17:30

SSEP: SECONDARY STRUCTURAL ELEMENTS OF PROTEINS
K. Sekar, V. Shanthi, P. Selvaran i, Ch. Kiran Kumar and C.S.Mohire

MS 12& 13-4

June 30 Wednesday
Plenary Lectures

Lecture Theatres B & C

9:00

PL3

FROM METAL STRING COMPLEXES TO METAL WIRES
Chih-Chieh Wang and Shie-Ming Peng

9:00

PL4

HIGH-THROUGHPUT PROTEIN CRYSTALLOGRAPY
Isao Tanaka

Morning Micro-symposia

MS-12&13: Bioinformatics and Computational Analysis II

Lecture Theatre B

Chair/ Co-Chair: M. Bansal/ N. Niimura
10:15

MS12&13-5

THE ROLE OF DATA DICTIONARIES IN KNOWLEDGE RETENTION
Sydney R. Ha ll and Nick Spadaccini

10:45

MS12&13-6

3D STRUCTURAL ANALYSIS OF PROSITE PATTERNS
Sukanla Mandai, Vasanthakumar B., S. P. Jaishankar and S. Ramakumar

11 :15

MS12&13-7

MATCHING STRUCTURE TO CELL DISTORTION IN TWINNED CRYSTALS .
A. David Rae

11 :45

MS12&13-8

DATA BASE OF HYDROGEN AND HYDRATION IN PROTEINS.
N. Niimura, I.Tanaka , K.Kurihara ,T.Chatake and M.Maeda

MS-14: Advanced Applications of Powder Diffraction

Lecture Theatre C

Chair/ Co-Chair: C . H oward/T. Kamiyama
10:15

MS 14-1

AB INITIO STRUCTURE DETERMINATION OF Co(dt), BY GENETIC ALGORITHM
Makoto Sakata , Yuichi Fujishiro , Eiji Nishibori , Masaki Takata , Akiko Kobayashi and
Hayao Kobayashi

10:45

MS14-2

APPLICATIONS OF LARGE 2D DETECTORS FOR NEUTRON POWDERDIFFRACTION.
Alan W. Hewat

11 :15

MS14-3

SCREENING STABILIZING POLYMERS FOR DRUG DEVELOPMENT USING
VARIABLE TEMPERATURE X-RAY DIFFRACTION
Z. Ping Wu , R. Hart, and D. Stirling

11 :35

MS14-4STUDY OF CRYSTAL STRUCTURE IN LaMn 1., Cu, 0 3 COMPOUNDS
S. Ravi and Manoranjan Kar

11 :55

MS14-5POWDER DIFFRACTION STUDIES OF BISMUTH DOUBLE PEROVSKITE
Ba 2A 3+B 5.06
Qingdi Zhou and Brendan J. Kennedy

June 30 Wednesday

MS-15: Materials Science II

Lecture Theatre E

Chair/ Co-Chair: J. Lin/X. -M. Chen
10:15 MS15-1

MOLTEN SALT SYNTHESIS AND CRYSTAL STRUCTURES OF PALLADIUM
PHOSPHATES AND ARSENATES
Kwang-Hwa Lii , Ling-1Hung and Sue- Lein Wa ng

10:40 MS15-2

SPIN DENSITY AND CHARGE DENSITY STUDIES ON AN ORGANIC MAGNET
Jey-Jau Lee and Yu Wang

11 :05 MS15-3

A NOVEL ALUMINOBORATE MOLECULAR SIEVERS CONTAINING
OCTAHEDRAL FRAMEWORKS OF 3D TUNNEL STRUCTURE
Jianhua Lin and Jing Ju

11 :30 MS15-4

MODULATED STRUCTURES IN THE Ta 20 5 -W0 3 SYSTEM FROM X-RAY AND
NEUTRON POWDER DIFFRACTION DATA
Sieg bert Schmid and Anja Bi nder

11:55 MS15-5

A CHIRAL METAL ZINCOBOROPHOSPHATE TEMPLATED BY ACHIRALTRIAMINE: SYNTHESIS AND CHARACTERIZATION OF(C 4 N3H, 6 )[Zn 3 B 3P6 0 2. )·H 20
Wei Liu , Hao-Hong Chen , Xin-Xin Yang , Man-Rang Li , Ming-Hui Ge and Jing-Tai
Zhao

Plenary Lectures
13:30

PL5

14: 15 PL6

15:00

Lecture Theatre B

CRYSTALLOGRAPHY WITHOUT CRYSTALS
Jianwei Miao, Keith 0 . Hodgson , Tetsuya Ishikawa , Bart Johnson Yosh iki Kohmura
and Yoshinori Nish ino

GRID-ENABLED HIGH THROUGHPUT CHEMICAL CRYSTALLOGRAPHY: A NEWOPPORTUNITY FOR STRUCTURAL CHEMISTRY.
Michael B. Hursthouse

Concluding Remarks

Lecture Theatre B

June 28 Monday and June 29 Tuesday
Poster sessions
P01

ANALYSES OF HYDROGEN BONDS IN AMINO ACID -INORGANIC ACID 2:1
COMPLEXES
B.Sridhar, K.Anitha and R.K .Rajaram

P02

BONDING AND AGGREGATIONS OF SOME AMINO ACID- INORGANIC ACIDCOMPLEXES
B.Sridhar, K.Anitha and R.K.Rajaram

P03

ELECTRONIC STRUCTURES OF La1-xSrxCo03 EXAMINED BY XMCD MEASUREMENSAT THE Co K ABSORPTION EDGE
Takayasu Hanashima, Satoshi Sasaki , Norio Shimizu , Kouji Yamawaki , Takeharu Mori and
Masahiko Tanaka

P04

COW FORMATION IN AN INCOMMENSURATE PHASE OF 1T-TaS2 STUDIED BY X-RAY
THERMAL DIFFUSE SCATTERINGYo Machida, Satoshi Sasaki , Takayasu Hanashima, Kouichi Ohkubo , Kouji Yamawaki and
Masahiko Tanaka

P05

CRYSTAL STRUCTURE OF ETHYL 4-(2 ,5-DIOX0-2 ,5-DIHYDR0-1H-PYRROL-1-YL)
BENZOATE
Vasu , K. A. Nirmala , MVishwas and Deepak Chopra

P06

X-RAY DIFFRACTION , XANES AND XMCD STUDIES ON THE SITE PREFERENCE AND
VALENCE STATE OF Co AND Fe IONS IN IRON COBALTITE
Kouji Yamawaki , Norio Shimizu , Satoshi Sasaki, Takayasu Hanashima, Tomoaki Watanabe ,Masahiro Yoshimura and Masahiko Tanaka

PO?

FERROMAGNETIC ORDERING MODEL OF A CoxTi1-x02 THIN FILM (x = 0.07)
Norio Shimizu , Satoshi Sasaki , Takayasu Hanashima and Kouji Yamawaki

P08

CRYSTAL STRUCTURE OF 2-AMINO-N-(2-CHLOROPHENYL)-5,6-DIHYDR0-4HCYCLOPENTA[b]THIOPHENE-3-CARBOXAMIDE
K.A.Nirmala , Vasu , S.Mohan , J.Saravanan and Deepak Chopra

P09

DEGREE OF DISORDER IN SPINEL-TYPE (Mn ,Zn ,Fe)304 EXAMINED BY THE TWOWAVELENGTHS ANOMALOUS DISPERSION METHOD
Syoichi Sakurai , Satoshi Sasaki , Kouji Yamawaki , Takayasu Hanashima and Norio Shimizu

P010

X-RAY STRUCTURAL STUDY OF IN-PLANE ATOMIC ARRANGEMENTS IN THE
COMPOUNDS MxTiS2 (M=Cu , Ni , Co)
LAYERED
Ken-ichi Ohshima , Yoshinobu Kasuga , Tomoko Kusawake , Makoto Yasuda and Hiraki Uratani

P011

CRYSTAL STRUCTURE OF 7-METHYL 6, 8-DINITRO 4-BROMOMETHYL COUMARIN
K.V.Ajuna Gowda , T. N.Guru Row, N.C.Shivaprakash and M.V. Kulkarni

P012

CRYSTALLOGRAPHIC ANALYSIS OF HYDROGEN BONDING IN SERIES OF CHOLESTBASED STEROIDAL MOLECULES
Dinesh and Rajnikant

P013

NEUTRON STUDIES OF CLUSTER BEHAVIOUR OF Pd40Ni22.5Fe17.5P20 SPIN GLASS
E.P. Gilbert, R. Woodward , D.H. Yu and R. A. Robinson

P014

AB-INITIO PHASING AT 1.7A RESOLUTION OF A PROTEIN FERREDOXIN I BY
COMBINED REAL SPACE -RECIPROCAL SPACE APPROACH
Krishna Chowdhury , Soma Bhattacha rya and Monika Mukherjee

P015

DIFFUSE NEUTRON SCATTERING FROM d-BENZIL, C14D1002, USING TIME-OF-FLIGHTLAUE DIFFRACTION
T. R. Welberry , D. J. Goossens, W. I. F. David, M. J. Gutmann, M. J. Bull and
A. P. Heerdegen

P016

S-SAD PHASING BY OASIS2004
J. W. Wang , Y. X. Gu , C. D. Zheng , F. Jiang and H. F. Fan

P017

TREATMENT OF EXPERIMENTAL ERRORS IN DIRECT-METHOD SAD PHASING
S. Hua ng, J. W. Wang , Y. X. Gu, D. C. Xian, H. F. Fan and M. M. Woolfson

P01 8

EFFECT OF SULFUR-ANOMALOUS SCATTERING SIGNAL ON SAD PHASING IN THE
PRESENCE OF IRON ATOMS
D. Q. Yao , J. R. Chen , J. W. Wang , C. D. Zheng , Y. X. Gu, F. Jiang , H. F. Fan and D. C. Xian

P019

SYNCHROTRON X-RAY POWDER DIFFRACTION STUDY OF THE STRUCTURAL PHASE
TRANSITION IN CaBr2
Brendan J. Kennedy and Christopher J. Howa rd

P020

CHARACTERIZATION OF THE!!.' PHASE- MATRIX INTERFACE IN 1420 ALUMINIUM
ALLOYS BY SAXSChai Zhi-Gang

P02 1

CATION ORDERING IN PENTLANDITE (Fe,Ni)(Fe,Ni)8S8
Kia S. Wallwork , Allan Pring and Chri stoph e Tenaillea u

P022

THREE-BEAM DIFFRACTION ANOMALOUS FINE STRUCTURE OF THIN FILMS
Hsueh-Hung Wu , Yen-Ru Lee , Hsin-Hung Chen , Wen-Shien Su n and Shih-Lin Cha ng

P023

CRYSTAL STRUCTURES OF ANHYDROBARAKOL AND ANHYDROBARAKOLHYDROCHLORIDE; AN EVIDENCE OF EXCEPTIONAL C=O/C-OH QUINONE
CHARACTERISTIC
P. Chimsook, N. Ngamrojnavanich, C. Chaichantipyuth , N. Chaichit, P. Kong saeree ,A. Petsom , N. Muangsin

P024

THE CLEAVAGE OF DIPEPTIDES BY Co(lll) COORDINATION COMPOUNDS
Ivan Berna l, Manas Saha and Uday Mukhopadhyay

P025

STRUCTURAL AND CONFORMATIONAL STUDIES OF DIHYDROPYRIMIDINES
G.Y.S.K. Swamy and K.Ravikumar

P026

TWO- AND THREE- DIMENSIONAL ORGANICALLY TEMPLATED OPEN-FRAMEWORKLANTHANIDE SULFATES: EFFECTS OF " LANTHANIDE CONTRACTION " ON THE
FRAMEWORK ARCHITECURES
Jiang-Gao Mao and Yan- Ping Yuan

P027

THE CRYSTAL STRUCTURES OF HYDRAZINIUM 2,3-PYRAZINEDICARBOXYLATES,N2H5Hpyz(C00)2, (N2H5)2pyz(C00)2 and N2H5Hpyz(C00)2.H2pyz(C00)2
T. Premkumar, S. Govindarajan , and Nigam P. Rath

P028

NEW TEN COORDINATED LANTHANUM 2-PYRAZINECARBOXYLATE DIHYDRATECONTAINING HYDRAZINIUM CATION
S. Govindarajan, T. Premkumar , V. Manivannan , K.R. Rad hakrishnan andJonathan W. Steed

P029

LADDER NETWORKS IN INCLUSION COMPLEXES OF 4,4-BIS(4-HYDROXYPHENYL)CYCLOHEXANONE
Srin ivasu lu Aitipamula , Ashwi ni Nangia, Mariusz Jasko lski and Ram Th aimattam

P030

rr-STACKING IN NOVEL FLUORESCENT NAPHTHALIMIDE SYSTEMSJim Simpson , C. John McAdam, Joy L. Morgan and Brian H. Robinson

P031

DL-THREONINE AND DL-PHENYLALANINE COMPLEXES WITH TRICHLOROACETIC
ACID
K.Rajagopal, R.V.Krishnakumar, K.Ravikumar and S. Natarajan

P032

COMPARATIVE INVESTIGATION FOR THE CRYSTAL STRUCTURE OF THE
COORDINATION COMPOUNDS OF THE RARE EARTH AND SHORT CHAIN ETHER E02 ,E03
Jianmi ng Gu and Xiu rong Hu

P033

REVERSIBLE SOLID-VAPOR SUBSTITUTION REACTIONS OF LAYERED CADMIUM
ORGANOSULFONATES
Jinse n Zhou , Li Wa ng and Jiwe n Ca i

P034

CONSTRUCTION OF SILVER (I) COLUMN WITH ENCAPSULATED ACETYLENEDIIDEAND A HYDROPHOBIC SHEATH PROVIDED BY ANIONIC AND ZWITTERIONICCARBOXYLATE LIGATION
Xiao-Li Zhao and Thomas C. W. Mak

P035

STUDIES ON IRON(III) COMPLEXES OF 2-PYRIDYL-6-(2-PYRIDYLCARBONYL)-2PYRIDYLMETHANONE
Xu- Dong Chen and Thomas C. W. Mak

P036

SUPRAMOLECULAR STABILIZATION OF OXOCARBON ANIONS IN UREA HOST
FRAMEWORKS
Chi -Keung Lam , T ho mas C. W. Mak

P037

SYNTHESIS, STRUCTURE, AND DNA CLEAVAGE OF AN OPTICAL REACTIVESPIROPENTACOPPER CLUSTER
Szu-M iao Chen , Yu Wang and Kuan-Jiuh Li n

P038

CHARGE DENSITY STUDY AND ROLE OF HYDROGEN BOND IN TRAN -[Ni(cyan kN)2(NH3)4] : COMPARISON BETWEEN EXPERIMENT AND THEORYHsi n-H ui Shen and Yu Wang

P039

PHOTOCHROMISM OF SALICYLIDENEANILINES DEDUCED BY THE ACID-BASE
COMPLEX FORMATION
Ko hei Johmoto, Hidehiro Uekusa and Yuji Ohashi

P040

SOLVOTHERMAL INDUCED TRANS-CIS ISOMERIZATION OF [Fe(TZPY)2(NCS)2](TZPY=3-(2-PYRI DYL)[1 ,2,3]TRIAZOL0[1 ,5-A] PYRIDINE)
K. W . Chen , C. F. Sheu , G. H. Lee andY. Wa ng

P041

A UNPRECEDENTED HOMOCHIRAL OLEFIN-COPPER(I) 2D COORDINATION POLYMER
Ren-Gen Xiong and Xi-Sen Wa ng

P042

FERROELECTRIC COPPER QUININE COMPLEXES
Ren-Gen Xiong and Hong Zhao

P043

STRUCTURE OF AN COMPLEX COMPOSED OF METHACRYLIC ACID AND PYRIDINE
K. Yoshida, H. Uekusa , and Y. Ohas hi

P044

X-RAY ANALYSIS OF REACTION PROCESS THROUGH ARYLNITRENE
Takah iro Mitsumori, Hidehiro Uekusa and Yuji Ohas hi

P045

X-RAY DIFFRACTION STUDY OF THE CRYSTALLINE-STATE PHOTORACEMIZATION OF
A BULKY ALKYL CROUP IN A COBALOXIME COMPLEX
H. Takeoka , H. Uekusa andY. Ohashi

P046

IONIZATION STATES, STOICHIOMETRY AND HYDROGEN BONDING PATTERNS INCOMPLEXES OF AMINO ACIDS WITH CARBOXYLIC ACIDS
R. V. Krish nakuma r and S.Natarajan

P047

SYNTHESES AND STRUCTURES OF NaCd(H20)2[BP208]·0.8H20 AND
NaZn(H20)2[BP208] ·H20 AT ROOM TEMPERATURE AND AMBIENT PRESSURE
Ming-Hui Ge, Wei Li u, Hao-Hong Chen , Xin-X in Yang and Jing-Tai Zhao

P048

A MIXED CATIONS NICKEL DIPHOSPHATE WITH A LAYERED INTERGROWTHSTRUCTURE: SYNTHESIS, STRUCTURAL AND MAGNETIC CHARACTERIZATION OF
Na(NH4)[Ni3(P207)2(H20)2]
Wei Li u , Xin-Xin Yang , Hao-Hong Chen , Ya-Xi Huang, Walter Schnelle and Jing-Tai Zhao

P049

NH4[BP04F] : A NOVEL OPEN-FRAMEWORK AMMONIUM FLUORINATED
BOROPHOSPHATE WITH A ZEOLITE-LIKE STRUCTURE RELATED TO GISMONDINETOPOLOGY
Man-Rang Li , Wei Li u, Ming-Hui Ge, Hao-Hong Chen , Xin-X in Yang and Jing-Tai Zhao

P050

TAILORING OF BOROPHOSPHATE STRUCTURES BY HALOGEN ANIONS AND/OR
ORGANIC TEMPLATES
Jing-Tai Zhao Wei Liu , Man-Rong Li , Ya-Xi Huang , Ming-Hui Ge,Hao- Hong Chen and
Xin-Xin Yang

P051

SYNTHESIS AND CHARACTERIZATION OF SILVER( I) 1 ,3-BUTADIYNEDIIDE AND ITSRELATED SILVER(I) DOUBLE SALTS CONTAINING THE C42- DIANION
Liang Zhao and Thomas C. W. Mak

P052

STRUCTURAL CHARACTERIZATION OF SPIN CROSSOVER COMPLEX TRANS[Fe(TZPY)2(NCS)2] (TZPY = 3-(2-PYRIDYL)[1 ,2,3]TRIAZOL0[1 ,5-A]PYRIDIN E)
C F. Sheu, J. J. Lee , G. H. Lee , I. J. Hsu, Y. C. Lin , K. Toriu mi, Y. Ozawa andY. Wang

P053

CHARGE DENSITY INVESTIGATION OF A NON-CENTROSYMMETRIC MN COMPLEX :Mn(mai)(H20)2
Yen-Chen Li n, 1-Jui Hsu , Gene-Hsia ng Lee and Yu Wang

P054

CRYSTAL ENGINEERING WITH SCORPIONATE LIGANDS
Stuart R. Batten and Ma rtin B. Duriska

P055

CRYSTAL STRUCTURE AND MELTING POINT CORRELATIONS OF ACETIC ESTERS
Hidehiro Uekusa , Hirokazu Suzuki and Yuj i Ohas hi

P056

COORDINATION POLYM ER WITH ZEOLITE OR ZEOLITE-LIKE TOPOLOGIES
Yu n-Q i Tian, Lin-Hong Weng, Zhen-Xia Chen, Dong Yua n Zhao and Xiao-Zeng You

P057

CRYSTAL STRUCTURES OF COMPLEXES OF AMINO ACIDS WITH ZINC AND CADMIUMCHLORIDES : IONIZATION STATES, STOICHIOMETRY, COORDINATION AND CRYSTALPACKING
R.V.Kri shnakumar, M.Subha Nandh ini and S.Natarajan

P058

CRYSTAL AND MOLECULAR STRUCTUR OF BIS(HYDRAZINIUM)
BIS(OXALATO)NICKEL(II) DIHYDRATE AND BIS(HYDRAZINIUM)
BIS(MALONATO)COBALT(ll) DIHYDRATE
V. Maniva nnan , K.R. Rad hakrishnan, K. Sa ravanan, S. Govindarajan and J.J. Vittal

P059

SYTHESIS AND CRYSTAL STRUCTURES OF POLYNUCLEAR TITANIUM(IV) AND
ZIROCONIUM(IV) COMPOUNDS SUPPORTED BY AN OXYGEN TRIPODAL LIGANDS
Xiao-Y i Yi, Tony C. H. Lam , E. Y. Y. Chan. Qian-Feng Zhang , lan D. Wi ll iams and
Wa-Hung Leung

P060

DIRECT OBSERVATION OF DIFFERENT REACTION ROUTE DUE TO STERICHINDRANCE IN CRYSTALLINE-STATE PHOTOISOMERIZATION
Yuji O hashi, Akira Hirano and Hidehiro Uekusa

P06 1NOVEL BIS-DIDENTATE NITROGEN LIGAND DERIVED FROM 1,4DIHYDRAZINOPHTHALAZINE
Ling-Kang Liu and Wen-Fu Chang

P062

SOLID CRYSTALLINE FORMS OF DICLOFENAC SODIUM AND DICLOFENAC ACID
Chuttree Phurat, Narong Praphairaksit, Malatee Taiyaq upt and Nongn uj Muangs in

P063

SELF-ASSEMBLY OF FOUR METAL-SQUARATE (Cd(ll) AND Zn(ll)) COORDINATIONPOLYMERS WITH FLEXIBLE 1 ,2-BIS(4-PYRIDYL)ETHANE LIGAND (OPE)
Chih-Chieh Wa ng , Hui-Wun Li n, Chin-Hui Liao, Cheng-Han Ya ng and Gene-H siang Lee

P064

HYDROTHERMAL SYNTHESIS, CHARACTERIZATION, AND SUPRAMOLECULARSTRUCTURE OF [Co(C6H402N)3) ·H20
Kittipong Chainok and Kenneth J. Hatler

P065

THE ORDER-DISORDER TRANSITION AT 150 K OF POLYMERIC AG(BIPY)N03
Weenawa n Somphon, Kenneth J. Halter and A. David Rae

P066

SUPRAMOLECULAR STRUCTURE OF AZIDONITROSYLBIS (TRIPHENYLPHOSPHINE)
NICKEL
Nongnaphat Khosavithitkul and Kenneth J. Hatler

P067

THE CRYSTAL STRUCTURE OF PYRIDINE-3,5-DICARBOXYLIC ACID
Sam roeng Krachodnok and Ke nneth J. Halter

P068

INVARIOMS FOR AUTOMATED LOW ORDER DATA CHARGE DENSITY ANAL YSI
B. Dittrich, M. Spackman , P Luger

P069

NEW FACE-CAPPING BONDING MODE FOR ARENES IN ORGANOMETALLIC METAL
CLUSTERS
Jasmi ne Po-Kwa n Lau and Wing-Tak Wong

P070

STRUCTURAL STUDY OF COORDINATION NETWORK BASED ON METAL ORGANICLIGANDS
Lap Szeto , Ya ng-Vi Yang and Wing-Tak Wong

P07 1

POWDER NEUTRON DIFFRACTION STUDY OF A CRYSTALLINE-STATE REACTION OF
AN UNSATURATED THIOAMIDE DERIVATIVE
Takashi Ohhara, Sus um u Ikeda , Kenichi Oikawa , Akinori Hoshikawa , Takashi Kamiyama ,Takaaki Hosoya and Yuji Ohashi

P072

STRUCTURAL CHARACTERIZATION OF THREE CRYSTALLINE MODIFICATIONS OF
CHLOROTHALONIL BY X-RAY POWDER DIFFRACTION
Xi urong Hu Ziqin Yuan Jianming Gu Guanglie Lu Xiaoyan Tu

P073

CRYSTAL STRUCTURE AND CONFORMATION OF GEM-CHLORO NITROSOCYCLODODECANE (CH2)n-1CNOCI , with n=12
C.R. Girija and Noor Shahina Beg um

P0 74

TOPOLOGICAL ANALYSIS OF [NH2Me2][H(HC404)2)
Chi-Rung Lee , Ching-Yi Lee and Yu Wang

P075

SYNTHESIS AND CHARACTERIZATION OF TWO POLYMORPH$ OF
Fe(2,2'- bpy)(HP04)(H2P04)
Wen-Jung Chang , Yau-Chen Jiang and Kwang-Hwa Lii

P076

SYNTHESIS AND CHARACTERIZATION OF THE FIRST METALOXALATOPHOSPHONATE : (C3H12N2)0 .5[Ga3(C204)(CH3P03)4) ·0.5H20
Chi a-Hui Lin and Kwang-Hwa Li i

P0 77

SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF A NEW URANIUM SILICATE:
K6(U02)2(Si4013)
Chih-S han Chen and Kwang-Hwa Lii

P078

SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF(H4APPIP)[V3(C204)2(HP04)3(P04)(H20)]·6H20(APPIP = 1,4-BIS(3-AMINOPROPYL)PIPERAZINE), A LAYERED VANADIUOXALATOPHOSPHATE CONTAINING DOUBLE-SIX-RING UNITS
Ming-Feng Tang and Kwang-Hwa Lii

P079

ELECTRONIC STRUCTURES OF POLYMORPHS IN MONOHALOGENATED BENZYLDERIVATIVES of 2,5-DIAMIN0-3 ,6-DICYANOPYRAZINE DYES
Shinya Matsumoto , Yoko Uchida and Mitsuhiro Yanagita

P080

HYDROGEN BONDING PATTERN AND n -n-INTERACTIONS IN 1,7-BIS-(4-HYDROXY-3METHOXYPHENYL)-HEPTA-3,5-DIONE (TETRA HYDRO CURCUMIN)
Noor Shah ina Begum, C. R. Girija and A A Syed

P081

LANTHANIDE CONTRACT AND pH VALUE CONTROLLED STRUCTURES CHANGE IN A
SERIES OF RARE EARTH COMPLEXES WITH P-AMINOBENZOIC ACID , CRYSTALSTRUCTURE AND LUMINESCENCE PROPERTY
Jun-Ran Li , Hao-Ling Sun , Chao-Hong Ye, Xin-Yi Wang and Song Gao

P082

BIS(ALKYNYL) MERCURY(II) COMPLEXES OF OLIGOTHIOPHENES AND BITHIAZOLESWai-Yeung Wong , Ka-Ho Choi and Guo-Liang Lu

P083

COMPARISON OF MOLECULAR PACKING MODES OF CHOLESTEROL DERIVATIVES
Young Ja Park

P084

STUDIES ON THE WEAK HYDROGEN BONDS IN CRYSTAL
Zhang-Yuan Zhou , Wing-Kong Kwan , Chi-Hung Yeung and AlbertS . C. Chan

P085

FIRST OBSERVATION OF HELICAL BUNDLES IN CRYSTAL STRUCTURE OF HELICALPEPTIDE SCAFFOLDS CONTAINING A, B- DEHYDROPHENYLALANINE RESIDUE
M. Gupta, Rudresh , S Ramakumar and V. S. Chauhan

P086

NEW STRATEGY TO SYNTHESIZE OSMABENZYNES
Ting Bin Wen , Wai Yiu Hung, Herman Ho Yung Sung , lan D. Williams and Guochen Jia

P087

SYNTHESIS AND NLO PROPERTIES OF NEW OCTUPOLAR MOLECULES
Quanyuan Hu , George K. L. Wong , Herman Ho Yung Sung , lan D. Wi lliams and Guochen Jia

P088

HEXAMERIZATION OF ALKYNES MEDIATED BY OsCI(PCP)(PPh3)(PCP 2,6- (Ph2PCH2)2C6H3)
Ting Bin Wen, Zhong Yuan Zhou and Guochen Jia

P089

OSMABENZENES FROM THE REACTIONS OF HC:CCH(OH)C:CH With OsX2(PPh3)3(X= Cl , Br)
Haiping Xia , Guomei He, Hong Zhang , Ting Bin Wen , Herman Ho Yung Sung , Ian D. Williams
and Guochen Jia

P090

RUTHENIUM-CATALYZED DIMERIZA TION OF TERMINAL ALKYNES
Peng Xue , Hoi Yan Leung , Ka Yin Cheng , Wai Bong Wong , Herman Ho Yung Sung , lan D.
Williams and Guochen Jia

P091

DILEAD tJ9-L-TARTRATE : A CHIRAL METAL-ORGANIC FRAMEWORK WITH NONACOORDINATION OF A SINGLE LIGAND
Andy L-F . Leu ng , Ricky W. Li, Herman H-Y. Sung and lanD. Williams

P092

ORGANO-CERAMIC SYNTHESIS : STRUCTURE OF A HYBRID SOLID with [Ln4(tJ3-0H)4]LANTHANUM-HYDROXIDE TETRAHEDRA
Candy Z-J . Lin , Herman H-Y. Sung and lanD. Wi lliams

P093

A NOVEL POLYMORPHIC PHASE TRANSITION IN A CADMIUM POLYMER[Cd(H20)(2 ,6-NAP)]INVOLVING A 7 -> 5 COORDINATION NUMBER SWITCH
early H-W. Tse , Samuel M-F. Lo and lan D. Williams

=

P094

SELECTIVE SYNTHESIS OF POLYOXOMETALLATE CLUSTERS USING STRUCTUREDIRECTING ORGANIC AND INORGANIC CATIONSIcy C-P . Lau , Yi Yu , Herman H-Y. Sung and ian D. Williams

P095

CHIRAL COORDINATION POLYMERS BY HYDROTHERMAL SYNTHESIS:CRYSTALLIZATIONS OF ALKALINE EARTH TARTRATESYu-Fong Yen , Andy L-F . Leung , Carly H-W. Tse , Ricky W. Li and ian D. Williams

P096

HYDROTHERMAL CRYSTALLIZATION AND STRUCTURE OF LUMINESCENT 1-D
LANTHANIDE POLYMERS [Ln2(BIPHENATE)3(H20)2]
Samadara Thu shari , Herman H-Y. Sung , Kam-Sing Wong and ian D. Williams

P097

STRUCTURES OF IMIDAZOLE MANGANESE VANADATES : CRYSTALLIZATION OF
TEMPLATED VERSUS HYBRID SOLIDS
Yi Yu , Teresa S-C. Law, Herman H-Y. Sung and ian D. Williams

P098

METAL FORMATE NETWORK SOLIDS : SOLVOTHERMAL SYNTHESIS, STRUCTURESAND MAGNETIC PROPERTIES OF a-[Co(02CH)2],13-[Ni(02CH)2] And [M(OH)(02CH)] M =Co, NiAlvin W-H. Siu , ian D. Wi lliams , Herman H-Y . Sung , John A. Cha , Candy Z-J. Lin andXi Xiang Zhang

P099

1:1 AND 1:2 AD DUCTS OF BIPYRIDINES WITH BIPHENIC ACID
Fanny L-Y . Shek , Wan-Yee Wong , Samuel M-F. Lo, Herman H-Y . Sung and ian D. Williams

P0100

EFFECT OF SOLVothermal CONDITIONS ON CRYSTALLIZATION OF METAL
COORDINATION POLYMERS: EXAMPLES OF THE ZINC AND COBALTPYROMELLITATE - BIPYRIDINE SYSTEMSSamuel M-F. Lo , Stephen S-Y. Chui , and ian D. Williams

P0101

A CHIRAL ORGANIC SALT FROM HYDROTHERMAL REACTION OF 4,4BIPYRIDINE AND L-TARTARIC ACID WITH 50% PROTON TRANSFER
Wan-Yee Wong , Fanny L-Y. Shek , Samuel M-F. Lo, Herman H-Y. Sung and ian D. Wi lliams

P0102

S-AKYLATION OBSERVED ON TRI(2-THIOPHENYL)PHOSPHINO Tin COMPLEXES
Michael Y. Chiang , Chi-Hui Chang and Jing-Wei Lin

P0103

ELECTRON DENSITY DISTRIBUTIONS ON WEAK INTERMOLECULAR INTERACTIONS:CH ...O INTERACTIONS IN TEMPO RADICALS
Masanori Yasui , Kansui Takino, Fujiko Iwasaki and Daisuke Hashizume

P01 04

RAPID DISMUTATION OF H202 BY COFACIAL BIS-CORROLE CATALASE MODELSFei Yam , Nga-Chun Ng , Hai-Yang Liu , Lam-Lung Yeung and C. K. Chang

P0105

TWO NEW DITERPENOIDS FROM EUPHORBIA EBRACTEOLATA : STRUCTURALSTUDIES OF A DIASTEREOMERIC PAIR
Herman H-Y. Su ng, ian D. Wi lliams , Hai-M ing Shi , Hua-Xu Zhu , Nancy Y. lp and Zhi-Da Min

P0106

X-RAY ABSORPTION FINE STRUCTURE INVESTIGATION OF VANADIUM ON Ti02/Si02
AND Si02 SUPPORTS
Hsiu-Mei Lin , Sheng-Tsang Kao , Jen-Ray Chang and Shin-Guang Shyu

P0107

THE RESEARCH OF CRYSTAL STRUCTURES BY ELECTRON CRYSTALLOGRAPHYTECHNIQUE
Liping You, Junliang Sun , Zhaofei Li , Guobao Li and Jianhua Lin

P0108

SYNTHETIC ROUTES TO A NEW CLASS OF BLUE-EMITTING OLIGOACETYLENICSILANESSuk-Yue Poon and Wai-Yeung Wong

P0109

TRIPLET EMISSION IN SOLUBLE MERCURY(II) POL YYNE POLYMERSLi Liu and Wai-Yeung WongP0110

GRAFTING Ti02 ON MCM-41 AS A Ti02 SUPPORT FOR VANADIA FOR CATALYTICOXIDATION OF ETHANOL-EXAFS AND XANES ANALYSES OF VANADIUM
Hsiu-Mei Lin , Sheng-Tsang Kao , Jen-Ray Chang and Shin-Guang Shyu

P0111

DIRECT OBSERVATION OF THE HYDROGEN TRANSFER IN THE SOLID-STATEORGANIC PHOTOREACTION WITH NEUTRON DIFFRACTION METHOD
Hosoya Takaaki , Ueku sa Hid ehiro, Ozeki Tomoji , Ohashi Yuji , Ohhara Takashi , Tan aka lchi ro
and Niimura Nobuo

P011 2SYNCHROTRON STRUCTURE DETERMINATIONS OF INORGANIC GIANT MOLECULES
Tomoji Ozeki , Shin-ichi Adachi and Toshihiro Yamase

P011 3

CRYSTAL STRUCTURES OF TWO ALDOL CONDENSATION PRODUCTS
Yin-Su WU and Jiwen Cai

P0114

SEPARATION AND CHARACTERIZATION OF CRYSTALLINE CEFUROXIME AXETIL
DIASTEREOMERS
Chuan-Qi Zheng and Jiwen Cai

P0115

THE CRYSTAL STRUCTURES OF A SREIES OF DINICKEL COMPLEXES BRIDGED BY
UNUSUAL (N,O,O' )- COORDINATED AMINO ACIDS
Li Wang , Jiwen Cai and Jin-Wang Huang

P0116

VARIATION IN THE COORDINATION MODES OF DIFFERENT ARENEDISULFONATES TO
TRANSITION METAL IONS
Dong-Sheng Deng and Jiwen Cai

P0117

A CONTEMPORARY APPROACH TO MORPHOLOGICAL CONTROL OF
NANOCRYSTALS
Mingmei Wu , Xianfeng Yang , Gan Lin , Caihong Wang , Wenjiao Lin , Lifang Liang , Xijiang
Chen , Ningsheng Xu and Qiang Su

P011 8CRYSTAL STRUCTURES AND MAGNETISM OF A SERIES OF TETRANUCLEAR
HETEROMETALLIC Co(III)-Ln(lll) COMPLEXES
Feng He, Yang-Yi Yang and Xiao-Ming Chen

P0119

CRYSTAL STRUCTURE OF DINUCLEAR COPPER (II) COMPLEX OF
DIMETHYLGL YOXIME WITH BRIDGING CHLORIDE
J. Kowiththaya , S. Siripisarnpipat, V. Ngumviriyakul , N. Chaichit andS . Sukvinich

P0120

CONFORMATION OF EIGHT MEMBERED RING: 6-[BIS (2-CHLORO ETHYL)AMINO ]-12OXO- DIBENZO [d,g],[1 ,3,2] DIOXAPHOSPHOCIN 6- OXIDE
M.Krishnaiah and N.Jagadeesh Kumar.

P0121

ELECTRON DENSITY AND ELECTRONIC CONFIGURATION OF BIOMIMETIC MODELDINITROSYL IRON COMPLEX [S5Fe(N0)2]I.-Jui H su , Jey-Jau Lee , Chung-Hung Hsieh , Tze-Yuan Wang , Gene-Hsiang Lee , Jin -Ming
Chen , Jyh-Fu Lee , Shyue-Chu Ke , Wen-Feng Liaw and Yu Wang

P0122

MULTIPLE-WAVE X-RAY DIFFRACTION AT RESONANCE: AN ITERATIVE BORNAPPROXIMATION
W.-H . Sun , Y -R Lee , S.-C . Weng , S.-Y. Cheng , W.-C . Sun and S.-L. Chang

P012 3C-C BOND CLEAVAGE OF ALKYL AND ARYL CYANIDES BY A DINUCLEAR COPPER(II)CRYPT ATE
Tongbu Lu , Xiaomei Zhuang , Danni Que , Yanwu Li , RuoQqiu Wu , and Shi Chen

P0124

CRYSTAL STRUCTURE AND CHARACTERIZATION OF A NEW CARBOXYLATO-MPO
ORGANIC-INORGANIC HYBRID MATERIAL
Yueh-Chun and Sue-Lein Wang

P0125

STRUCTURAL CHARACTERIZATION OF TWO ORGANICALLY TEMPLATED GALLIUM
PHOSPHATE
Yu-Lun Lai and Sue-Lein Wang

P0 126

MIMICRY OF DIMETALLIC HYDROLASE$ : SYNTHESES, STRUCTURES AND ACTIVITIESOF ASYMMETRIC HOMO- AND HETERO-DINUCLEAR MODELS
Gen-qiang Xue , Ian D. Will iams and Xiao-Yuan Li

P0127

STRUCTURAL ANALYSIS OF FIVE -COORDINATE TRANSITION METAL BORYLCOMPLEXES WITH DIFFERENT D-ELECTRON CONFIGURATIONSKing Chung Lam , Wai Han Lam , Zhenyang Lin , Todd B. Marder and Ni cholas C. Norman

P0128

X-RAY CRYSTAL STRUCTURE OF PLASMODIUM VIVAX DIHYDROFOLATE
REDUCTASE : ANTIFOLATE RESISTANCE MECHANISM
Palangpon Kongsaeree , Puttapol Khongsuk , Ubolsree Leartsakulpanich , Penchit Chitnumsub
and Yongyuth Yuthavong

P0129

SELF-ASSEMBLY OF MULTINUCLEAR RUTHENIUM THIOSALICYLATESUPRAMOLECULESStephen Sin-Yin Chui , Sharon Lai-Fung Chan and Chi-Ming Che

P0130

THE CRYSTAL STRUCTURE OF SODIUM DIVANADYLDICITRATE DODECAHYDRATE
Pham Than h Huyen and Kenneth J. Haller

P0131

TROILITE WITH SPACE GROUP P31c FOUND IN METEORITE
Takeshi Nakagawa, Michael E. Zolensky , Katsuhiro Kusaka , Yoshikazu Miyatac andKazumasa Ohsumi

P0132

A RE-INVESTIGATION OF THE CRYSTAL STRUCTURE OF NATURAL CHEVKINITE
Li Guowu , Ma Zhengsheng , Shi Nicheng , Xiong Ming and Fan Haifu

P01 33

STRUCTURE CHANGE OF Mn203 UNDER HIGH PRESSURE CAUSED BY CHARGEDISPROPORTIONA TION
Takamitsu Yamanaka , Takaya Nagai , Tomoo Fukuda and Koichi Kittaka

P01 34

THE STRUCTURAL BASIS OF STABILITY AND SUBSTRATE SPECIFICITY OF A PLANT
CYSTEINE PROTEASE FROM AN INDIGENOUS FLOWERING PLANT, ERVATAMIACORONA RIA
Chandana Chakrabarti, Piyali Guha Thakurta , Sampa Biswas and J.K. Dattag upta

P0135

STRUCTURAL BASIS FOR CATALYTIC RACEMIZATION AND SUBSTRATE SPECIFICITY
OF N-ACYLAMINO ACID RACEMASE FROM DEINOCOCCUS RADIODURANS
Wen-Ching Wang , Wei-Chun Chiu , Chun-Li Wu , Cheng-Yu Chen , Jai-Sh in Liu , andWen- Hwei Hsu

P0136

COMPARISON OF THE STRUCTURE AND FUNCTION OF INFLUENZA VIRUS
NEURAMINIDASE AND PARAINFLUENZA VIRUS HAEMAGGLUTININNEURAMINIDAS(HN)P.M . Colman

P01 37

STRUCTURAL INVESTIGATION OF MYCOBACTERIUM SMEGMA TIS DPS
Siddhartha Roy , Satyabrata Das , Surbhi Gupta, K . Sekar, Dipankar Chatterji and M. Vijayan

P01 38AWAY FROM THE EDGE: SAD PHASING FROM THE SULFUR ANOMALOUS SIGNAL
MEASURED IN-HOUSE WITH CHROMIUM RADIATION
C. Yang , J. W. Pflugrath , D. A. Courville , C. N. Stence, S. P Williams , K. P. Madauss andJ. D. Ferrara

P01 39CRYSTAL STRUCTURE OF DISINTEGRIN A DOMAIN SWAPPED HOMODIMER FROMSAW-SCALED VIPER (ECHIS CARINATUS) AT 2.5A RESOLUTION
Punit Kaur, Sameeta Bilgrami, Shail ly Tomar, Savita Yadav, Janesh Kumar, Talat Jabeen,
Sujata Sharma and T. P. Singh

P0140INTRODUCTION OF THE PROTEIN DATA BANK JAPAN (PDBJ)
T. Kosada , R. Igara shi, Y. Kengaku, S. Saek i, Y. Morita, M. Kusunoki , K. Kobayashi ,A. Paehler, N. Ito and H. Nakamura

P0141

REFOLDING , PURIFICATION AND CRYSTALLIZATION OF APICAL MEMBRANE
ANTIGEN 1 FROM PLASMODIUM FALCIPARUM
Tao Bai , Aditi Gupta and Adrian H. Batchelor

P0142

CRYSTAL STRUCTURE OF A NOVEL SIGNALLING GLYCOPROTEIN FROM BOVINEREVEALS A NEW RECOGNITION SITE
Janesh Kumar, Jayshankar Jasti, Sujata Sharma, Bhaskar Singh , Ash a Shushan and
Tej P. Singh

P0143

CRYSTAL STRUCTURE OF THE SMALL FORM OF GLUCOSE-INHIBITED DIVISIONPROTEIN A FROM THERMUS THERMOPHILUS HB8
W . Iwasaki, H. Miyatake and K. Miki

P0144

CRYSTAL STRUCTURE OF SPHERICAL PARTICLE OF TOBACCO NECROSIS VIRUS
COAT PROTEIN LACKNG N-TERMINAL ARM AT 2.6 A RESOLUTION
Keiichi Fukuyama , Shu lshitobi and Kazuhiko Saeki

P0145

X-RAY CRYSTAL STRUCTURE ANALYSIS OF A COMPLEX BETWEENCARBOXYPEPTIDASE YANDA PROTEIN INHIBITOR
Yasuo Hata, Minoru Hayashida , Tomomi Fujii , Joji Mima, Rikimaru Hayashi and Yoshimi Ueda

P0146

CRYSTALLIZATION AND PRELIMINARY X-RAY STUDY OF CARNOSINASE FROM MICE
Tetsuo Yamashita , Hirota Otani , Genji Kurisu , Masamni Kusunoki , Nobuaki Okumura and
Katsuya Nagai

P0147

FACTORS THAT INFLUENCE SUCCESS IN PROTEIN CRYSTALLIZATION
Heather M. Baker, Ivan lvanovic and Edward N. Baker

P0148

CONCENTRATION AND CALCIUM DEPENDENT MONOMER-DIMER AND ACTIVITYINACTIVITY TRANSITIONS IN PHOSPHOLIPASE A2 : CRYSTAL STRUCTURE OF ACALCIUM INDUCED DIMER AT 1.6 A RESOLUTION
Talat Jabeen, Sujata Sharma, Nagendra Singh , Rajend ra K. Singh , Punit Kaur and
Tej P. Singh

P0149

NATIVE PEPTIDES AS POTENT INHIBITORS OF SERINE PROTEASES : CRYSTALSTRUCTURE OF A COMPLEX FORMED BETWEEN a-CHYMOTRYPSIN AND ITS
AUTOCATALYTICALLY PRODUCED OCTAPEPTIDE AT 2.2A RESOLUTION
Nagendra Sing h, Talat Jabeen , Sujata Sha rm a, lpsh ita Roy, M. N. Gupta, Sameeta Bilgrami ,A. P. Baxla , Sharmistha Dey, Ma rcus Perbandt , Ch. Betzel and Tej P. Singh

P0150

ANAEROBIC AND AEROBIC STRUCTURES OF FERREDOXIN II FROM DESULFOVIBRIOGIGAS REVEAL ELECTRON TRANSFER MECHANISM
Chun-Jung Chen , Yin-Cheng Hsieh , Ming-Yih Liu and JeanLeGall

P0151

CRYSTAL STRUCTURE OF CHORISMATE SYNTHASE: A NOVEL FMN-BINDING FOLDAND FUNCTIONAL INSIGHTS
Se Won Suh and Hyung Jun Ahn

P0152

PROBING THE DNA KINK STRUCTURE INDUCED BY THE HYPERTHERMOPHILIC
CHROMOSOMAL PROTEIN SAC7D USING SITE-DIRECTED MUTAGENESIS AND X-RAY
CRYSTALLOGRAPHY
Chin-Yu Chen , Ting-Wan Lin , Chia-Cheng Chou , Tzu-Ping Ko and Andrew H.-J. Wang

P0153

SECONDARY BINDING SITE OF TRYPSIN REVEALED BY CRYSTAL STRUCTURE OFTRYPSIN-OVOMUCOID INHIBITOR COMPLEX
B. Syed Ibrahim and Vasantha Pattabhi

P0154

CRYSTAL STRUCTURE OF THERMOSTABLE LIPASE FROM NEW SPECIES OF
GEOBACILLUS STRAIN T1
Raja Noor Zaliha Raja Abd . Rahman , Takahiko Yamamoto , Leow Thean Char, Abu Bakar
Salleh , Mahiran Basri , Kazufumi Takano , Shigenori Kanaya , Hiroyoshi Matsumura, Tsuyoshi
Inoue and Yasush i Kai

P0155

STUDIES ON THE CRYSTAL STRUCTURE AND FUNCTION OF CUCURMOSIN , A
RIBOSOME-INACTIVATING PROTEIN FROM SARCOCARP OF CUCURBITA MOSCHATA
Ming-Huang Chen , Shan Liu , Zhi-Ren Wang and Liqing Chena

P0156

CRYSTAL STRUCTURE OF INORGANIC PYROPHOSPHATASE FROM HELICOBACTERPYLORI
Y.-J . Sun , T.-C. Chao , C.-Y. Huang and H.-M . Huang

P0157

AVAILABILITY OF THE X-RAY DATA COLLECTED WITH A CR ROTATING-ANODE FOR
PHASING PROTEIN CRYSTALS
Takashi Yamane , Atsuo Suzuki , Seiji Okazaki , Hideki Tanizawa , Tatsuo Hikage ,Venkatachalam Rajakannan , Devadasan Velmurugan and Kanagaraj Sekar

P0 158FIRST DETERMINATION OF THE INHIBITOR COMPLEX STRUCTURE OF HUMANHEMATOPOIETIC PROSTAGLANDIN D SYNTHASE
Yuji Kado,a Tsuyoshi Inoue , Yousuke Okano , Kousuke Aritake , Daisuke lrikura, Nobuko
Uodome, Nobuo Okazaki , Shigehiro Kinugasa , Hideyuki Shishitani , Hiroyoshi Matsumura ,Yasushi Kai and Yoshihiro Urade

P0159

THE NEW MACROMOLECULE CRYSTALLOGRAPHY BEAMLINE 3W1A AT BSRF
Peng Liu , Yu Hui Dong , Sheng Huang, DeQiang Yao and DingChang Xian

P0160

CRYSTAL STRUCTURE OF A DISSIMILATORY NITRITE REDUCTASE FROMHYPHOMICROBIUM DENITRIFACANS
Yang Xie , Tsuyoshi Inoue and Yasushi Kai

P0161

CRYSTAL STRUCTURE OF THE SHANK PDZ-LIGAND COMPLEX REVEALS A CLASS I
PDZ INTERACTION AND A NOVEL PDZ-PDZ DIMERIZATION .
Y.J. lm, J.H. Lee , S.H. Park , S.J. Park , S.H. Rho, G.B. Kang , E. Kim and S.H. Eom

P0162

THE STRUCTURE OF IMPORTIN-13 BOUND TO SREBP-2 : INSIGHTS INTO NUCLEAR
TRANSPORT OF A TRANSCRIPTION FACTOR
Sao Jae Lee , Toshihiro Sekimoto , Eiki Yamashita , Emi Nagoshi, Atsushi Nakagawa, Naokolm amoto , Masato Yoshimu ra, Hiroaki Sakai , Khoon Tee Chong , Tomitake Tsukihara andYoshihiro Yoneda

P0163

MOLECULAR REPLACEMENT SOLUTION FOR AN ACYLPHOSPHATASE FROMPYROCOCCUS HORIKOSHII
Yuk-Yin Cheung and Kam-Bo Wong

P0164

CRYSTALLIZATION , DIFFRACTION AND MOLECULAR REPLACEMENT OF A NOVELORANGE FLUORESCENT PROTEIN FROM CERIANTHUS SP.
Denis T.M. lp, David C.C. Wan and Kam-Bo Wong

P0165

APPLICATIONS OF ACORN TO ATOMIC RESOLUTION DATA I TRUNCATED DATA AT
1.5 A RESOLUTION OF CATALASE (-57 kDa)
S. Selvanayagam , D. Velmurugan and T. Yamane

P0166

STRUCTURAL BASIS OF NLS- BINDING SPECIFICITY OF IMPORTIN a ISOFORMS
S.N.Y. Yang , J Harris and B. Kobe

P0167

STRUCTURAL AND FUNCTIONAL INSIGHT INTO NONSPECIFIC NUCLEASESINVOLVED IN CELL DEFENSE
Hanna S. Yuan , Chia Lung Li , Kuo-Chiang Hsia and Woei-Chyn Chu

P0168CRYSTAL STRUCTURE AND CONFORMATION ANALYSIS OF A TETRAPEPTIDE
BOC-B -ALA-LEU-AIB -VAL-OM E
R. S. Rathore

P0169

CRYSTAL STRUCTURE OF THIAPYRAN REVEAL HERRING -BONE P ··· P
INTERACTIONS
T. Narasimhamurthy, J. C. N. Benny, K. Pandiarajan and R. S. Rathore

P0170

SINGLE-CRYSTAL NEUTRON DIFFRACTION STUDIES OF RUBREDOXIN AND OTHER
SMALL PROTEINS.
Robert Bau

P0171

WATER ENHANCED CRYSTALLINITY IN CYRTOPHORA SPIDER DRAGLINE
Hwo-Shuenn Sheu , Khin Win Phyu , Yung-Ping Chiang , Yuch-Cheng Jean and 1-Min Tso

P0172

TWISTING OF PEPTIDE BOND BY HYDRATION WATERS AND LOCALIZATION OF
DEUTERIUM ATOMS OBSERVED IN HUMAN LYSOZYME BY NEUTRONCRYSTALLOGRAPHY
Kaori Chiba-Kamoshida, Takuro Matsui, Toshiyuki Chatake, Takash i Ohhara , Andreas
Ostermann, lchiro Tanaka, Katsuhide Yutani and Nobuo Niimura

P0173

DESIGN OF PEPTIDES WITH a, b- DEHYDRO-RESIDUES : SYNTHESES, CRYSTALSTRUCTURES AND MOLECULAR CONFORMATIONS OF TWO TETRAPEPTIDES :Cbz- OVal - Val - DPhe- lie- OCH3 AND Cbz- OVal -Leu- DPhe - Leu - OCH3
V. K. Goel , A. P. Baxla, R. K. Somvanshi , R. Padma , S. Dey and T. P. Singh .

P0174

EXPRESSION , PURIFICATION AND CRYSTALLIZATION OF MOB1 FROM
Sacchromyces cerevisiae
Shannon W. N. Au , J. Wade Harper and David Barford

P0175

THE C-TERMINAL REGION IN TRICHOSANTHIN IS IMPORTANT FOR ACTIVITY AND
CONFORMATIONAL STABILITY
Hiu-Mei Too ,Yi Ding, Siu-Hong Chan , Zhilong Wang , Yiwei Liu , Mark Bartlam, Yicheng Dong ,Kam-Bo Wong , Zihe Rao and Pang-Chui Shaw

P01 76

PURIFICATION AND STUDY OF ITS EFFECT OF POL YTYPISM IN SOLUTION GROWNCADMIUM IODIDE CRYSTALS USING X-RAY DIFFRACTION
S.K.Chaudhary and Harjeet Kaur

P0 177

PHENOMENON OF POLYTYPISM IN MELT-GROWN LAYERED CRYSTAL OF Cdl2 , Pbl2
AND CdBr2.
S.K.Chaud hary and Harjeet Kaur

P0178

CRYSTALLIZATION OF SOME ORGANIC CONSTITUENTS OF URINARY STONES IN GELAND CHARACTERIZATION
E. Ramachandran and S. Natarajan

P0179

SOME AZIDO-BRIDGED COORDINATION POLYMERS : STRUCTURES AND MAGNETISMSong Gao, Hao-Ling Sun , Yuan-Zhu Zhang and Bao-Qing Ma

P0180

BISMUTH DISORDER IN PYROCHLORE OXIDES
Brendan J Kennedy , Leqing Li and Qingdi Zhou

P0181

XRD, FTIR AND TGA/DTA STUDIES OF GEL GROWN GLYCINE AND DL-SERINE
E. Ramachandran and S. Natarajan

P01 82CRYSTAL GROWTH BY CHEMICAL TRANSPORT OF PEROVSKITE TUNGSTEN
BRONZES, LixW03, AND THEIR OPTICAL PROPERTIES
K. R. Dey , A. Hussain and C. H. ROscher

P0 183

3X3X1 SUPERSTRUCTURE OF LITHIUM MANGANESE SPINEL
Nobuo lshizawa, Douglas du Boulay, Kenji Tateishi , Katsumi Suda and Shuji Oishi

P0184

MICRO-STRUCTURAL STUDY ON THE ALLOY MLNi3.75C00.75Mn0 .3AI0.2(ML : LA-RICH MISCH METAL) DURING THE HYDROGEN ABSORPTION AND
DESORPTION CYCLING
Guanglie Lu and Zhiq ing Yuan

P0185

RESIDUAL STRESS MEASUREMENT FOR GRANITE BY TOF NEUTRON DIFFRACTIONMETHODT . lshigaki , H. Obana , J. Kodama , S. Harjo and T. Kamiyama

P0186

HYDROGEN-BONDED CRYSTALLINE FRAMEWORK BASED ON RESORCIN[4]ARENE
AND 4,4'-BIPYRIDINEDIENE
Shu-Qun Liu , Qian- Feng Zhang and Wa-Hung Leung

P0187

OXYGEN-INDUCED FORMATION OF A NOVEL TETRA-NUCLEAR P-CYMENERUTHENIUM COMPLEX WITH OXO BRIDGES
Lihua Liu , Qian-Feng Zhang and Wa- Hung Leung

P0188

CRYSTALLOGRAPHY OF MICROSTRUCTURAL TRANSITIONS IN COPPER BASEDSHAPE MEMORY ALLOYS
0 . Ad1gOzel

P0189

POSITIONAL DISORDER AND DIFFUSION PATH IN OXIDE-ION CONDUCTORS
Masatomo Yashima, Katsuhi ro Nomura, Daiju lshimu ra, Syuu hei Kobayashi , Hiroyuki
Kageyama , Wataru Nakamura , Kenjiro Oh-uchi and Kenji Ohoyama

P0190

HIGH-TEMPERATURE NEUTRON POWDER DIFFRACTION STUDY OF CERIA UP TO
1500C
Syuuhei Kobayashi , Masatomo Yashi ma, Daiju lshimura, Kenjiro Oh-uchi , Wataru Nakamura ,Kenji Ohoyama , Katsuhiro Kawach i and Tadahi Yasui

P01 91STRUCTURAL CHANGE OF THE Li-DOPED LANTHANUM TITANATE PEROVSKITE
La2/3-xli3xTi03
Wataru.Nakamura, Masatomo Yashima , Daiju lshimu ra, Syuuhei Kobayashi , Kenjiro Oh-uchi ,Mitsuru ltoh and Kenji Ohoyama

P0192

AN ORGANICALLY TEMPLATED NICKEL GALLOPHOSPHATE WITH A UNIQUE LAYERSTRUCTURE
Chia-Her Lin , Yu-Lun Lai and Sue-Lein Wang

P0 193

GRASS FORMIG AT THE LIMIT: HOW GLASS FORMS WHEN THERE IS INSUFFICIENTNETWORK FORMER TO GO AROUND
Shinji Kohara , Kentaro Suzuya , Ken Takeuchi , Chu n-Keu ng Loong , Marcos Grimisditch , J.K.
Richard Weber, Jean A. Tangeman and Thomas S. Key

P0194

NEW RESULTS BY USING TEM TO STUDY OF THE MAGNETIC MATERIALS NbFeB
V. Vong , D.M. Thuy and N.V. Vuong

P0195

ROLE OF THE DOPED ELEMENTS IN MATERIALS FOR GAS SENSORS
V. Vong and L.T. Hung

P0196

CRYSTAL STRUCTURE X-RAY ANALYSIS OF TWO SPIRO-BIFLUORENE COMPOUNDSWITH REMARKABLE INTENSE SOLID-STATE RED FLUORESCENCE
Ch in-Ti Chen , Chih-Long Chiang , Wei-Ching Wu and Yuh-Sheng Wen

P0197

CORRELATION BETWEEN CRYSTAL STRUCTURE AND FERROELECTRIC
PHASETRANSITION TEMPERATURE FOR KTP MATERIALS.
Stefan T. Norberg, Joacim Gustafsson and Nobuo lshizawa

P0 198SYNTHESIS, STRUCTURE, AND PHASE RELATIONSHIP IN LITHIUM MANGANESEOXIDE SPINEL
Masao Yonemura , Atsuo Yamada , Stefanus Harjo, Takashi Kamiyama and Ryoj i Kanno

P0199CRYSTAL STRUCTURE ANALYSIS OF Ti-Cr-Mo HYDROGEN ABSORBING ALLOYS
K. lwase , Y.Nakamura , E.Akiba and T.Kamiyama

P0200

CARBON MICRO-RODS IN LOW-TEMPERATURE HYDROGENATED AMORPHOUS
CARBON
Prabal Dasgupta , D.P. Bhattacharyya, Nikhilesh Chowdhuri and Aru p Banerjee

P0201

EVOLUTION OF GROWTH MODE, MICROSTRUCTURE, AND PHOTOLUMINESCENCE IN
MG- DOPED GAN EPILAYERS ON Al203 (0001)
Hsueh-Hsing Hung, Chin-Pin Chuang and Ling-Yun Jang

P0202

STRUCTUAL ANALYSIS OF SLIDE-RING GEL BY SMALL ANGLE X-RAY SCATTERINGAND CONTROL OF THE PULLEY EFFECT
Kentaro Kayashima , Yuya Shinohara , Eiji Takeuchi , Yoshiyuki Amemiya , Yasushi Okum ura
and Kohzo Ito

P0203

METAL-BASED MOLECULAR FUNCTIONAL MATERIALS OF FLUORENES
Wai-Yeung Wong

P0204

CRYSTAL STRUCTURES OF MOLECULAR COMPLEXES BETWEEN SURF ACT ANTS
AND HYDROQUINONE
Akiko Sekine, Yuko Fuj imura, Hidehiro Uekusa, Yuj i Ohashi and Nahoko limura

P0205

LITHIUM DIFFUSION IN LITHIUM MANGANESE SPINEL
Kenji T ateishi , Douglas du Boulay and Nobuo lshizawa

P0206

NUMERICAL CONVERSION BETWEEN THE PEARSON VII AND THE VOIGT FUNCTIONS
H. Wang and J Zhou

P0207

ON EQUIVALENCE OF COLORINGS OF PATTERNS ASSOCIATED WITH
DECOMPOSITIONS OF THEIR SYMMETRY GROUPS
Rene P . Felix and Maria Veronica P. Qui ling uin

P0208

THE AUSTRALIAN REPLACEMENT RESEARCH REACTOR
R A. Robinson and S. J. Kennedy

P0209

IMPROVEMENT OF SPATIAL RESOLUTION OF IMAGES TAKEN WITH X-RAY CCD
DETECTOR BY MAXIMUM LIKELIHOOD METHOD
Y. Shi nohara , E. L Kosarev, Y. Ueji ,a K. Uesugi , Y. Suzuki , N. Yagi and Y. Amemiya

FOX 20 focusing x-ray optic ...
... simply unique

The UNIQUE combination of the precision graded multilayE

coating along the mirror length with a SINGI

mirror substrate allows the capture <a part of the source larger tha
any

other

multilayermirrc

system of equ ivalent length.

The single reflection brings
more 11ux to vour sample• enhanced useful flux compa red to standard tv
reflection designs• reduced co llection time

• enhanced lifetime and lower cost of ownersh ip (u nc
vacuum)• compact mechanical design• easy to align (10 m inutes procedure)• adaptable to all X-ray generators( rotating anode generators. sea led
tubes or micro-focus sources)

Data courtesy of R. Kahn, L. Nauton. ISS Grenoble

Before upgradelysozyme crystal

After Upgradewith classicalconfocal multilayer

0.4x0.4x0.4 mm and
Gd as a phasing agent

with Fox 20 single
reflection multi-layer

systemUnit ceii (A) a:b•77.12 c•38.6

3 Minutes Exposure

Data collection:
360 images at 1 ° steps

--

----

optic from Xenocs
1 Minute Exposure

0.55

Mosaicity

0.55

0.209

Rsym from 1.86 to 1. 75

0.209

0.262
0.053

Rsym from 1. 75 to 1.66
_sym mean_ _ _R

0.27
0.048

0.053

Rfac

0.048

0.074

R ana

0.074

99.8

Completion

99.9

23.4

Multiplicity

23.3

9.0

lmean/Sig

10.2

2.5

1/Sig from 1.75 to 1.66

3.3

Xenocswww.xenocs.com

sales@xenocs.con

phone +33 4 76269540 fa x +33 4 7626954

INTERNA TIONAL TABLES
for CRYSTAL LOGRAPH Y

Coming soon
Volume A1
Symmetry relations between space groups
Volume G
Definition and exchange of crystallographic data

www.iucr.org/it

-ku lAn advanced
analvticaltool
to deal with abroad,in-depth analvsis
1 ..

The D/MAX-Uitima ~s a versatile X-ray diffractometerequipped with crossbeam optics, an incident opticalsystem unique to Rigaku. This analytical tool, as asingle unit, can handle a wide variety of analyses
ranging from routine powder sample analysis to thinfilm material evaluation analysis by in-planemeasurement.

High-resolution parallel beam optics
Quite effective for high-precision analysis oforganic compounds, ceramics, samples
characterized by strong preferred orientation ,those difficult for crushing and shaping ,as well as structure analysis.

JADE 6.5
JADE 6.5 provides comprehensive information on crystals
simply, accurately and rapidly just by clicking the aimed
program . Included are qualitative and quantitative analysis,
crystallite size calculation , lattice parameter refinement,
structure analysis with powder patterns, and much more.

Rigaku Corporation

Rigaku/ MSC, Inc.

Beijing Offi ce : Rm.1505, No.22, FANLI Bldg.,
Chaowai Street, Chaoyang District , Beijing 100020, China
Phone : 86-10-6588-3370 Fax :86-10-6588-3372
http :1l www. rigaku. com .en/

9009 New Trails Drive The Woodlands, TX 77381 -5209, USA
Phone : 281-363-1033 Fax: 281-364-3628
e-mail: info@ rigakumsc.com
http :/Jwww. rigakumsc. com/To meet the needs
tor high throu
crvstalloura_=""'
Rigaku offers a new standard
for the structure anal~isof living macromolecules.

?\-AXIS HTC• Suitable for the high intensities of asynchrotron or the perfect complement
to the Rigaku FR-EsuperBright highbrilliance rotating anode generator
and high-throughput crystallography.

•Innovative three IP design with 10
second deadtime and dual readheads, provides the throughput ofa ceo with the large apertureand superlative dynamic rangeof an image plate detector.
• Fitted with a partial-x, 3-axis, Automated Crystal Transport,goniometer to provide for full' Orientation, and Retrieval
sampling of reciprocal space.

,------------:ACTOR'-------------

Rigaku Corporation

Rigaku/ MSC, Inc.

Beijing Office: Rm.1505, No.22, FANLI Bldg.,
Chaowai Street, Chaoyang District , Beijing 100020, China
Phone: 86-10-6588-3370 Fax: 86-1 0-6588-3372
http ://www.rigaku. com.cn/

9009 New Trails Drive The Woodlands, TX 77381-5209, USA
Phone:281-363 -1033 Fax:281-364-3628
e-mail: info@rigakumsc.com
http: / /www. rigakumsc. com/~ FUJIFILM
1&1- lmaging & Info rmation

0>111~('11±71' II,. A'f''t. :fitllfl::~fJ\€>~~fi.HiiJlft~~'f''ZiiMi0>~-::1.~1,
T·~-~U"··~~BU"·~-~~&U"-~MU".7~~~'~*11,.7-r ::1. 7v-f (FPD) """· ilitllfm1!:U"O>•& · &tl ·iii .Pail::if

Ji:'Zfit.:-::>TI. '~1" .

Jll:Ji\tB;;!!Ri1!i li;H\i 2-26-30 'i' 106-8620.A.lll$ : Wilt. Tel : 03 (64 18)2896
IMJ:I;I:HP (http://www.fujifilm .eo.jp/) (JJ!~IIlfflij/F.~t'l~lll/:t/71'/ffi~~;::jn~c ',t~LHit:iJ'il'0~UlHf5$l'l1~iii~~~~lkt9 f.IO)It:i•ll;(~~o 71JvO)~Jfi6JJ

t111W~Mtli~lcif <$J'f0)7 t - Jvf 1 'J 7

t lf!fll'?·y1'\0)$]'f7tJ1;;

tX~§Jii0)1f!fll?·dO)~Jfi6Jf ·~iii

X~@ltfif'-j9Jl~fi:~;f- ~I a'\~ ·Y7l-\ip:!- ~~~;f-/l'~iii
tlh~ltc$l':nHeap7711v, PB, PDB~iN¥1¥

1~r~~xm. ~r~~~7~ryr7
Turbo-Frodott 5Hff' 1J'J 'f:H:tH 7.l5ir~~'J7 ~?I 7l't.
t 7Jv 17 !- /l'O)$l'-HVF-~ttt-- ~t CPKfTiv, .:::HilHf'IV. Ball and StickUiii

TURBO· FRODOOOJRffl>=r 323-0022 *m*~/J\~lrr=P.~*im IJI-6-2 r v17-t" JvsF
TEL:0285-24-9731 FAX:0285- 24-9751 URL:www. las.jp E-mail:support@las.jp;f*r\~1±IJvi~ YA -r L.~'· (t , ~ ) O).:::oo~l!lll!lf-r/1-\'lvf- ;ri-l· 3J 7J ·y11J /?IE~, 1J ca!Hn ·111! /?IE~' J.J..'@,T7J ·d i)Jij, /;D'J..J~Ir1 3 /l~/l,ifO)!Jl•1H/Ca!Oil!il*:o ~ ~~~, 13Ca ,l3CP7 H~t IH17 H~, NOEIJ, ;JtiiHlM~r~O)ilJI~I~· NKRIJ' ;Jtii~M ::Ji~~~~l1/~77f11M7f - ~~iii

t~III!MM ~3 ;;O)tl\nliiiill;(n;;~~~

v-:;t NVRICJ: 0fM~O)/R/EO)tcN.>O).!j!IJilt ~ tltcn~
I IHil'-0) 7711v t ~Jrl!O) J..ntii~~t =oo~O)~l0)$l'f~n~

DYNAMOI::l: , V .::1 ~ 1.----T ·;; 1·7 .::.-1) /7'(-l;:li-~? t~~lf!irf!-~ 7' t:I 7'7 L 1"9.

DYNAM QMolecular Structure Engine<NMRffl>Molecular Operating Environment
JJ 7 ~tCCGf:I:!JUftf-illtJ'Ht~ ~ 7. 7 A

sceratr eSoftwsre Sceleti eSc lenceMOEtJ .;; c7J =r- "Z' Jf!j rt ;5 -tt ?.> JJi '- p ::u~ rt !f- .w 1ft
MOEicti1JiifiJt~0)1t~O)I!Iftfi~Jf8L.1t './7 t-?:r.7/ ~~7-::l"t::"J" ollllftllilc~fflltJI~-i*ft"J" ~;:eli:~!:>, ~*0)'.17 t-? :r.rO)"mi&~D~tt ,
if::>Tt<iil..l.\lt.ft!i!~:A7 ~~J!Utl..if9 0·~·57-<~A
if!:5:l''Tt.J 1 S$'::;1(~JG'. DNA . RNA ~O) ~i$1l!i5:l''T .
§alltii-*~lJqti.~;;n:~mo. ~::;t::''T~5-·('::1'51)-H(~· ? 5A9-Wft/T. 7 -{:;!;!j-:;11)::11-0)flJifj· Similarity/ DiversityWft/T

5:l''TIJI~. liillll!m~ml£o· ~~~ 'E 5"Jv i ;:J;7.J*~~miti3'#.!5-1':t5u-;i51!Wftn-~~7-~"l:lt-~.)(::;t-5:l''T!Jiii t.J1Sillil 7'-$'il:c, A :tl.lyr::; -Hf~itc-~W~c~~7-$'W~:;A7~~~1£o. $'::1 1 (?JG'~immt!T. l);lj::; r:*Sti&flili~*• ?'IJyr:r:Y:t'::l?'PC c~ll!i3JJi!l=5:l''TCD~~t.JiliJii~o•••••asVLtlll~11!l~l!iSVLc7':11)'T-:;3::;0)111J~~!JI'E>tibtt
L'l!i~ o MOECD7':11)'T-:;3::;I<J:SVL cl2iillc!:tt .
~-A ~-r:CDil:il:m~<!:tt~~~ - ~-if-0)~~1:>· 7 7 --;;'~7 ::r7''!:5"Jvi;:M::5<3 D 5"-$'r< - A~*

11!ll'fo. ~'T1J~, 11J1J~!t·· 112i!M*fi. 51'3"7'5·0 ,.:::;t. • •iK7::;:;;.Jvtt•. t:y:t:::;?·:;.:::J.l.l-:;3::;. 7' .::./llft291j0)';(' 1!177'5-1'::1 .)(::I I. 7'.::./mtiJIUMD-$'-;;'-5-1'/51J. $'::1 1 (? f("'~7 7.:: 1J- 7'-9"'-A· $'::1 1 (? J( i!\'!:D ~-'!:5"1)::; ::;/·. ~?1.\~Jti$0)'1: 5"1)::;~7'· $'::;I (?fliilli!M*IT• Linux (Redhat6.21:.tf4)· 5:l''TI 2iill'TCD.tll· QSAR'E5"JvCT.>IJI·· ..Iilli• Windows 98l:.tlll• SGI IRIX 6.5J.:.ti!f• HP HP·UX11 l:lllll• Recursive partitioning)%;•'SI:JN Solaris 5.81:11lf• ~5A~· iiSi!.Y;J~U
CCGU 8 :$f.1lf'l:llfo!i**it~t± JfftV:A7 b.

'fW:1~l;f.JV:A:T~:<Is:E!B ~Jf'f!I~E!B'f279·0012 'f.IJ\'<iiliSi'm.AAfl1·5·2 SJli~Si'EB~if;¥/iii!i Si'l::J~4F
FAX: 047-380-1239 (ia)TEL: 047-380-1231 (ii!i: )E-mail : ccg@cubs.bio.rsi.co.jp

URL : http :l/www.rsi.co.jp/science.html• rai!OJi!liol'o'!;OJ;I:~u

OJ:ItUi!li l, , :>tdii!lillO)iAt'IJ<'~ I J~"t o• :t!l;i!rOJl±IJI;t'fi!;t,:(~t!'t.Qil.g-1)"~1)~9 ..

0 §- 7Lt-l--1d:7D:~:7'5 ~ I;:J;GilY'LiJl~lh *6~0)f[fm1d: §IJJ!¥U)5UL*9o~ M~imiimO)§mJJQXi6J.t.1JiiJJfj~c9o@ ~MO)~sma~~ma<~~c~*~a SBS7Lt-H;:~~ttiiJJfi~c9o

H~:Ytm1d:~"L:h'5:::Z (D7:h'5:A, 7'YJ\-jj'5:::Z)c~~PXL L'l ';Qt.: ~:Yt~~tJ:~LtlO)tJ:l, ' I' D 'Y:tii!~~~I~'7')-A

ijif-1\

ill illlllo\l\:ll.l- t-

9IJIA,l!il11• *~ i!! lcl:W1t!:FtiJf~pfi ( HI!~tiJf~pfi) c:l=tf6Jc !UJ ~L.~L.i.: o@ 6JIIIIftWifiiJfbtiifi:gllllllJl'T l 40-0014llm:ml/ffill lll';;;l;:;l:t l -22-13 * Lll J:::JI,

TEL (03)3778 -7925

FAX(03)3778 -7952

ifi-1...~ - V': http//www.iic-hq .co.jp

®Hitachi High-Technologies Corporation
Tokyo, Japan
http://www.hitachi-hitec.com
24- 14 Nishi-S himbas h.i 1-chome , Minato-ku , To kyo, 105-87 17, Japan
Te l: +8 1·3·3504-7 111 Fax: +8 1·3·3504-7 123

AsCA-2004
2 0 0 4if. 6 J=J 2 7 B ( B ) ~ 6 J=J 3 0 B (7.1<)(/:B ftt'*~: ~m: ( l=j:l00)

1T 0) C' ~ P'J )ilti ffl~
oo~~tY::>z -t;t, :/YH;f-;tr~ C9 z±F), ;\Y::J-7:*4~ C9 sif) , ? ~:/T::k§: C9si:F.l,;\Y:;iJo -;t;::k~ Co l if:), -t-L 'l 7"; Lr- L.::k~ ( 0 3$) O)~:ll! t m.RJ:IJ~@U:Eit!fll~~-8~a~O)C~ ~~m~, ~-a~ fi O) ~ ~~fi~~~@~ ~ct~ ~ l? :tLk oc-~~t.:lr~< 0)1JI.zt<=c"~-1J[lf!~IJt.:: <, 1iiJ~IJ t:tf!~~:t c- c"tEJ~; < ti~ tt '.

Jll[l.z•

AsCA-200 4· ~ WI: 2004 $6 .Fl2 7 B (B) ~3 0 B (7)<)• rwHtti±t!l : ~~~oo · ~~· $~t~ : ~~f!ii'S(::k$ (HKU ST)· f iJ m; t; : a ~n:~~ c~~f.'f:f5(7\$0)mts/li!i~li:'b-¥~£3& L :t ~ 0 )· i:l!iii!Ht~~Mii1J 13 : 2004 if 2 .Fl 15 El* : ;-· $~!H.:'R~ C!l!¥t±t<=-r i2S~ -=HJ't t:J~/ c'f'l fflr~tt' )4 .Fl I Bl-.:J.iifi

4 .Fl 1 Bl-.:J. fl~

Fu l l pa r t i c ipa nt

US$2 75. -0

US$225 . -Stud e nt pa r t i c i pa nt

US$ 125.-

US$175. -Acco mpa ny i ng perso n

US $100 .-US$100 . --B:ft\ J=JB (Uti! B)
1

6 .Fl27 BCB)2

6 F1 28 B (J=I)

3

6 F!29 B(;k)

4

6 F!30 8(7)<)

5

7 F! I B(;;f:)

-

ffll

m iJ

~L'Tt J{ :*:JgxJ{ -xilli~oo

rli't Fa,~~~

J L- 731(09 : 45/ 13 : 15)~~~

JL -70 1(09 : 45/ 12: 35)

iJtl~~ - ~CX-533(10: 00/ 13 : 35)

ti\li

~

~Jm, ~~-".

~f~, wffl;\.A c-* 7 Jv-"m6~mr::.?7Mtfr'~Jt~;W

C'Yi'-7. 7i;t<= -at YJJM'i::@)~i'{i:iit\'1±

B #Jfi;J-; 7 Mi#i:E
wi'Jl£Jt - iJ tl~~ CX-532(16 : 15/ 21 : 00)~~}{ - :*: fgx~

JL - 702(15 : 05/ 19 : 35)~~}{

JL -732(14 : 30/ 19 : 40)

-

~L?,~

~1m, ~f'i OOO)i£-"-~·f~, illiOOWi~~"~~ U nO)::J - 7-~MAh~O)jj, ~~B · ftOOBO)C~~'b~IJ:t~~~2M~t<::t;t~rJl£#t ~fi~{~~tl &lf- Al5~~fiJffltf~ C¥28 , 000) t;t"@l:t tl :t-ltlvo• • • - ~~ti~ D0 7~ - 0 A ~ • • •J ATA" · ~I±xilli : k:liHHJ!l~ f'T*m343~

T 103-00 13*Ji('/:l[Si:J:I:!k:JRB/.js:jw,AJ~ IHJ 2-33-8

TEL : 03 -5 641-1225, 1201
(E- mai l ) t. wata na b e@ gior ia-to u rist. co . jp

~AJB II!Jt::';t; 2 F
FAX : 03-564 1- 1223
tEl~ : i!till (fi}j(), ±[hl;\t. ®~Love your neighborLove your country
Love your work

The Spirit of Three Loves

Corporate Philosoph y

ICD©®DO

http://www.ricoh.com/

RICOH COMPANY,LTD.

d a complete
you wilh theBrul<.er AXS \-losduel line \hOI p h ul slruclurol
pro\ ( r high tl-lroug p\o~~~~Jes\OO S TO. g system
g enomics.
d® \m09'n\he Crystal form d incubation on
I le storageu integrateole
II as crystal p abrings yo. aging as we . l·k, and autorn
I I simP II]\mand relrievo o 1\·za\ion process.
. cryslo 1
X y screening
the pro\elnItomales -ro
strucluro
d
au
BruNo
Our
ded tor high spe~- h crystal ot many.
nl<. wn1C
nee
genomics, ~~ rt~r tull dolo collec\IOnislo be uselaborotory

HIGH
PROlE~~ :~~:Is c_ompl~~;:~y
THROUGHPUT
BIOLOGICAL~CRYSTALLOGRAPHY \EUJv\ C .
h"
TOOLS

Our
and
d taster, using lh
research sy
dolo beller on \CROSIAR source RO. tosl readout P_
hi h brilliancedittrocllon
g L· 1-\esl sensi\IVI\y,the nlg CD deleclor lo see

1-\er reso\ullon .
ore aboullgh" hto learn m\ulions tor _'g -1
Contocl us now
these exciflng new_so ce applicallons .
1 lite Se~enL
tl-lrougnpu

D

DISCOVERY PARTNERSINTERNATIONALBRUKER ADVANCED X-RAY SOLUTIONS
Norlh Americo'

BRUKER AXS INC. • Tel. I+ 1I 16081 276-3000 • Fax I+ 1I 16081 276-3006 • www.bruker-axs.cam • infa@bruker-axs.com

fhe Netherland"

BRUKER NON IUS B.V. • Tel. 1+31 I 115 I 2698400 · Fax 1+31 I 1151 2627500 • www.bruker-axs.com • info@bruker-nonius.com

KE

NIL

we won' I
d non on ddbe improve u.- ,introduce otne besl con·,nee we noveEven\ocl. Especio\\y, s
CO detector \ororgue tneel o\ tne besl cn b 11er version Y. \ Crystol\ogrop Ye. \ d Moteno s
Cnemtco ontne new P..,PE'f.. II

APEX II

The Best is Better. 4\( chip
NeW \oW ootseh. requires no toper
Large 62 rom c 'P
. 1 sensitivity
Still the ultimo e.
f o\ reso\ulton
Beller spa I.
•· \ distortion\ long• Still no spolia .
d deeper cooling or1<. notse on•
lower d orsures
doul and user
expo.
'th 4-porl reo .
\icolionselectrontCS WI\ \oW notse opP
N ew•
ds \or u tro
selectable speeb site to \earn more
ow or visit ou r we
ystol\ ogropny.
Contact us n\ulions \or cr
·mole
so
\\
oboul our u I•

BRUKER ADVANCED X-RAY SOLUTIONS-Jmth Amer;co: BRUKER AX$ INC. n Tel. (+I I (608) 276-3000 n Fox (+I I (6081 276-3006 n www.bruker-ox..com n ;nfo@bruker-ox..com"he Netherlands: BRUK ER NON IUS B.V. n Tel. (+31 ) ( 15) 2152 400 n Fox (+31) {15) 2152 500 n www.bruker-oxs.com n inlo@bruker-nonius.com

3ermony: BRUKER AX$ GMBH n Tel. (+491 (721 J 595-2888 n Fox (+49} (721 I 595-4587 n www.bruker-oxs.de n ;nfo@bruker-oxs.de

KER

IUS

Cryogenic sample changer

Ultrahigh-performance X-ray

IIIBP~World Leaders in X-ray Detectors

d n1trogen... but cooler ~Man everIntroducing the Cobra, the new NON-LIOUID Cryostream
from Oxford Cryosystems ...

~..._­....411- systems

OxfordCryo

Head Office
3 Blenhe1m Office Park
lower Road · Long HanboroughOxford OX29 8LN UK
T. +44 (0)1993 883488
F +44 (0)1993 883988
E. mfo@OxfordCryosystems.co.uk
North Arneocan OH1ce
7 Jackson Road Devens
MA 01432 USA
T. 1-866-0 XCRY0-8
978 772 7930
f_ 978 772 7941
E. lnfo@OxfordCI)'osystems.corn

Cryostream·like efficiency andreliability without
the liquid: Cobra
truly offers the bestof both worlds.
The Cobra offers:• Temperature range

80-SOOK• Fast coo l down time
[30 mins to lOOK]• Complete programmabilit~,J from a Cr~JOStream-st~,Jie controller• Turbo mode [ lDUmin gas flo w] for fast cooldown
The Cobra can be supplie d with or without a nitrogen gas generator, so IJOU
can use !JOUr laborato r ~,J dr!J nitrogen gas suppi!J if available_
We will even offer IJOU a trade-in on !JOur old nitrogen S~,JStem -JUSt contact
us for details.

We look after our technology so you can look after yours!

ww . O x f o r d C ros

s t e m s . com

It might sound illogical,
but it works!

And with generous options available for trading in or
upgrading your old system, this could be the perfectopportunity to turn up the heat on your research!

The new Cryostream Plus is as stable at SOD
Kelvin (22?°C) as it is at 80 Kelvin (-193°[).
giving you the flexibility to heat & cool your samp le

We look after our technology so you can lookafter yours I

at the touch of a button.

~~­-._...41

Maintaining the low nitrogen consumption , highstability and excellent performance for which the
Cryostream is renowned, the Plus simply offers that

OxfordCryosystems

little bit more: 100° C more to be precise.
North Amer,con OffKe
220 Wood Road · Braintree
MA 02184·1403 · USA
T. 1-866-0XCJIYO·B
781·843·5900
F. 781-843·5945
E. lnfoOOKfordCI)'OSYStems.com

www.

Hea(J Off1ce

3 Blenheim Office Park
Lowtr Road · Long HanboroughOxford · OX2 9 BLN · UK
T. +44 (0)1993 883488
F +44 (0)1993 883988
E. infoCOxfordC I)'osystems.co.uk

OxfordCryosystems.

comIPDS 2~
Single Crystal Diffractometer System- 340mm imaging plate5- Dynamic range > 1x1 0- Two circle goniometer, w from 0 - 180°, cp unlimited- 5 positions: 0°, 15°, 30°, 45°, 60° 28- 28 max. = 13 7o- Structure solutions for small molecules as well as for proteines- Electron density calculations- Investigations of powder samples- High- and low-temperature attachments
STOE & Cie GmbH P.O.Box 101302 D-64213 Darmstadt
Phone (+49) 6151 98870 Fax: (+49) 6151 988788
E-mail: stoe@stoe.com Homepage: http://www.stoe.com

The TOPAZ™System forprotein crystallization
Only one system addresses your needs fromcrysta llization setup to diffraction data. Every systemcomponent has been optimized around our provenchip technology for free interfa ce diffusion. Yo u'llappreciate th e very sma ll sample requirements(nanog ram quantities) and the integrated hardware
and software that stream line your projects. With Topazproducts, you can easily screen thousands of reagents
per d ay to identify promising co ndit ions, automatica lly
scan for and score crystall ization activity, and growlarge, high -quality crystals for diffraction stud ies. And
because the Topaz system has an open arch itecture,
yo u ca n interface it with third-party pi petting robotics
t o further supercharge your throughput. In so many
ways, we keep you moving toward your ultimate
goal-reliable structural data.

If you're ready for a complete solution-fromscreen to beam-visit www.fluidigm.com/TOPAZ
or call us today at 1-866-FLUIDLINE to learn more.

B?a TOPAZ'"PROTEIN CRYSTALL I ZATION BY FLUIDIGM

Frost & Sullivan
Scientific American 50

www.fluidigm.com

~
'1>-

!i

Ol

~

~

WindNJave~D~

g, Gas Station

Southern
Entrange~
Car Park

Towersso
5-7~~ower40--, so

Staff Quarters {SO)Tower 3Preside11t 's
Lodge

Jockey Club
Biotechnology
Research
Institute

GeotechnicalCentrifuge~~

Tunnel"<·'%.

"'~~-..,

Bus' \

CLP Power~~?'o<7q(Jilivers. ·~Towers1-2

Visitor Center& Staff Quarters

StationStaff Quarters(Houses 1·8& Apts 1-48)

\0

.,.,

~

~
~

r

-"

~~

"

~

~..._- Staff Quarters~- Blocks A • D

~~·

~

-~~~

'1>

' To Kowloon I
Sai Kung~<7....~

C

i~~l ~~~ ~ ~~ers15-19

Swimming

Port Shelter

CAMPUS MAP
THE HONG KONG UNIVERSITY OF SCIENCE AND TECHNOLOGY

N
A

B

e

5

Lecture Theaters

lifts

6

PiazzaEntrance~16 ) ( 17) ( 1820 ll 19

21

23)

122

Academic Building Directory
THE HONG KONG UNIVERSITY OF SCIENCE AND TECHNOLOGY

11·28

24

..
I 0

l

~

PL1
SUPERCONDUCTIVITY OF BORIDE AND CARBIDE SYSTEMS
Jun Akimitsu
Department of Physics , Aoyama-Gakuin University, 5-10-1 , Fuchinobe , Sagamihara,
Kanagawa , Japan, 229-8553 (jun@phys.aoyama .ac.jp)
After the discovery of MgBz, much attention has been paid to the boride andcarbide systems. In this conference , we mainly review the following themes.
(1) First is the present situation of the superconductivity of MgBz, which can be mainlyinterpreted in terms of BCS-type phonon mediate pairing .
In particular, we will focus on the relationship between the superconductivity and thechange of crystal structure in MgBz.
(2) We review our present status for the new superconductors including the boron andcarbon systems found in my laboratory.
We should emphasize here that we discovered the superconductivity at 18 K in YzC3,
although this material with a maximum Tc of 11.5 K has already investigated by
Krupka eta/ (J. Less-Common Met. 17 (1969) 91) (Fig .1). The crystal structure of
Y2C3 is body centered cubic (Pu 2C3-type) structure, and Y 3+ ions are onedimensionally aligned along [111] axis (Fig. 2). The lattice parameters , a, obtained in
our work exist between 0.818-0 .823 nm , and are smaller than those previously
reported (0.821 -0.825 nm).

Tc= \ SK
LO,-~~~~---'-~---"'-.-::--~~--,? -~ .0:.0·g. -3.0~ · -1.0
Tcmpcralurc [ K J

Fig . 1: Temperature dependence ofsusceptibility in Y2C3.

Fig. 2: Crystal structure of Y2C3. The
large circles show Y atoms and thesmall circles show C atoms .

PL2
STRUCTURES OF NOVEL SIGNALING PROTEINS SECRETED DURING
INVOLUTION AND INVOLVED IN APOPTOSIS
T. P. Singh
Department of Biophysics, All India Institute of Medical Sciences, New Delhi 110 029,
India. (tps@aiims.aiims.ac.in)

A novel class of 40 kDa glycoproteins (SPX-40) have been detected in the dry
secretions of non-lactating animals , culture supernatants of MG-63 human osteosarcoma
cell lines, cultures of human synovial cells and human cartilage cells. The increased
levels of similar protein have also been reported in certain types of breast and coloncancers. These proteins are implicated as protective signaling factor that determines
which cells are to survive during the processes of drastic tissue remodeling. Sequence
analysis and biochemical characterization have revealed a moderate similarity withchitinases and chitinase-like proteins but has indicated a completely altered combinationof the so called active site residues. The three-dimensional structures , functions , natureof ligands and mode of ligand binding of these proteins are not yet known . In order todevelop a detailed structure-function relationship , mechanism of ligand binding and theirprecise physiological role, we have determined structures of several of these proteins froma number of species. The detailed structure analyses has shown that these proteins
contain a classical Wa ) 8 barrel fold of triose phosphate isomerase (TIM) with an insertionof a small a/ ~ domain similar to that of chitinases. Although , the TIM barrel in these
proteins is very similar in shape to those of chitinases and chitinase-like proteins but it ispacked very differently indicating that these proteins might be involved in a different kindof recognition. Unlike chitinases and chitinase-proteins , these proteins are glycosylated .
The glycan moieties in these proteins contribute to the final folding particularly to theneighboring chains of the molecules. We speculate that these proteins may interact withcell surface receptors through protein-protein interactions as their carbohydrate binding
capabilities appear to be greatly impaired due to a tightly packed TIM barrel. It is probablethat the proteins of SPX-40 family might have originally evolved from chitinases , retainedsome sequence homologies and maintained similar structural framework but changed
selectively and critically to acquire new functions.

PLJ
FROM METAL STRING COMPLEXES TO METAL WIRES
Chih-Chieh Wang and Shie-Minq Penq
Department of Chemistry, National Taiwan University, Taipei , Taiwan
Tel No. : 886-2-23638305; Fa x No. : 886-2-83693765 (smpeng@ntu.edu.tw)
Owing to their fascinating bonding nature , the metal-metal (M-M) multiple bonds in
dinuclear metal complexes have been an interesting and vital research topic. During thepast decade , our seminal and systematic approaches on the all-syn oligo-(a-pyridyl)amido
ligands coordinated metal ions have successfully opened up a new chapter, extending thisterritory from dinuclear to linear oligonuclear metal complexes. Their unique features instructures and bonding characterization have been thoroughly investigated , which ,according to the M-M bonding strength , can be classified into two categories , namely theoligonickel(ll) complexes lacking an M-M bond and the oligochromium(ll) complexes witha strong M-M bonding formation. Depending on the specificity and number of metal ions ,structures and magnetic behaviors of the corresponding metal complexes are
systematically analyzed. Their potential application as a molecular metal wire is conveyedon the basis of the band structures calculated from hypothetical one-dimensional metal
strings. Moreover, self-assembled monolayers of n-alkanethiols are employed as a twodimensional matrix to isolate the metal string complexes , of which the scanning tunnelingmicroscopy (STM) image exhibits remarkable protrusion characteristics. For tricobalt andtri chromium complexes , the topographic STM images reveal that the protruding features
are , respectively, 0.3 nm and 0.6 nm higher than that of the trinickel complexes. The trendof increasing conductivity correlates well with their associated bond orders , and is also in
consistence with qualitative EHMO approaches.
Keyword: Metal String Complex, Molecular Metalwire , STM Spectroscopy
References
1
Lin S. Y. ; Chen I W .; Chen C. H.; Hsieh M. H.; Yeh C.Y.; LinT. W .; Chen Y. H.;
Peng S. M., J. Phys. Chern. B, 2004, 108, 959-964.

PL4
HIGH-THROUGHPUT PROTEIN CRYSTALLOGRAPY!sao Tanaka
Division of Biological Sciences, Graduate School of Science , Hokkaido University,
Sapporo , 060-081 0, Japan (tanaka@castor.sci.hokudai.ac.jp)
The genome-sequencing projects have determined a plenty of DNA sequences of
the genomes including entire human genomes or those of many important microbial
pathogens and useful organisms. The information of these sequences will benefit on avariety fields like medical science , agriculture and fundamental biology. In this postgenomic era , an enormous number of genes can be target for the research. The term
"structural genomics" is meant to be used for this situation in the field of protein
crystallography. Thus, the structural genomics requires the determination of protein
structures in a high-throughput manner with respect to sample preparation , crystallization ,diffraction data collection , and structure analysis.
Japanese structural genomics project has been established in fiscal .OO fJ under thename of "National Project on Protein Structural and Functional Analyses. " In this project,
our consortium "The Structural Genomics Consortium for research on Gene Expression
System (SGCGES)" aims to elucidate the structures and functions of the proteins that are
involved in gene expression . As one of the centers for the structural genomics project, wehave been developing an automatic system for high-throughput protein crystallography.
Since protein crystallization is influenced by a number of parameters, developmentof a small-scaled and automated crystallization method is necessary. We have beenworking on the development of a micro-array chip device for high throughput screening forprotein crystallization condition . In order to hold various precipitant solutions in gels, thehollow fibers arrayed on the chip are used. We have already determined polymerization
conditions of gels for almost all precipitants with wide range of pH conditions. The
prototype device has already been made.
For realizing the manual-intervention-free refinement, we have developed a Localcorrelation-coefficient-based Automatic Fitting for REfinement program (Lafire ). Thissystem consists of evaluation of existing model , automatic model modification , partial
model building , a graphic monitor system and an interface with existing refinement
programs. For the model modification , the backbone and side chains are independently
fitted to the electron density based on the correlation coefficient. In addition , the system
can build the regions (like loop regions) that are not able to be built by the automatic
programs like Solve/Resolve or ARP/wARP. In conjunction with the refinement programs
such as CNS and REFMAC , Lafire system has been successfully used to refine more thanten protein structures nearly in full-automatic manner.

PL5
CRYSTALLOGRAPHY WITHOUT CRYSTALS
Jianwei Miao ,a Keith 0 . Hodgson ,a• Tetsuya Ishikawa ,< Bart Johnson ,a Yoshiki Kohmura ,cand Yoshinori Nishinoc•Stanford Synchrotron Radiation Laboratory, Stanford Linear Accelerator Center, Stanford
University, Stanford , CA 94309-0210 , USA; "Department of Chemistry, Stanford
University, Stanford , CA 94305 , USA; <SPring-8/RIKEN , 1-1-1 , Kouto, Mikazuki , Sayo @Un,
Hyogo 679-5198 , Japan. (Miao@SLAC .Stanford .EDU)

When a coherent diffraction pattern is sampled at a spacing sufficiently finer thanthe Bragg peak frequency (i.e. the inverse of the sample size) , the phase information is inprinciple embedded inside the diffraction pattern , and can be directly retrieved by using an
iterative process . In combination of this oversampling phasing method with either coherent
X nays or electrons , the methodology of crystallography has recently been image nanocrystals , nanostructured materials and biological samples. In this talk, I will present the
principle of the oversampling method , discuss the first demonstration experiment, andillustrate some applications in nanoscience and biology.
References1
Miao , J. , Charalambous , P. , Kirz, K. and Sayre , D. (1999) Nature 400 , 342-345 .
2Miao J., Ishikawa T. , Johnson B., Anderson E.H., Lai B. and Hodgson K.O. (2002)
Phys. Rev. Lett. 89 , 088303(1-4).
3
Miao J. , Hodgson K.O., Ishikawa T, Larabell C.A. , LeGros M.A. and Nishino Y.
(2003) Proc. Nat/. Acad. Sci. USA 100, 110-112.

PL6
GRID-ENABLED HIGH THROUGHPUT CHEMICAL CRYSTALLOGRAPHY:A NEW OPPORTUNITY FOR STRUCTURAL CHEMISTRY
Michael B. Hursthouse
School of Chemistry and Combinatorial Centre of Excellence ,University of Southampton , UK. (mbh@soton.ac.uk)
The great sensitivity of current CCD X-ray detectors and the availability of highlyorganised structure determination software packages facilitate rapid X-ray structure
determination . The ever increasing demand from the synthesis labs for characterisation
support is proving to be a challenge , but this can also be viewed as an opportunity - toaccumulate structural knowledge at a pace greater than ever before. We are attempting tomeet this challenge and take the opportunity provided with both hands . We have put inplace procedures and equipment to provide a fully automated capability - from mounted
crystal to validated and archived structure data with minimal operator intervention. The
impact of this for structural science will be two-fold . Characterisation studies will become
even faster and inexpensive , providing further valuable support for chemical structureproperty studies , but with reduced operator overload . At the same time , the increasing
volume of available structural data will offer more scope for increasing our structureproperty knowledge .
However, high throughput data gathering then requires automated help in the sifting
and assessment processes . In our lab we are focussing some of our work on the latterarea. In the Comb-e-Chem project we are exploring the feasibility of an e-Science
approach to provide an integrated , GRID-enabled , Chemical Structure and Property
Environment, incorporating our high-throughput structure determination and someassociated high-throughput property measurement capability, with distributed structure
and property calculations and data-base mining . As an example of this approach , we aredeveloping new software to search for patterns in crystal structures , with a view to learning
more about crystal structure assembly, polymorphism and materials properties. At thesame time , we are investigating alternative ways to disseminate structural results,
recognising the fact that current publication strategies are unable to cope with current
output, let alone increasing future output. This presentation will report and review thestatus of all of these activities .

MS01-1

CRYSTAL STRUCTURE OF A HEMOLYTIC LECTIN CEL-111 FROMMARINE INVERTEBRATE CUCUMARIA ECH/NATA AT 1.7 A
RESOLUTION
Tatsuya Uchidaa, Tomomitsu Hatakeyamab, Takayuki Yamasaki b, Seiichiro Etob, Hajime
Sugawara<, Kurisu Genjia, Atsushi Nakagawaa, and Masami Kusunoki aalnstitute for Protein Research , Osaka University, 3-2 Yamadaoka , Suita Osaka 565-0871
Japan , bFaculty of Engineering , Nagasaki University, Bunkyo-machi 1-14, Nagasaki
852-8521 ,Japan, <Plant Science Center, RIKEN , 1-7-22 Suehiro-cho , Tsurumi-ku ,Yokohama City, Kanagawa 230-0045 , Japan(kusunoki@protei n.osaka-u .ac.jp)

The lectin CEL-111 derived from the marine invertebrate Holothuroidea Cucumariaechinata binds N-acetylgalactosamine or galactose-containing carbohydrates and causes
hemolysis or hemagglutination toward erythrocytes Ca 2•-dependently(1 ). Here we reportthe X-ray crystal structure of CEL-111 at 1.7 A resolution determined by single isomorphous
replacement with anomalous dispersion of a Pb derivative.
The protein consists of two b-trefoil domains on the N-terminal side and a C-terminal
domain , the latter of which is composed of two a helices and one large b-sheet. No
sequence homology was found for the C-terminal domain with other proteins . Five calcium
ions bound to five of the six 310 helices in the two b-trefoil domains. We assume that theseions are important for the structural integrity of CEL-111 and are directly involved in the
carbohydrate-binding , considering the structural and carbohydrate-binding similarity of thisprotein with other lectins , ricin B-chain and ebulin B-chain , with the same b-trefoil folds .
The b-sheet of the C-terminal domain has large regions of non-polar residues on thedomain surfaces and there are no disulfide bonds between the two b-trefoil domains andthe C-terminal domain . This strongly suggests together with our biochemical data thatupon binding of CEL-111 to the ery1hrocyte membrane , six to seven molecules of CEL-111
oligomerize by forming hydrophobic bonds between these molecules accompanied bysome conformational change, leading to hemolysis by forming ion-permeable pores in themembrane.
Reference
1
Kouzuma , Y. , Suzuki ,Y. , Nakano, M., Matsuyama, K., Tojo , S. , Kimura , M. ,Yamasaki , T. , Aoyagi , H. and Hatakeyama, T. (2003) J. Biochem. 134, 395-402 .

MS01-2
CRYSTAL STRUCTURES OF ARTOCARPIN-SUGAR COMPLEXES:
VARIATION IN THE LENGTH OF A LOOP AS A STRATEGY FOR
GENERATING LIGAND SPECIFICITY
M. Vijayan, Anand Srivastav, A. Surolia and A. Arockia Jeyaprakash
Molecular Biophysics Unit, Indian Institute of Science , Bangalore 560 012 , INDIA(mv@mbu .iisc.ernet.in) .
Lectins are carbohydrate binding proteins which exert their effects through specificrecognition of different sugar structures. They adopt widely different folds and quaternary
structures. For example, plant lectins , the most widely studied group in the family , exhibit
five different folds. One of them , the ~ -prism I fold , was first identified in jacalin[1], one of
the two lectins found in the seeds of jackfruit. The carbohydrate specificity of this lectinhas been thoroughly characterized[2] . The other lectin from jackfruit seeds , artocarpin ,also adopts ~ -prism I fold , although it has different carbohydrate specificities[3]. The
structures of the complexes of artocarpin with mannotriose and mannopentose reported
here show that the lectin has a deep-seated binding site formed by three loops. The
primary site made up of two loops forms hydrogen bonds with the sugars while the secondsite comprising the third loop has mainly van der Waals interactions with them . A detailed
comparison with the sugar complexes of heltuba , the only other mannose specific jacalinlike lectin with known three-dimensional structure in sugar-bound form , establishes therole of the sugar binding loop constituting the secondary site , in conferring different
specificities at the oligosaccharide level. This loop is four residues longer in artocarpin
than in heltuba , providing an instance where variation in loop length is used as a strategy
for generating carbohydrate specificity.
References
Sankaranarayanan , R. , Sekar, K. , Banerjee , R. , Sharma , V ., Surolia , A . & Vijayan ,1
M. (1996). Nat. Struct. Bioi. 3, 596-603.
Jeyaprakash, A. A. , Katiyar, S. , Swaminathan , C. P. , Sekar, K., Surolia , A . and2
Vijayan , M. (2003). J. Mol. Bioi. 332 , 217-228.
Pratap , J. V., Jeyaprakash , A . A. , Rani , P. G., Sekar, K. , Surolia , A. & Vijayan , M.
3
(2002). J. Mol. Bioi. 317 , 237-247 .

MS01-3
CRYSTAL STRUCTURE OF ZINC CONTAINING MONOFERRIC C-LOBE
OF BOVINE LACTOFERRIN AT 1.9 A RESOLUTION
Sujata Sharma , Talat Jabeen, Jayashankar Jasti , Janesh Kumar, Ashok K. Mohanty and
Tej P. Singh
Department of Biophysics , All India Institute of Medical Sciences , New Delhi-110 029 ,India (afrank2@hotmail.com)

Lactoferrin is an 80 kDa glycoprotein with two homologous lobes each containing asingle ferric ion. The purified samples of bovine lactoferrin were incubated with proteinase
K in 50 mM Tris-HCI , 5 mM CaCI 2 , pH 8.0 at a 100:1 ratio. The hydrolyzed productcontained N-Iobe , C-lobe and inactive proteinase K. The N- and C-lobes were purified tohomogeneity. The purified iron saturated samples of C-lobe were crystallized in 0.1 M
MES buffer, pH 6.5 containing 25 % v/v polyethylene glycol monomethyl ether 550 and
0.01 M zinc sulphate heptahydrate. The structure was determined by molecularreplacement and refined to an R-factor of 0.193 for all the data to 1.9 A resolution . The
final model comprises 2593 protein atoms (residues 342-676 and 681-685), 124
carbohydrate atoms (from 10 monosaccharide units , in three glycan chains) , 1 Fe 3•,
1C0 3 2• , 2 Zn 2• and 230 water molecules. The C-lobe folds in a similar manner as
observed for the C-lobes of other lactoferrins. The domain orientation is characterized by
six interdomain hydrogen bonds. The presence of two Zn 2• ions at sites other than theiron-binding site is a novel feature of this structure. This structure is also notable forextensive intermolecular hydrogen bonding in the crystals. This appears to be one of thebest packed crystal structures among the proteins of transferrin superfamily.

MS01-4

STRUCTURAL BASIS OF BACTERIAL LIPOPROTEIN TRANSPORT
Kazuki Takeda•, Hideyuki Miyatake•,
Naoko Yokotab, Shin-ichi .Matsuyamab, Hajime Tokudab, and Kunia Miki•.c"RIKEN Harima Institute/SPring-S , Hyogo, Japan , blnstitute of Molecular and Cellular
Biosciences , University of Tokyo , Tokyo , Japan , <Department of Chemistry, Graduate
School of Science , Kyoto University, Kyoto , Japan ,(miki@kuchem .kyoto-u .ac.jp)

Bacterial lipoproteins are anchored on the membranes with acyl chains attached tocysteine residue at the N-termius. In Gram-negative bacteria such as Escherichia coli, thetransport of hydrophobic lipoproteins from the inner membrane to the outer membrane
through the periplasm is mediated by Lol system . The Lol system is composed of aperiplasmic lipoprotein carrier LolA, a lipoprotein receptor LoiB , and the LoiCDE complex(ABC transporter) .
The structures of LolA and LoiB are surprisingly similar to each other andcharacterized by an unclosed P-barrel and three a-helices plugging the sheet, while thesequence identity between two proteins is about 8% [1] . For both proteins , the innersurface of the p-sheet and a-helices consist of hydrophobic residues . The cavities are
possible binding sites of the lipid moiety of the lipoprotein . In the LolA structure , the side
chain of Arg43 is oriented toward the interior of the molecule , and is hydrogen bonded tothe main chain of residues in the helices. The helices are expected to undergo opening
and closing upon the accommodation and release of lipoproteins , respectively. LoiA(R43L)
with a mutation at the residue in question can bind a lipoprotein but cannot transfer the
associated lipoprotein to LoiB [2], and the Lo1A(R43L)-Iipoprotein comple x accumulates in
the periplasm. In the structure of the mutant, three a-helices are highly disordered.
References
Takeda , K., Miyatake, H., Yokota , N., Matsuyama , S. , Tokuda , H. and Miki , K. (2003)
1
EMBO J. 22, 3199-3209 .
Miyamoto, A. , Matsuyama, S. and Tokuda , H. (2001) Biochem. Biophys. Res.
2
Commun. 287 , 1125-1128.

MS01-5
CRYSTAL STRUCTURE OF LEUA, AN ESSENTIAL BIOSYNTHETICENZYME FROM MYCOBACTERIUM TUBERCULOSIS
Edward N. Baker a Nayden Koon ,• and Christopher J. Squire••School of Biological Sciences , University of Auckland , Private Bag 92019 , Auckland , New
Zealand (ted .baker@auckland .ac.nz).

Mycobacterium tuberculosis , the cause of TB , is responsible for more deaths
worldwide than any other infectious agent. With the rise of multi-drug resistance and thelong treatment regimes currently required , there is an urgent need for the development of
new therapeutic drugs . As part of a structural genomics initiative focused on M.
tuberculosis, we have targeted enzymes from the amino acid biosynthesis pathways.
LeuA (a -isopropylmalate synthase) is a dimeric (2 x 70 kDa) enzyme that catalyses
the first committed step in the biosynthesis of the amino acid leucine , and has beenshown to be essential for the viability of the organism . Since there is no equivalent
enzyme in humans, LeuA is a potential drug target. The gene encoding LeuA in M.
tuberculosis (Rv371 0) was cloned and the protein expressed in E. coli, purified andcrystallized . The selenomethionine (SeMet)-substituted protein was also prepared , purified
and crystallized , seeding with the native crystals [1]. The structure was then solved by
MAD methods , using synchrotron data collected at 3 wavelengths and refined at 2.0 A
resolution in complex with its substrate , a-ketoisovalerate (a-KIV). The final R-factor was
0.169 (R 1,•• 0.197).
The structure [2] reveals a tightly-associated , domain-swapped dimer in whi ch eachmonomer comprises an (a/!3)8 TIM barrel catalytic domain, a flexible linker domain and a
regulatory domain of novel fold . Mutational data indicate the latter as the site for leucine
feedback inh ibition of activity. Domain swapping enables the linker domain of one
monomer to sit over the catalytic domain of the other, inserting residues into the active sitethat may be important in catalysis . The a -KIV substrate binds to an active site zinc ion ,adjacent to a cavity that can accommodate acetyi-CoA. Sequence and structuralsimilarities point to a catalytic mechanism similar to that of malate synthase and an
evolutionary relationship with an aldolase that catalyses the reverse reaction on a similar
substrate.
The structure also identifies possible opportunities for inhibitor design aimed at thedevelopment of new anti-TB drugs .
References
1
Koon , N., Squire , C. J . and Baker, E. N. (2004). Acta Cryst. sect. 0 , in press .
2
Koon , N ., Squire , C . J . and Baker, E. N. (2004). Proc. Nat/. Acad. Sci. USA ,submitted .

MS02-1SYCHROTRON RADIATION AND SAD PHASING IN PROTEIN
CRYSTALLOGRAPHY
Hai-fu Fan and Yuan-xin Gu
Institute of Physics , Chinese Academy of Sciences, Beijing 100080, China(fan@mail .iphy.ac.cn)

Over the past decade , advances in synchrotron technology and genetic engineering
led to the great success of MAD (multiple anomalous diffraction) phasing in protein
crystallography. However, MAD phasing may encounter problems when crystals of thesample protein are sensitive to radiation or the selena-methionine substitution is not
successful .
Recent advances in synchrotron technology and methods of introducing anomalous
scatterers open new possibilities for SAD (single-wavelength anomalous diffraction)
phasing . In comparison with MAD, SAD phasing has the following advantages: (1) the
exposure time is shorter, (2) the sample preparation is easier, (3 ) the intensity-scaling
process is simpler and (4) there is no need to fine tune the wavelength to the peak andinflection point of the anomalous scattering curve , data collection can be performed at awavelength within a wide range next to the absorption edge on the high-energy side .
A drawback in SAD phasing is the intrinsic phase ambiguity. Up until recently the initial
SAD phases have been derived mostly from the combination of the Sim distribution andthe experimental bimodal phase distribution from SAD data. Recent study [1) on typicalcases has shown that by incorporating direct methods of breaking enantiomorphous
phase ambiguity [2 , 3, 4], much better initial phases can be derived leading toconsiderably improved quality of the resultant electron density maps .
The direct-method SAD phasing procedure has been further improved and successfully
tested with synchrotron-radiation SAD data from a number of proteins. Anomalous
scatterers include selenium , xenon , bromine , copper and sulfur. Bijvoet ratios <t:. F>/<F>
are ranging from 7.0 to 0.6 . Diffraction data were kindly provided by Dr. Z. Dauter and Dr.
M. S. Weiss.
References
1
J. W. Wang , J. R. Chen , Y. X. Gu , C. D. Zh eng , F. Jiang, H. F. Fan , T. C. Terwilliger& Q. Hao , (2004). "SAD phasing by combination of direct methods with the
SOLVE/RESOLVE procedure". (Submitted for publication)
2
Fan Hai-fu & Gu Yuan-xin , Acta Cryst. A41 , 280-284 (1985) . "Combining direct
methods with isomorphous replacement or anomalous scattering data Ill. The
incorporation of partial structure information".
3
Fan Hai-fu , Hao Quan , Gu Yuan-xin , Qian Jin-zi , Zheng Chao-de & Hengming Ke ,Acta Cryst. A46 , 935-939 (1990). "Combining direct methods with isomorphous
replacement or anomalous scattering data VII. Ab-in itio phasing of the OAS datafrom a small protein ".
4
Q. Hao, Y .X. Gu , C.D. Zheng & H.F. Fan , J. Appl. Cryst. 33 , 980-981 (2000).
"OASIS - a computer program for breaking the phase ambiguity in one-wavelength
anomalous scattering or single isomorphous substitution (replacement) data".

MS02-2
HIGH-RESOLUTION XRD AND IMAGING POLYCRYSTALLINEMICROSTRUCTURES BY MOVING AREA DETECTOR METHOD WITH
HIGH-ENERGY SYNCHROTRON RADIATION
L. Wcislak ," H.J. Bunge," H. Klein ,< U. Garbe ," and J.R. Schneider"•Department of Physics and Astronomy at the University of Denver, Colorado 80208, USA;
"Department of Physics and Ph ysical Technologies , Technical University of Clausthal , Germany;<Department of Crystallography, University of Gottingen , D - 37077 Gottingen , Germany;"Hamburg Synchrotron Radiation Laboratory (HASYLAB) at Deutsches Elektronen Synchrotron(DESY) , D- 22603 Hamburg , Germany(wcis lak@boulder.nist.gov)

The crysta lline solid materials are usually polycrystalline and often also polyphase. They
consists of ve ry many, small crystalline units ( crystallites ) separated from each other by grainboundaries. The polycrystalline aggregate is characterized by the locations and orientations of al l
crysta llites, the orientation stereology. The majority of physical properties of single crysta ls, e.g.
mechanical (elasticity-plasticity), magnetic, electric, thermal , optical, acoustic properties areanisotropic. Hence, the physical properties of polycrystalline solid materials depend both on theanisotropy of individual crysta llites and their orientation distribution ( texture ) in the material. This
holds for all classes of crysta lline materials including metals, their all oys, ceramics , glasses, po lymers
and composites but also geological and biological materials. Nano- and microstructure determination istherefore necessary in order to understand and shape the physical properties of polycrystalline
materials of any kind . Thi s is particularly the case for materials used in advanced technologies(superconductivity, magnetism , electronics, optics , and photonics) where optimum property va lues ofthe material must be guaranteed.
The classical technique to study polycrystalline structures is by x-ray diffraction. Later thesame technique has become avai lable with neutrons and electrons. The main differences between
these radiations are their penetration depths, orientation or location resolutions and more practicalaspect; the beam intensity and source brilliance . The large penetration power in mm to em range(even for medium and large Z number elements) of high-energy synchrotron x-rays photons in matter
opens quite new possibilities of structural analyses in polycrystalline materials. It becomes possible tomeasure non-destructively the fundamental structural parameters of matter including the size, shapeand arangement of grains of seve ral phases as well as crysta llographic orientations of the crystallites ineach phase. Thi s allows the quantitative determination (rea l-time imaging and I or mapping) of nano-,meso-, and microstructures (layers, interfaces, coatings, textures , strains, size , stereology, anisotropy)
and the prediction , shaping , controlling the macroscopic physical properties of the material such as
deformability, fatigue strength , and variou s electrical , magnetic, optical properties.
At HASYLAB , hard x-rays up to 100 keV (photon wavelength - 0.1 A) are available at thestorage rings DORIS and PETRA . This radiation has penetration depths up to several mm or even em ,in most materials , comparable with neutrons. It has small beam divergences in the range of somemilliradians and extremely high intensities so that sma ll beam spots in the range of iJm can be used .
The BW5 diffractometer is equipped with a 4-circle goniometer, an on- line image plate detector for theregistration of diffraction images and additionally with a Bragg-angle slit system to se lect a sector of a
In order to attain highest measuringchosen Debye-Scherrer cone to reach the area detector.
resolution , conventiona l 'step-scan' technique was replaced by a continuous 'sweeping' techniqueusing a moving area detector mode. The results obtained give quite new insight into the microstru cturedevelopment in crysta lline materials, processes kinetics , phenomena dynamics (including phasetransitions , time , pressu re and I or temperatu re dependent structura l changes in advanced materials;
polymers, shape memory all oys, ceramics, glasses, composites) and the underlying physicalprocesses.

MS02-3
X-RAY SCATTERING STUDY OF SELF-ASSEMBLED QUANTUM DOTS
C.-H . Hsu•, Yuri P. Stetsko•, Mau-Tsu Tang•, Hsin-Yi Lee•. Yung-Wei Hsieh•, Chih-Mon
Huang•, W. -S Liub, N.T. Yehb, J .-1. Chyib, and K.S. Liang••Research Division , National Synchrotron Radiation Research Center, Hsinchu , Taiwan ;bDepartment of Electrical Engineering , National Central University, Chung-Li , Taiwan(chsu@nsrrc.org .tw)
The size , shape , strain distribution , compositional profile and spatial distribution are
the critical factors determining the electronic level and thus the opto-electronic propertiesof semiconductor quantum dots. For these mesoscopic objects , surface segregation .
interface diffusion and various kinetic effects make their formation mechanism very
complicated . In fact , the structure and the formation mechanism of these self-assembled
nano-structures are still not well understood. In this work, we applied grazing incidence Xray scattering methods including reciprocal space map and small angle X-ray scattering tostudy the strain field , compositional profile. shape and spatial distribution of the lnGaAsquantum dots grown by molecular-beam epitaxy[1] . In addition , the application of theresonant X-ray scattering technique greatly enhances the compositional sensitivity andallows us to accurately determine the In distribution within the dots with high resolution .
References
C.-H . Hsu. H.-Y. Lee , Y.-W. Hsieh, Y. P. Stetsko , N.T. Yeh , J .-1. Chyi , D. Y. Noh ,1
M.-T. Tang , and K.S. Liang (2003) Physica B 336, 98-102.

MS02-4
NOVEL TECHNIQUE OF NON-RESONANT X-RAY MAGNETICSCATTERING
Hiroyuki Ohsumi•, Masaki Takata• and Hiroyoshi Suematsu••Japan Synchrotron Radiation Research Institute, 679-5198 , Japan(ohsumi@spring8.or.jp)

Non-resonant X-ray magnetic scattering (NRXMS) utilizing synchrotron radiation isa promising way of magnetic structural investigations especially on microcrystals and/or
thin films. Although a highly brilliant X-ray beam is indispensable , NRXMS provides
extremely useful information on ratio of orbital (L) and spin (S) magnetic moment inaddition to the magnetic structure factor [1] . In order to utilize the advantage of NRXMS ,the polarization of the scattered beam needs to be analyzed in detail. In the conventionalpolarization analysis technique , the polarization of the scattered beam is determined by
the use of an analyzer crystal with scattering angle of approximately 90 degrees. Then ,the scattered beam intensity is extremely reduced by the diffraction process on theanalyzer crystal. In order to overcome the intensity loss by the analyzer crystal , we havedeveloped a novel polarization analysis technique without using an analyzer crystal.
In our novel technique , the polarization analysis of the scattered beam is attainedby measuring the dependence of its intensity on an inclination angle of the scattering
plane [2]. Charge and magnetic reflections can be easily distinguished by the novel
technique . It is noteworthy that quantitative information on the orbital magnetic moment
still remains available. We have performed NRXMS experiments on the rare earth metal
dysprosium and holmium . The experiments have been carried out at the BL46XU
undulator beamline at SPring-8. With our novel technique, we have succeeded in
distinguishing magnetic satellite reflections from charge ones induced by lattice
modulation. We are investigating the subtle feature of magnetic scattering with our novel
NRXMS technique. Not only the methodology but also the results of this investigation will
be presented .
References
M. Blume and Doon Gibbs , Phys . Rev. B 37 (1988) 1779.
1
2
H. Ohsumi , M. Mizumaki , S. Kimura , M. Takata and H. Suematsu , Physica B 345(2004) 258 .

MS02-5
OBSERVATION OF TRANSIENT ROTATOR PHASE OF N-HEXADECANE
IN EMULSIFIED DROPLETS BY SMALL- AND WIDE-ANGLE X-RAY
SCATTERING
Y. Shinohara ,a N. Kawasaki," S. Ueno ,b I. Kobayashi ,c M. Nakajima ,c andY. Amemiya••Department of Advanced Materials, The University of Tokyo, Kashiwa , Chiba , Japan ;bFaculity of Applied Biological Science , Hiroshima University, Higashi-Hiroshima ,Hiroshima , Japan ; cNational Food Institute, Tsukuba , lbaraki , Japan(amemiya@k.u-tokyo.ac.jp)

Normal alkanes (n-alkanes) are among the most basic components of soft
materials such as surfactants , lipids and liquid crystals. It is, therefore , important to study
the crystallization kinetics of n-alkanes for further understanding of soft materials . In spiteof a large number of studies , precise mechanism of crystallization of n-alkanes, especiallyn-Hexadecane (C 16), has not been clarified yet. Although Sirota and Herhold firstobserved the transient-rotator phase which lacks long-range order in the rotational degreeof freedom of the molecules about their long axis, of C16 in bulk sample in 1999 [1] , it was
detected only for 9 out of 85 measurements and not detected by other experiments.
Simultaneous measurement of small- and wide-angle X-ray scattering(SAXS/WAXS) is a powerful tool for studying structures of wide-range scales at once. In
the present study, we have performed time-resolved two-dimensional SAXS/WAXS
measurements of C16 during crystallization to observe the behaviour of initial stage ofcrystallization . The droplets of C16 of an oil-in-water (0/W) emulsion prepared by
microchannel method [2] were used as a sample. The experiments were performed at
BL44XU , SPring-S (Hyogo , Japan) and BL-15A , Photon Factory (Tsukuba , Japan). At
BL44XU , Imaging Plate (IP) was used as an X-ray detector and precise structure of C16
near its freezing point was studied . At BL-15A, we used an X-ray CCD detector coupledwith Image Intensifier and performed time-resolved SAXS/WAXS measurements together
with Differential Scanning Calorimetry (DSC) .
It has been shown that C16 in emulsion droplets also nucleates via a rotator phaseand its structure is the same as that observed at bulk sample. The rotator phase was
detected in every measurement. It has also been shown that the addition of impurities(lypophilic surfactant) to the emulsion increases the scattering intensity from the rotatorphase , which indicates the surface of emulsion plays a key role in the nucleation of therotator phase. Further study is needed to reveal the origin of the rotator phase in emulsion
droplets.
References1
Sirota , E. B. , Herhold , A. B. , (1999) Science 14, 529-532.
2
Kawakatsu , T., Kikuchi , U., and Nakajima, M., (1997) J. Am. Oil. Chem. Soc, 74,317

MS03-1

VERY SHORT OACID-H···OWATER HYDROGEN BOND STUDY BY VARIABLE
TEMPERATURE NEUTRON DIFFRACTION
Ashwini Nangia ,a P. Vishweshwar,a John A. Cowan ,b Sax A. Mason ,b Horst Puschmann ,cand Judith A. K. Howardc
aDepartment of Chemistry , University of Hyderabad , Hyderabad 500 046 , India(ansc@uohyd.ernet.in); blnstitut Laue-Langevin , BP 156, 38042 Grenoble Cedex 9,France ; cDepartment of Chemistry, University of Durham , South Road , Durham DH1 3LE ,UK
Very short 0-H· ··O hydrogen bonds (0···0 2.2-2.5 A) are often found in
intramolecular situations when the H-bond is stabilized by negative or positive charge , orby resonance assistance. We present the shortest intennolecular Oac;d-H···Owater H-bond to
be characterized by variable temperature neutron diffraction in the crystal structure of
2,3,5,6-pyrazinetetracarboxylic acid dihydrate 1 (0···0 2.4751 (11 ), 2.4765(1 0) , 2.4807(12)and 2.4906(16) A at 20 , 100, 200 and 293 K) [1] . The COOH donor is activated by rrcooperative assistance and the water acceptor ability is enhanced by polarization
assistance (a-cooperative) in the VSHB. There is no proton migration in 1 between 20-293
K in the neutral H-bond array I. The proton resides in an unsymmetrical double wellpotential with EH8 "' 16 kcal mol-' . The very short H-bond has quasi-covalent character
calculated from valence bond order function (sH 0 = 0.27-0.30) , and 0-H 115 of solid 1 isred shifted in the IR spectrum (1200-1400 em-' ). Shortening of the Oadd-H·· ·Owaterhydrogen bond by synergistic rr- and a-cooperativity in finite , neutral array I, named assynthon-assisted hydrogen bonding (SAHB) [2], adds new insight to the current thinking
that very short hydrogen bonds belong to three fundamental types: (+)CAHB , (-)CAHB ,and RAHB. Short 0-H···O H-bonds in pyrazine di- and tricarboxylic acids will also be
discussed .
R

0~0HO"-..,/I R

I

~

II
Q
PAHB
/

·H,
~R
O ·· H- 0

1'/.{)

Ocooperative

0~

VSHB (0 ..0 2.40-2 .50 A)

I

Crystal structure at 20 K
References

1
2

For X-ray study, see P. Vishweshwar, A. Nangia and V. M. Lynch. (2001) Chern.
Commun. 179-180.
Manuscript in preparation .

MS03-2
TOPOLOGY AND SUBMOLECULAR PARTITIONING OF BIOLOGICALLYACTIVE MOLECULES BASED ON EXPERIMENTAL CHARGE DENSITYDETERMINATIONS AT 100 K AND AT 20 K
Peter Luger, Marc Messerschmidt, Stephan Scheins and Birger Dittrich ,Institute for Chemistry/Crystallography, Free University Berlin , Takustr. 6 , 14195 Berlin ,Germany, (luger@chemie .fu-berlin.de)
The substantial progress charge density work has seen in the last decade rests on threepillars:
Advances in experimental techniques: High brilliant x-ray sources and area detection , allowing
to collect high resolution data sets in a reasonable time[1].
Methodological developments , e.g . Bader's AIM theory, making use of the charge density for aproper definition of atomic and bonding regions[2) .
Development and distribution of sophisticated computer programs for refinement , analysis andvisualization of experimental charge densities.
Through these developments which happened almost at the same time charge density
studies on an entire class of compounds[3) or on larger molecules became feasible .
We will give a brief introduction in our experimental experiences with data collections usingsynchrotron and conventional MoK" radiation . Moreover we will report on a recently improved ultra
low temperature setup that allows data collections down to 15-20 K[4).
As further examples some of our recent results will be discussed :In a comparative study we investigated intra- and intermolecular topological properties of anumber of amino acids and oligopeptides focused on the transferability of submolecularproperties.
Preliminary results of 20 K charge density studies of the oligocyclic strychnine , morphine andcodeine molecules will be reported .
On a number of pharmaceutically active compounds (an antithrombotic agent and an active
and inactive penicillin derivative) preferred sites of intermolecular interactions were identified
from the reactive surface and the electrostatic potential.
Finally we will present some concepts to derive charge density distributions and related
properties of macromolecules even from low order data making use of the recently introduced"invariom" library[5).
References
1
T. Koritsanszky, R. Flaig , D. Zobel, H.-G . Krane , W. Morgenroth , P. Luger, Science 279(1998) , 356 .
R. F. W. Bader, Atoms in Molecules , Clarendon , Oxford , 1994.
2
R. Flaig , T. Koritsanszky, B. Dittrich , A. Wagner, P. Luger, J. Am. Chern. Soc. 124 (2002),
3
3407.
4
M. Messerschmidt, M. Meyer, P. Luger, J. Appl. Cryst. 36 (2003), 1452-1454.
5
B. Dittrich , T. Koritsanszky, P. Luger, Angew. Chern. 116 (2004), in press.

The investigations were funded by various grants of the Deutsche Forschungsgemeinschaft DFG (grant no . Lu 222/18-3, Lu 222/21-1 , Lu 222/22-1-3 , Lu 222/24-1 -3, Lu
222/27-1 ).

MS03-3
STUDIES ON THE VARIANT COORDINATION MODES OF
ARENESULFONATE
Jiwen Cai and Jin-Sen Zhou
School of Chemistry and Chemical Engineering , Sun Yat-Sen University, Guangzhou
510275 , P. R. China (puscjw@zsu .edu.cn)

Recent progress in solid state coordination and structure chemistry of arenesulfonates
will be outlined. Due to the weak coordination strength , in comparison with other organic
acidato ions such as carboxylate and phosphonate , most of the meta l sulfonates obtained
from aqueous solution are water-coordinated metal sulfonate salts . However, we havebeen found that, by employing arenedisulfonates or by using amines as auxiliary ligands ,stable sulfonate-coordinated metal complexes , with variant dimensionalities , could beobtained from aqueous solution. The sulfonate groups show variant coordination modes
tuning by the auxiliary ligands and thus result in sulfonate-coordinated compounds withrich solid-state structural chemistry. Most of the alkali and alkali earth metal form 3dimentional coordination structures with 1,5-naphthalenedisulfonate . While among thedivalent transition metals we investigated , including NF•, Cu 2•, Co 2• , Zn 2• and Cd 2•, Cd 2•
shows the strongest coordination strength toward the sulfonate groups. Furthermore ,layered sulfonate- and water-coordinated Cd 2• complexes can absorb , reversibly at room
conditions , up to 5 equiv of amine-vapors and form stable crystalline materials, whi chcould be further grown into single crystals in situ.
We thank the financial support from the National Natural Science Foundation of China(Grand No. 20271 053).
References
1
Chen , C.-H ., Cai ,J., Liao , C.-Z. , Feng , X.-L. , Chen , X.-M . and Ng, S.-W. (2002)
lnorg. Chern , 41 , 4967 ;
2Cai , J. , Chen , C.-H. , Feng , X.-L. ,Liao , C.-Z . and Chen , X.-M. (2001) J. Chern. Soc.,
Dalton Trans. , 2370 ;3Cai , J. , Chen , C.-H. , Liao , C.-Z ., Yao , J.-H ., Hu, X.-P. and Chen , X.-M. (2001) J.
Chern. Soc., Dalton Trans., 1137;
4
Cai , J. , Zhou , J.-S . and Lin , M.-L.(2003) J. Mater Chern. , 13, 1806.
5
Cote , A. P. and Shimizu , G. K. H.(2003) Coord. Chern. Rew. 245 , 49 .

MS03-4
NTHU-2: A HIGHLY POROUS ORGANO-METALLOPHOSPHATESTRUCTURE DETERMINED FROM A NON-MEROHEDRAL TWIN
Yueh-Chun Liao , Fen-Ling Liao and Sue-Lein Wang
Department of Chemistry, National Tsing Hua University, Hsinchu 300 , Taiwan(slwang@mx.nthu .edu.tw).

Transparent brown crystals of NTHU-2 were prepared from the reaction mixture of
ZnCI 2 , C,3 N2 H,. (tmdp), p-C 6 H4 (COOH) 2 (terephthalic acid or BDC) , H3 P0 4 , ethylene glycoland Hp under a mild solvothermal condiation . They grew in clumps wherein the swordshaped lamellar crystals were entirely twinned . The conclusive structure was solved andrefined using the intensity data collected from a lamellar twin. The 30 anionic framework is
built up with neutral ZnHP0 4 layers and BDC anions acting as pillars. In the inorganic
layers , each Zn0 4 tetrahedron shares three oxygen atoms with HP0 4 tetrahedra , resulting
in three-connected two-dimensional nets [4 .82]. Being the first open-frameowrk of metal
carboxylatophosphate, NTHU-2 has large pores with the least diameter of 1.36 nm ; N2
sorption isotherms reveal both micro- and meso-porosity. This new material isphotoluminescent and disassemble in water wherein the discharged organic fragments
form mixed crystals . Crystal data for NTHU-2: Zn 2 Pp, 2 N2C2 ,H22 , monoclinic, space group
P2 ,fc; a = 27 .581 (4 ), b = 9.111 (1 ), c = 9.979(2) A, ~ .= 92 .213(3) 0 , V = 2505 .9(7) A3 , and Z=4.

Reference
Liao , Y.C. , Liao, F.L. , Chang , W.K. , Wang , S.L. "A Zeolitic Organo1
Metallophosphate Hybrid Material with Bimodal Porosity", J. Amer. Chem. Soc,
2004, 126, 1320-1321 .

MS03-5
REACTION CAVITY GEOMETRY DEPENDENT CONFORMATIONAL
TRANSFORAMTION ON MIXED CRYSTAL FORMATIONChampika Vithana ,a Hidehiro Uekusa ,b Akiko Sekine,b and Yuji Ohahshib• Department of Chemistry, University of Peradeniya , P 0 Box 25 , Peradeniya , Sri Lanka ;DOepartment of Chemistry, Tokyo Institute of Technology, 0-okayama , Meguro-ku , Tokyo
152-8551 , Japan (champikav@pdn.ac.lk)

Mixed crystal formation is considered as one of the crystal engineering strategies todesign new materials. Upon mixed crystal formation , only in very few instances, guest
component adopted the molecular and crystal structures of the host component and thiswas suggested as Structural Mimicry.[1]However, still the information available about the factors governing thisphenomenon is enigmatic. Hence four mixed crystals were formed between selected pairsof cobaloxime complexes consisting of flexible cyanoalkyl groups and rigid cobaloxime
moieties to investigate the factors causing this conformational transformation.
Molecular conformations of the two components in each mixed crystal and reaction
cavities drawn for the flexible parts clearly revealed that shape and size of the void spacearound the flexible part of the guest compound are the main driving forces for theconformational change on mixed crystal formation . In order to minimize the lattice
distortions in host crystal lattice, when guest molecules are incorporated , the flexible partof the guest obtains a conformation , which is the most suitable for the surroundings .
References1
Sacconi , L., Ciampolini , M. and Speroni , G. P. (1965) J. Am. Chern. Soc., 87 ,3102-3106 ; Theocharis , C. R. , Desiraju , G. R. and Jones , W . (1984) J. Am.
Chern. Soc., 106, 3606-3609 .

MS04-1

CRYSTAL STRUCTURE OF BACTERIAL MULTIDRUG EFFLUXTRANSPORTER AcrB
Satoshi Murakamia.b.d.e, Takashi Matsumoto•·•, Ryosuke Nakashima•, Eiki Yamashitac, andAkihito Yamaguchi•.b.e•Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka , lbaraki ,Osaka 567-0047 , Japan , bFaculty of Pharmaceutical Science , Osaka University, 1-6
Yamadaoka , Suita , Osaka 565-0871 , Japan, clnstitute for Protein Research , Osaka
University,3-2 Yamadaoka , Suita , Osaka 565-0871 , Japan, d RESTO , •CREST, Japan
Science and Technology Agency. (mura@sanken.osaka-u.ac.jp)

The emergence of bacterial multidrug resistance is an increasing problem in thetreatment of infectious diseases. AcrB and its homologues are the major multidrug
exporters in gram-negative bacteria , which confer intrinsic drug tolerance and multidrug
resistance when they are overproduced . AcrB exports wide range of toxic compounds
directly out of the cells bypassing periplasm driven by proton motive force. It cooperates
with membrane fusion protein AcrA and outer membrane channel ToiC. We havedetermined the crystal structure of AcrB at 3.5 A resolution [1]. This structure is not only
the first structure of a multidrug transporter, but also the first atomic structure of amembrane transporter that couples with proton translocation across the membrane .
Three AcrB protomers are organized as a homotrimer. Each protomer is composedof a 50 A-thick transmembrane region and a 70 A-protruding hydrophilic headpiece. The
transmembrane domain of each protomer contains 12 alpha-helices. In the lower part ofheadpiece , there exists a central pore composed of three alpha-helices. The conformationof the top of AcrB is consistent with the possibility of a direct interaction between AcrB and
ToiC . The transport mechanism and the whole construction of AcrA-AcrB-ToiC system will
be discussed.

References
Murakami ,S ., Nakashima,R. , Yamashita ,E. and Yamaguchi , A . (2002) Nature 419 ,1
587-593.

MS04-2
CRYSTAL STRUCTURE OF CYTOCHROME B 6 FCOMPLEX OFOXYGENIC PHOTOSYNTHESISGenji Kurisu ,a.b.c Huamin Zhang ,b Janet L. Smith ,b and William A. Cramerb•Institute for Protein Research , Osaka University, Suita , Osaka 565-0871 , Japan ;bQepartment of Biological Sciences, Purdue University, West Lafayette , IN 47907-2054
USA; <current address, Department of Life Sciences , Graduate School of Arts andSciences , The University of Tokyo , Komaba , Meguro-ku , Tokyo 153-8902, Japan(kurisu@protein .osaka-u .ac.jp ).
The cytochrome bsf complex provides the electronic connection between thephotosystem I (PSI) and photosystem II (PSI I) reaction centers of oxygenic photosynthesis
and generates a transmembrane electrochemical proton gradient for adenosine
triphosphate synthesis. Three-dimensional structures exist for PSI at 2.5 A and PSII at 3.7
A . The cytochrome bsf complex from the thermophilic cyanobacterium , M. /aminosus , hasbeen crystallized [1] and its structure was solved to a resolution of 3. 0 A resolution [2].
thus completing the structural description of the architecture of the electron transport chainof oxygenic photosynthesis . The crystal structure shows that two monomers of an eightsubunit dimeric complex surrounded a large inter-monomer cavity stabilized by lipids. The
cavity reveals the quinone exchange pathway through a plastoquinone near a uniqueheme on the electronegative side of the cavity, and a quinone analogue inhibitor on theelectropositive side that occludes a portal to redox centers , such as the [2Fe-2S] cluster
and bP-heme. Based on the structural arrangement of redox centers , It is proposed thatthe mechanism of electron transfer from plastoquinol to the cytochrome f heme involves asmall amplitude tethered rotation of the [2Fe-2S] protein about its hinge and the possible
electron transfer around the unique heme for FSerredoxin dependent cyclic electrontransport .

Fig . Schematic View of the Cytochrome bsf complex
References1
Zhang , H., Kurisu , G., Smith , J.L. and Cramer, W .A. (2003) Proc. Nat/. Acad. Sci.
USA. 100 , 5160-5163.
2
Kurisu , G., Zhang , H., Smith , J.L. and Cramer, W.A. (2003) Science 302 ,
1009-1014.

MS04-3
THE ATOMIC STRUCTURE OF RICE DWARF VIRUS REVELAS THE
SELF-ASSEMBLY MECHANISM OF COMPONENT PROTEINS
Atsushi Nakagawa•, Naoyuki Miyazaki•, Junichiro Taka•, Hisashi Naitow•, Akira Ogawa•,
Zui Fujimotob, Hiroshi Mizunob, Kyoji Hagiwarac, Takahiko Higashic, Yasuo Watanabec,
Toshihiro Omurac, R. Holland Chengd, and Tomitake Tsukihara••Institute for Protein Research , Osaka University, Suita , Osaka 565-0871 Japan; b National
Institute of Agrobiological Sciences , Tsukuba , lbaraki 305-8602 Japan ; cNational
Agricultural Research Center, Tsukuba , lbaraki 305-8666 , Japan; dQepartment of
Biosciences at Novum, Karolinska Institute, Halsovagen 7, 14157 Huddinge, Sweden(atsushi@protein .osaka-u.ac.jp)

Rice dwarf virus (RDV) , the causal agent of rice dwarf disease , is a member of thegenus Phytoreovirus in the family Reoviridae. RDV is a double-shelled virus with amolecular mass of approximately 70 million Dalton.
This virus is widely prevalent and it is one of the viruses that cause the mosteconomic-damage in many Asian countries . The atomic structure of RDV was determinedat 3.5 A resolution by X-ray crystallography [1] . The double-shelled structure consists of
two different proteins, the core protein P3 and the outer-shell protein P8. The atomic
structure shows structural and electrostatic complementarities between both homologous(P3-P3 and P8-P8) and heterologous (P3-P8) interactions , as well as overall
conformational changes found in P3-P3 dimer caused by the insertion of amino-terminal
loop regions of one of the P3 protein into the other.
The P3 proteins with serial amino-terminal deletions, expressed in a baculovirus
system , formed particles with gradually decreasing stability. The capacity for selfassembly disappeared when 52 of the amino-terminal amino acids had been deleted.
These results demonstrated that insertion of the amino-terminal arm of one P3 intoanother appear to play an important role to stabilize the core particles [2].
These interactions suggest how the 900 protein components are built into a higherordered virus core structure .

References
Nakagawa, A. , Miyazaki , N, Taka , J. , Naitow, H. , Ogawa , A. , Fujimoto , Z ., Mizuno ,1
H., Higashi , T., Watanabe , Y., Omura , T., Cheng , R. H. and Tsukihara T . (2003)
Structure 11 , 1227-1238.
Hagiwara , Higashi , T. , Miyazaki , N., Naitow, H, Cheng , R. H., Nakagawa , A. , Mizuno,
2
H., Tsukihara , T. , Omura , T. (2004) J. Virol. , in press.

MS04-4
STRUCTURAL BASIS OF MEMBRANE-INDUCED CARDIOTOXIN A3
OLIGOMERIZATION
C.-D. Hsiao•, F. Forouhar•, We .N. Huangb, J.-H . Liu•, K.-Y. Chienb, and W.-g . Wub•Institute of Molecular Biology, Academia Sinica , Taipe 115, Taiwan ; blnstitute of
Bioinformatics and Structural Biology, National Tsing Hua University, Hsinchu , 300 Taiwan(mbhsiao@ccvax.sinica .edu.tw)

Cobra cardiotoxins (CTXs) have previously been shown to induce membranefusion of vesicles formed by phospholipids such as cardiolipin or sphingomyelin. It canalso form pore in membrane bilayers containing anionic lipid such as phsphatidylserine or
phosphatidylglycerol. Herein , we show that the interaction of CTX with negativelycharged lipids causes CTX dimerization , an important intermediate for the eventual
oligomerization of CTX during the CTX-induced fusion and pore formation process. The
structural basis of the lipid-induced oligomerization of CTX A3 , a major CTX from Najaatra , is then illustrated by the crystal structure of CTX A3 in complex with sodium dodecyl
sulfate (SDS), likely mimics anionic lipids of the membrane , under micelle condition at 1.9
A resolution [1] . The crystal packing reveals a distinct SDS free and SDS rich regions, inthe latter of which two types of interconnecting CTX A3 dimers , D1 and D2 , and several
SDS molecules can be identified to stabilize D1 and D2 by simultaneously interacting withresidues at each dimer interface. When the three CTX-SDS complexes in theasymmetric unit are overlaid, the orientation of CTX A3 monomers relative to the SDS
molecules in the crystal is strikingly similar to that of the toxin with respect to model
membranes as determined by NMR and FTIR methods. These results not only illustrate
how lipid-induced CTX dimer formation may be transformed into oligomers either as
inverted micelles of fusion intermediates or as membrane pore of anionic lipid bilayers,
but also underscore a potential role for SDS in X-ray diffraction study of proteinmembrane interactions in the future.
Reference
1
Forouhar, F. , Huang, W.-N. , Liu , J.-H ., Chien , K.-Y. , Wu , W.-g . and Hsiao, C.-D.
(2003). Structural basis of the membrane-induced cardiotoxin A3 oligomerization.
J. Bioi. Chem. 278 , 21980-21988.

MS04-5
VESICLE TRANSPORT MACHINERY: X-RAY STRUCTURES OF HUMAN
GGA PROTEINS AND THEIR PARTNERS IN THE TRANS GOLGINETWORK
Soichi Wakatsuki•, T. Shiba•, T. Nogi•, M. Kawasaki•, R. Kato•, Y. Yamada•, M. Inoue•, S.
Kametakab, M. Shibatab, S. Waguri b, Y. Uchiyamab, Y. Shibac, K. Nakayamac•structural Biology Research Center, Photon Factory, IMSS , KEK, Tsukuba , lbaraki ,bQsaka University, cKyoto University, Japan(soichi.wakatsuki@kek.jp)

Intercellular vesicle transport relies on an intricate network of interactions of adaptor
proteins (AP) with cargo receptors , clathrin and various accessory proteins . International
efforts to search for human proteins homologous to the y-ear domain of the AP complexes
have lead to the identification of a novel family of adaptor proteins , called GGAs (Golgilocalizing , y-adaptin ear homology domain , ARF-binding proteins). Later, they have beenshown to be important for clathrin-coated vesicle transport between the TGN andendosomesl lysosomes instead of classical AP-1 complexes (see review [1]). GGA is anadapter protein with three domains and a hinge region, each of which interacts with othertransport proteins. The N-terminal VHS domain forms a right-handed superheli x with eighta-helices and binds TGN sorting receptors , such as mannose 6-phosphate receptors [2] ,sortilin and phosphorylated ~ -secretase [3] by recognizing their acidic cluster dileucine
sequences. The GAT domain uses its hydrophobic residues of the N-terminal helix-turnhelix motif to dock onto Switches I and II of GTP-bound ARF , thereby tethering GGA to
the TGN membrane for efficient recruitment of cargo receptors by the VHS domain [4] . Its
C-terminal half interacts with ubiquitin [5] and Rabaptin-5 , thus modulating the GGA's
function . The proline-rich hinge region recruits the N-terminal ~- propeller of clathrin to
initiate clathrin cage formation . Finally, the y-ear domain of AP-1 [6] and the GAE domain
adopt very similar immunoglobulin folds to interact with Rabaptin-5 and y-synergin . These
complex structures will be used to illustrate the molecular mechanisms of this new class ofadaptor proteins in vesicular transport.
References
1
K. Nakayama & S. Wakatsuki , Cell Struct. Funct. 28 , 431 , 2003
2
T. Shiba et al. Nature 415 , 937, 2002
T. Shiba et al. Traffic, in press
3
4
T. Shiba et al. Nature Structural Biology 10, 386 , 2003
Y. Shiba et al. , J. Bioi. Chern. 279 , 7105 , 2004
5
6
T. Nogi et al. Nature Structural Biology, 9 , 527 , 2002

MS05-1
A NEW OPPORTUNITY OF NEUTRON SCIENCE- J-PARC PROJECT IN JAPAN Yasuhiko FUJII
Neutron Science Research Center, Tokai Research Establishment Japan Atomic Energy
Research Institute (JAERI) 2-4 Shirakata-Shirane , Tokai , lbaraki 319-1195, Japan(fujii@neutrons .tokai.jaeri .go.jp)

Neutron scattering research in Japan started in early 1960's when JAERI built its
JRR-2 reactor (1 OMW) in Tokai. Soon after both JRR-3 (1 OMW) in Tokai and Kyoto
University's KUR reactor (5MW) in Kumatori became online. In addition to these research
reactors, in mid 1960 Japan pioneered an accelerator-based neutron source by using anelectron linac of Tohoku University in Sendai and twenty years later in 1980 the first
dedicated spallation neutron facility KENS based on a proton accelerator (3kW) was built
at KEK in Tsukuba. In 1990, JRR-3 was refurbished and renamed JRR-3M by doubling its
power (20MW) and installing a cold source. Currently it is one of the busiest neutron
facilities in the world providing users as many as more than 12,000 person x day per yearwith totally 25 neutron scattering , 2 neutron radiolgraphy and 2 prompt v-ray analysis
instruments capable to cover a wide variety of research fields .
In 2001 furthermore , JAERI and KEK started their 6-year joint project of J-PARC(Japan Proton Accelerator Research Complex) in Tokai where a new 1 MW neutron source(3GeV/3331JA , 25Hz) is a central facility to be completed in 2007 (tentatively named JSNS,
Japan Spallation Neutron Source). A total number of beam lines are designed as 23
aiming at appropriate one of three kinds of moderators. The joint project team between
JAERI and KEK has proposed 10 state-of-the-art instruments not only for their use but
also for worldwide general users. Other beam lines can be proposed by any groups .
Thus both 20MW reactor (JRR-3M) in operation and 1MW pulse source JSNS
under construction are located within less than 1km , which offer a very unique opportunity
not only to Japanese but also to worldwide users for their complementary use of thesewell-balanced neutron sources. We have planned a wide range of research programs tolead forefront science and technology including industrial application.

MSOS-2
ON STRUCTURAL PHASE TRANSITIONS IN PEROVSKITES
Christopher J. Howard ," Michael A. Carpenter,b and Kevin S. Knight c•Australian Nuclear Science and Technology Organisation , Private Mail Bag 1, Menai ,NSW 2234 , Australia ; bOepartment of Earth Sciences, University of Cambridge, Downing
Street, Cambridge CB2 3EQ UK; 0 ISIS Facility, Rutherford Appleton Laboratory, Chilton ,Didcot, Oxfordshire OX11 OQX, UK (cjh@ansto.gov.au).

Structural phase transitions in perovskites are often characterised by a nearcontinuous volume variation , even when those transitions are discontinuous. It is shown ,from a simple free energy expansion including strain-order parameter coupling terms, thatfor a volume- conserving transition , the magnitude of the order parameter remains
unchanged even when its direction changes discontinuously. The result explains why themagnitude of the B-cation displacement (BaTi0 3 ) or octahedral tilt angle (in SrZr0 3 orNa074W0 3 ) changes nearly continuously though first order transitions at which the directionof displacement or tilt axis switches suddenly, while leaving the volume practicallyunchanged. The influence of higher order terms (or temperature dependent coupling
coefficients) in the free energy expansion will also be considered.

MSOS-3

STRUCTURAL DISTORTION, CHARGE AND SPIN ORDERINGS IN
Pro.ssCao.2sSro.1MnOJ
W .-H . Li," C. C. Yang ,a F. C. Tsao,a P. J. Huang," J. W. Lynn ," and H. D. Yangc
8

Department of Physics , National Central University, Chung-Li , Taiwan ; bNIST Center for
Neutron Research , NIST, Gaithersburg, MD USA; c Department of Physics , National Sun
Yat Sen University, Kaohsiung , Taiwan (whli@phy.ncu.edu.tw)

A polycrystalline sample of Pr0 _65 Ca 0 _25 Sr0 ,Mn0 3 was prepared by the standard
solid state reaction technique . The detailed crystalline structure was studied based on
the high-resolution neutron powder diffraction measurements.
An orthorhombic
symmetry belongs to the space group Pnma was found for the compound at 300 K. No
symmetry changes were observed between 10 and 300 K, but a lattice distortion of the
Jahn-Teller type occurs at -190 K, which was clearly revealed in the temperaturedependencies of the unit-cell volume and the lattice constants. Electric resistivity,
specific heat, ac magnetic susceptibility, and neutron magnetic diffraction measurements
were all performed to investigate the basic magnetic and transport properties of thecompound . An insulator-to-metal transition is clearly seen at 82 K, which shifts to 120 K
when a magnetic field of 1T was applied. The Jahn-Teller distortion that results in an
increase in the resistivity was also observed . Five transitions of various origins were
found. A charge ordered state was evident at around 205 K. Mn moments ordered
antiferromagnetically below 190 K, with the Mn moments point along the c-axis direction.
A spin reorientation occurs between 100 and 82 K, which resulted in a net ferromagnetic
moment that in terms induced the insulator-to-metal transition , triggered by the double
exchange interaction. The Pr spins were also found to be ordered ferromagneticallybelow 38 K, with the moments parallel to the Mn moments. This may indicate that theferromagnetic ordering , commonly related to insulator-to-metal transition , is of metastable characteristic and is ascribed to electronic and magnetic instability induced byspin fluctuations. The interplay between the transport and magnetic behavior will be
discussed .

MSOS-4
IN SITU NEUTRON DIFFRACTION DURING DEUTERIUM ABSORPTION
OF Pd PARTICLES EMBEDDED IN Zr0 2 MATRIX
Stefan us Harjo ,a Takashi Kamiyama ,a Toshimitsu Yamazaki ,b Wataru Higemoto, a Akinori
Hoshikawa , a Shin -ichi Yamaura , c Hisamichi Kimura , c Akihisa lnoue ,c and Yoshiaki Arata dalnstitute of Materials Structure Science , High Energy Accelerator Research Organization ,Tsukuba , Japan, bRI Beam Science Laboratory, RIKEN , Saitama , Japan , clnstitute forMaterials Research , Tohoku University, Sendai , Japan , d0saka University, Osaka , Japan(harjo@post.kek.jp ).

A nanocomposite consisting of monoclinic Zr0 6 , cubic Zr0 6 and Pd particles(Zr0 6+Pd), that was fabricated by oxidizing a melt-spun amorphus Zr65 Pd 35 at 553K for 64
h in static air, was reported to show anomalous hydrogen absorption[1]. It was reported
that , the nanocomposite Zr0 6 +Pd could absorb hydrogen mass roughly two times higher
than Pd metal in bulk and powder forms . It was also reported that, since thisnanocomposite can absorb more than 300% hydrogen/deuterium , locally deuterium-lumps
can be included and therefore a solid-state nuclear fusion at room temperature may begenerated when an intense sonoimplantation of deuterium gas was conducted[6 ,3] .
To clarify more clearly the behaviour of deuterium absorption in the nanocomposite
Zr0 6+Pd , described above , we carried out in situ neutron diffractions during deuterium
absorption and desorption . The material used in this investigation was the nanocomposite
Zr0 6 +Pd fabricated due to procedures in Ref. [1]. The nanocomposite powders wereinserted in a steel holder which was completed with pipe arrangement in such a way that
deuterium gas implantation and evacuation could be conducted in situ at the sample
position of neutron diffractometer. The in situ neutron diffractions during deuterium
absorption and desorption were conducted at a time-of-flight neutron diffractometer,
VEGA, installed at the pulsed spallation neutron facility KENS , High Energy Accelerator
Research Organization . The deuterium implantation was conducted in a step-by-stepmanner, and the diffraction pattern at each step was measured for 5 - 10 h. The obtained
diffraction patterns were analysed using a multi-peak fitting procedure . As the results ,existence of PdO was determined in the starting state , i.e. , before the deuterium
implantation . At the beginning stage of deuterium implantation , PdO changed to Pd,
showing that deuterium was used for redu ction firstly. When the amount of the implanted
deuterium was increased , the absorption of deuterium to form Pd deuteride was observed.
This deuterium implantation behaviour was observed firstly in this study, in which slightly
different with the behaviour described above[1-3] . The detailed results and discussion will
be presented.
References
Yamaura , S ., Sasamori , K., Kimura , H., Inoue, A., Arata , Y. and Zhang , Y.-C . (6006)
1J. Mater. Res. 17, 1369-1334.
Arata , Y. and Zhang , Y.-C. (6006) Proc. Japan Acad. 78(8), 57-66 .
6
Arata , Y. and Zhang , Y.-C . (6006) Proc. Japan Acad. 78(8), 63-68.
3

MSOS-5
THE NEW QUASI-LAUE DIFFRACTOMETER AT THE REPLACEMENTRESEARCH REACTOR
Wim T. Klooster
Bragg Institute, ANSTO , PMB 1, Menai , NSW 2234 , Australia (wim@ansto.gov.au)

The new single-crystal diffractometer for the Replacement Research Reactor inAustralia will be a quasi-Laue diffractometer, similar to VIVALDI at ILL, France. It will becompetitive with the best instruments currently available. Data collection times for anormal structure determination will be less than a day, a considerable improvement oncurrent data collection times , typically a few weeks at HI FAR. Also , the crystal size needed
for an experiment can as small as about 0.1 mm 3 , opening up new research areas where it
has proved difficult to grow crystals sufficiently big (several mm 3 ) which are currently
needed. An area of research opening up will be multiple temperature and/or pressure
measurements .
This new instrument will be a useful tool to obtain structural information in a timely
fashion , where x-rays do not provide enough detail.
More detailed information on the instrument will be presented.

MS06-1
RECENT ADVANCE IN CONSTRUCTION OF NEW TOPOLOGICALCOORDINATION POLYMER NETS
Xiao-Minq Chen , Ming-Liang Tong , Jie-Peng Zhang , Xiao-Chun Huang
School of Chemistry and Chemical Engineering , Sun Yat-Sen University, Guangzhou
510275 , China (cescxm@zsu.edu.cn).

Extended framework solids are of current interest and importance because they may
offer new materials with a range of potentially useful properties. Network topology is an
important consideration in the design , construction , analysis and exploitation of newcoordination polymers or hydrogen-bonded networks. The most explored nets in crystal
chemistry are those "simple" ones such as uniform or uninodal low connected nets
constructed by 4-connected or 3-connected nodes and simple bridging linkers.
We recently exploited different kind of simple exo-bidentate and exo-tridentate
ligands , e.g. triazolate , imidazolate , di-Schiff bases , dicarboxylates to generate a numberof coordination polymers through conventional solution and hydrothermal methods. These
coordination polymers [1] exhibit a rich topological and structural chemistry including new
topological networks. The structures [Ag 2 (H 2 L) 3](N0 3 ) 2 and [Ag 2(H 2 L) 3](CI0 4 ) 2 [H 2 L = N,N'bis(Sali-cylidene)-1 ,4-di-aminobutane] exhibit Borromean links in 30 arrays , which arecomprised of layers that are entangled in an uncommon topological fashion.
The structure [2] of -Ni(pyaraMHP) 2 (Hpyara = 3-(3-pyridyl)acrylic acid) represents
the first (8,4) Platonic uniform net, containing square-planar 4-connecting nodes. The
structure of a mixed-valence Cu 1/Cu 11 imidazolates Cu 2 (im) 3 , synthesized through precise
control of the hydrothermal reaction condition , exhibit an unprecedented 4 .85 net, in whichsome of the 8-membered circuits Cu 11 8 Cu 14 (im) 12 catenated by other 8-membered circuits.
Two new 3-connected three-dimensional networks of copper(l) triazolates Cu(mtz)(Hmtz = 3,5-dimethyl-1 ,2,4-triazole) and Cu(ptz) (Hptz = 3,5-dipropyl-1 ,2,4-triazole) [3],were prepared by hydrothermal reactions involving in-situ ligand cycloaddition from nitriles
and ammonia. Interestingly, the two complexes exhibit novel double-interpenetrating
4.8.16 and 4 .122 nets.
A controlled synthetic approach via metal valence tuning has been utilized togenerate a series of new mixed-valence Cu 1/Cu 11 coordination polymers [4], in which
Cu 2 (im) 3 is an unprecedented uninodal 4-connected 4.8 5 topological net which can befurther simplified to be an 8-connected CsCI-Iike net.
The synthetic strategies, crystal and topologic structures , factors influencing thestructures will be described.
References
1 Tong , M.-L., Chen , X.-M ., Ye , B.-H., Ji , L.-N. (1999) Angew. Chem. Int. Ed. 38 , 2237.
2 Tong , M.-L. , Chen , X.-M ., Batten , S. R. (2003) J. Am. Chem. Soc. 125, 16170.
3 Zhang , J.-P. , Zheng ,S.-L., Huang, X.-C ., Chen , X.-M . (2004) Angew. Chem. Int. Ed.
43 ,206.
4 Huang , X.-C. , Zhang , J.-P ., Lin , Y.-Y ., Chen, X.-M . (2004). unpublished results.

MS06-2
CRYSTAL STRUCTURE OF 2D GRID-LIKE POLYMER BASED ON 3d-4d
MIXED METALSPeng Cheng , Bin Zhao
Department of Chemistry, Nankai University, Tianjin, 300071 , P. R. China(pcheng@nankai.edu.cn)
Metal-based coordination polymer has been mushrooming recently due to theirintriguing topological structures and unique functions , such as ion-exchange , adsorption ,separation , sensor, and molecular recognition . However, the most of them focused on thepolymers containing 3d transition metals rather than 3d-4d mixed ones. To date , few multidimensional polymers comprising both 3d blocks and 4d blocks transition metals havebeen reported .
In previous work, we successfully synthesized a series of 3d-4f mixed metal-based
3D polymers through hydrothermal methods P-21 Recently, a 2D 3d-4d mixed metal-based
polymer: [(V0 2)LAg]n (L = pyridine-2,6-dicarboxylic acid anion) was obtained , which
crystallized in orthorhombic crystal system and space group of C222(1) with a = 6.534(2) ,b = 15.441 (5) , c = 9.230(3) A and a=~= y = 90°. Z = 4 . R1 = 0.0194 and S = 1.042. Jach
V center chelates to a tridentate ligand L, four 0 atoms and one N atom complete
distorted square pyramidal geometry of V ion . While the tetrahedral conformation of Ag
center consists of four 0 atoms . V and Ag centers alternate by either carboxyl or IJ-0
bridges to further form a unique 3d-4d heterometal-based 2D grid motif (see Figure 1).

Figure 1. The 20 grid structure of polymer [(V02)LAg]nReferences
1
B. Zhao , P. Cheng , Y. Dai , C. Cheng , D. Z . Liao , S. P. Yan , Z. H. Jiang , G. L. Wang.
(2003) Angew. Chem. , Int. Ed. 42 , 934.
2
B. Zhao , P. Cheng , X. Y. Chen , C. Cheng , W. Shi , D. Z. Liao , S. P. Yan , Z. H. Jiang.
(2004) J. Am. Chem. Soc., 10, in press.

* This work is supported by the NNSF of China (Nos . 90101028 , 50173011 ), and the
TRAPOYT of MOJ , P. R. C ..

MS06-3
THE ROLE OF DOUBLE C-H ... N WEAK HYDROGEN BONDING MOTIFSIN N-HETEROAROMATIC INCLUSION CHEMISTRY
Roger Bishop. Solhe F. Alshahateet, Donald C. Craig ,A. Noman M.M . Rahman and Marcia L. Scudder
School of Chemical Sciences, The University of New South Wales ,UNSW Sydney NSW 2052 , Australia (r.bishop@unsw.edu.au)
The importance of the C-H ... O weak hydrogen bond in structural chemistry andcrystal engineering is now thoroughly established , but much less information has been
published about the related C-H ... N interaction [1].
We find that the C-H ... N interaction really comes into serious contention in the solidstate packing of N-heteroaromatic compou nd s. The X-ray crystal structures of designed
lattice inclusion hosts such as 1-3 will be described. In these compounds , it is the double
C-H ...N weak hydrogen bond that is of greatest significance.
Both double cyclic motifs and bifurcated cyclic motifs, as illustrated , play key roles
in encouraging the host molecules to assemble in an edge-edge manner that is
inaccessible to their aromatic hydrocarbon analogues [2-5].

References
Desiraju , G.R. and Steiner, T. The Weak Hydrogen Bond in Structural Chemistry and1
Biology, Oxford Science Publications, Oxford (1999).
Marjo , C.E., Scudder, M.L., Craig , D.C. and Bishop , R. J. Chern. Soc. , Perkin Trans.
2
2 (1997) 2099 .
Marjo , C.E., Bishop, R. , Craig , D.C. and Scudder, M.L. Eur. J. Org. Chern. (200 1)
3

863.
4
5

Rahman , A.N.M.M ., Bishop , R. , Craig, D.C. and Scudder, M.L. Eur. J. Org. Chern.
(2003) 72.
Alshahateet, S.F. , Bishop , R., Craig , D.C. and Scudder, M.L. (2004) Cryst. GrowthDes. (paper submitted for publication).

MS06-4
HYDROGEN-BONDED POLYROTOXANE STRUCTURE CONTAININTCYCLIC (H 2 0) 4 in [Zn(OAc) 2 (1J-bpe)]"2Hp: X-RAY AND NEUTRONDIFFRACTION STUDIESJagadese J. Vittal ,• Ng Meng Tack,• Wim T. Kloooster,b and Garry J. Mclntyrec•Department of Chemistry, National University of Singapore , 3 Science Drive 3, Singapore
117 543 (E-mail: chmjjv@nus .edu.sg). bBragg Institute, Australian Nuclear Science andTechnology Organization , PMB 1, Menai NSW 2234 , Australia . clnstitut Laue-Langevin ,PP 156, 38042 Grenoble Cedex 9, France

The reaction of 4,4 '-bipyridylethane (bpe) and 4,4'-dipyridyldisulfide (dpds) with
Zn(OAc) 2 ·2Hp has led to the formation of two coordination polymers , [Zn(OAcM JJbpe)] ·2Hp (1) and [Zn(OAc) 2 (J,J-dpds)] (2) . Both the compounds have zigzag coordination
polymeric structures as revealed by X-ray crystallography. However the presence of twolattice water in 1 resulted in an interesting change in the crystal structure . In 1, thecarboxylate carbonyl oxygen atoms of the Zn(0Ac) 2 groups from two different adjacentzigzag polymers and four lattice water molecules form 24-membered hydrogen-bonded
ring (graph set notation , R 66(24)) . One of the two bpe ligands associated with each Zn(ll)passes through the centre of this ring to form 2D hydrogen-bonded coordination
polyrotaxane structure . In the solid state , the adjacent 24-membered hydrogen-bonded
rings further fused together through 0-H .. O hydrogen bonds among four waters to form
cyclic (Hp)4 . This resulted in one dimensional hydrogen-bonded ribbon-like polymer
comprised of 24- and 8- membered 0-H .. ·O hydrogen-bonded rings fused together
alternatively and hence produce 3D hydrogen-bonded polyrotaxane network. The neutron
diffraction study provides a detailed description of the hydrogen bonds involved .

MS06-5
FROM HEXANUCLEAR TO DODECANUCLEAR AZAMETALLACROWNS
Shi-Xiong Liu ,a Shen Lin ,a.b Wen-Shi Wu ,a.c Chi-Chang Lina andJian-Quan Huanga
aoepartment of Chemistry, Fuzhou University, Fuzhou 350002 , P.R. China ;bDepartment of Chemistry, Fujian Normal University, Fuzhou 350007 , P.R. China ;cCollege of Material , Huaqiao University, Quanzhou 362011 , P.R. China(shixiongliu@yahoo.com)

Metallacrowns are a kind of the metallamacrocycles which exhibit selective
recognition of cations and anions. Interest in the metallacrowns stems not only from theirhigh symmetry and aesthetic molecular frameworks , but also from the special magnetic
properties associated with them.[1] The earlier reported metallacrowns are with repeating
pattern of 0-M-N-0 (M=metal)[1]. Most recently, some hexanuclear azametallacrowns
with repeating pattern of N-M-N-N have been prepared by Lah and us[2-4]. Several
octanuclear, decanuclear and dodecanuclear azametallacrowns have been obtained
firstly by our group[5] .
The structural characterizations of these metallacrowns were discussed here. All themetal atoms in the core rings of these metallacrowns adopt a propeller configuration , andhave alternating A/t:,. stereochemistry due to the binding modes of the multidentate
ligands. There are several encapsulated solvent molecules in the 'host' cavity of the someazametallacrown complexes , while there are no any guest molecules in the 'host' cavity ofthe other azametallacrown complexes. The relation between the nuclear number andneighboring M .. -M .. ·M interatomic angles or average neighboring M.. ·M separation was
discussed. The factors affecting formation of multinuclear azametallacrowns , such as theflexible multidentate 0/N-donor ligands and oxidation state of metals , were summed.
We are grateful for financial support from the National Natural Science Foundation ofChina (No . 20171 012), Natural Science Foundation of Fujian Province , China(No.G011 001 0).
References1
Pecoraro V.L. , Stemmler A.J. , Gibney B.R. , Bodwin J.J. , Wang H. , Kampf J.W. ,Barwinski A. (1997) Progress in Inorganic Chemistry; Karlin , K. D., Gd. ; John Wiley &Sons: New York, Vol. 45, p 83.
2
Kwak B. , Rhee H. , ParkS. , Lah M.S. (1998) lnorg. Chern. 37 , 3599-3602.
3Lin S., Liu S.-X. , Huang J.-Q., Lin C.-C. (2002) J. Chern. Soc., Dalton Trans.
1595-1601.
4Lin S. , Liu S .-X. , Lin B.-Z . (2002) lnorg. Chim. Acta 328 , 69-73.
5
Liu S.-X., Lin S. , Lin B.-Z., Lin C.-C ., Huang J.-Q. (2001) Angew. Chern. Int. Ed.
Engl. 40 , 1084-7.

MS07-1
DRUG-RECEPTOR INTERACTIONS : CRYSTAL STRUCTURE OF ACOMPLEX FORMED BETWEEN PHOSPHOLIPASE A2 AND ASPIRIN AT
1.9 A RESOLUTION
Rajendra Kumar Singh . A. S. Ethayathulla , Tala! Jabeen, Sujata Sharma , Punit Kaur, A.
Srinivasan and Tej P. Singh
Department of Biophysics , All India Institute of Medical Sciences , New Delhi -110029 ,INDIA (rajendra84@hotmail.com)
Phospholipase A2 (PLA2) stereospecifically hydrolyzes acyl esters at sn-2 positionof 3-sn phosphoglycerides. Pharmacological interest in this reaction stems from the belief
that PLA2 may catalyze the release of arachidonate and thereby precipitates the
inflammatory cascade involving eicosanoids . The enzyme was isolated from cobra venom
and purified to homogeneity. Its inhibition was studied with 0-oxy acetyl phenol. The
complex was crystallized in 30 % ethanol. X-ray intensity data were collected using MAR
research imaging plate scanner to 1.9 A resolution. The structure was determined bymolecular replacement and refined to an R factor of 0.17. The model consists of 906
protein atoms , 105 water molecules, 1 calcium ion and 11 atoms of the inhibitor. The
difference electron density (Fo-Fc) clearly indicated the presence of 0-oxy acetyl phenol
molecule at the binding site of phospholipase A2. The structure shows that inhibitor iscompletely buried in the binding site of PLA2. The OH group of the inhibitor interacts with
Asp 49 and the calcium ion. The presence of several interactions between the enzyme
and the inhibitor indicate the specificity of 0-oxy acetyl phenol towards PLA2.

MS07-2

CRYSTAL STRUCTURE OF AN INHIBITORY ANTI-FACTOR IX FAB INCOMPLEX WITH FACTOR IX GLA DOMAIN
Minqdong Huanq ,a.b Barbara Furie ,b Bruce Furieb•Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou , Fujian , P. R. China (mhuang@fjirsm .ac.cn)
bDivision of Hemostasis, Thrombosis , and Vascular Biology, Department of Medicine,
Harvard Medical School and Beth Israel Deaconess Medical Center, 330 Brookline Ave ,RE319 , Boston , MA 02215 .
The binding of Factor IX to membranes during blood coagulation is mediated by the
N-terminal gamma-carboxyglutamic acid-rich (Gia) domain, a membrane anchoring
domain found on vitamin K-dependent blood coagulation and regulatory proteins.
Conformation-specific anti-Factor IX antibodies are directed at the calcium-stabilized Gla
domain and interfere with Factor IX-membrane interaction . One such antibody, 1OC12 ,recognizes the calcium-stabilized form of the Gla domain of Factor IX. We prepared thefully carboxylated Gla domain of Factor IX by solid phase peptide synthesis andcrystallized Factor IX (1-47) in complex with Fab fragments of the 10C12 antibody. The
structure of the Factor IX (1-47)-antibody complex was determined at 2.2 A. The complex
structure shows that the CDR loops of the 1OC12 antibody form a hydrophobic pocket toaccommodate the hydrophobic patch of the Gla domain , consisting of Leu 6, Phe 9, andVal 10. Polar interactions also play an important role in the antibody-antigen recognition .
Furthermore , the calcium coordination network of the Factor IX Gla domain is different
than in Gla domain structures of other vitamin K-dependent proteins . We con clude that
this antibody is directed at the membrane binding site in the omega loop of Factor IX andblocks Factor IX function by inhibiting its interaction with membranes.

MS07-3
STRUCTURE OF THE N1 DOMAIN OF XpsE PROTEIN FROMXANTHOMONAS CAMPESTRIS
Nei-Li Chan , Yeh Chen , Jiun-Li Chang , and Nien-Tai Hu
Institute of Biochemistry, College of Life Sciences , National Chung Hsing University,
Taichung City, Taiwan (nlchan@dragon.nchu.edu.tw & nthu@nchu.edu.tw).

The type II protein secretion pathway (also known as the general secretion pathway(GSP)) is widely used by Gram-negative bacteria , especially by animal and plant
pathogens , for secreting hydrolytic enzymes or toxins across the bacterial outermembrane. At least 12 - 15 conserved gene products are required for the assembly of agigantic secretion apparatus that spans the entire periplasm and penetrates both the outerand the cytoplasmic membranes. Among these essential protein components, the XpsE isunique in two aspects: it is the only cytoplasmic protein , and is the only protein componentof this system with the potential to exhibit ATPase activity due to the presence of a
nucleotide-binding motif. The integrity of this motif is crucial for the functions of XpsE and
its orthologues because protein secretion is greatly perturbed by mutations in this region.
Since the periplasmic space is in general short of energy sources such as ATP, it has been
proposed that the XpsE may function as an energy-generating component for protein
secretion . Although isolated XpsE does not associate with the cytoplasmic membrane , itis recruited to the cytoplasmic face of the membrane-anchored secretion machinery
through the Xpsl. It has been well established that the protein-protein interactions
between orthologues of the XpsE and Xpsl are required for secretion. Recent studies
suggest that the XpsE/XpsL interaction is probably mediated by the N-terminal region of
XpsE . Results from limited proteolysis revealed a protease-sensitive site near the Nterminus of the XpsE that divides it into an N-terminal and a C-terminal region . Speciesspecificity was found to be determined by the N-terminal region . Interestingly, despite its
lower sequence similarity with other NTPases involved in type II secretion (termed
GSPII_E protein family) , the 21 kDa N-terminal region of the XpsE protein (XpsEN, residue
1 to 152) shares significant similarity with those in a GSPII_E subfamily involved in type IV
pilus assembly. Collectively, the XpsEN polypeptide and its homologues are classified as a
distinct protein family GSPII_E_N (PF05157) in the Pfam Protein Family Database. As thefirst step toward structural studies on this complicated machinery, we have recently
determined the crystal structure of XpsEN using Se-MAD approach. Details of thestructural determination and analysis will be presented.

MS07-4
CRYSTAL STRUCTURE OF A SECRETORY ANTIAPOPTOTIC GLYCO PROTEIN FROM SHEEP (SPS-40)
Devendra B. Srivastava , Janesh Kumar, K. Sarvanan , Nagendra Singh , Sujata Sharma ,A. Srinivasan and Tej P. Singh
Department of Biophysics , All India Institute of Medical Sciences , New Delhi -110029(devendrabhusrivastav@rediffmail.com)

The transition period between lactating and non-lactating states of the mammary
gland is a period of active involution during which the mammary gland undergoes
intensive ultra structural changes and the secretions contained in the gland undergo
dramatic compositional changes . As a prominent protein in the whey secretions of nonlactating animals , this protein shows a sequence identity (70 %) with a protein present inspecific type of breast cancer cells (BRP-39). It is speculated that these proteins act as aprotective signalling factors that determine which cells are to survive the drastic tissue
remodeling . In order to understand the precise role of SPS-40 during involution and
BRP-39 in breast cancer, we have determined the crystal structure of SPS-40 at 2.0 A
resolution . The protein crystallizes in space group P2,2,2, with unit cell dimensions a=62.7
A, b=66.4 A and c=107 .5 A. The 55 % of crystal volume is occupied by the solvent. The
structure has been determined by molecular replacement method and refined to an Rfactor of 0.19. The protein has been cloned and sequenced as well. It is glycosylated as 5
units of sugar have been identified in the electron density. The TIM barrel in the protein istightly packed by several hydrophobic residues thus impairing its carbohydrate binding
capability and indicating its potential of recognition through protein-protein interactions.
Although the overall folding of this protein shows a high degree of similarities to the thoseof chitinases and chitinase-like proteins, the point mutation of consensus active site
residues and other sites result in the loss of catalytic activity and an altered folding ofcarbohydrate binding sites. Thus , the protein has acquired a new function on common
framework of proteins containing TIM barrel.

MS08-1
3D POROUS MAGNETS OF M3(HCOO)s (M=Mn and Co)
Zheminq Wanq ."b Bin Zhang ,ac Hideki Fujiwara ," Takeo Otsuka ," Hayao Kobayashi• andMohamedally Kurmood•institute for Molecular Science and CREST, JST, Okazaki 444-8585 , Japan ; bColleqe ofChemistry and Molecular Engineering , Peking University, Beijing G0087G , China ~ lnstituteof Chemistry, Chinese Academy of Sciences , Beijing G00080 , China ; dlnstitut de Physiqueet Chimie des Materiaux de Strasbourg , CNRS-UMR 7504 , 23 Rue de Loess , BP 43 ,F-67034 Strasbourg Cedex2 , France (wzm@chem.pku .edu.cn)

To create porous magnets is a long sought academic goal in molecular magnetism
research since porosity and magnetism are inimical to one another[G]. The possibility ofmodulating magnetic properties of porous magnets upon guest exchange renders themattractive for applications as magnetic sensors and devices[2,3]. We report here two novel
3D porous magnets of [MJ(HCOO)B] (M=Mn , Co) . The two materials possess an unusual
diamond framework with nodes of metal-centered MM4 tetrahedron and open channels of
4x5 A wide. All metal atoms have octahedral coordination geometry. Both open
frameworks show thermally stable up to -260°C, high stability and flexibility for the
inclusion of many kinds of guests , as well as long-range magnetic ordering . Guest
inclusion compounds of series of guestc [Mn3(HCOO)B][4] exhibit guest-modulated criticaltemperatures.
-o-- lf'Cior 1- • - FC 10f 1-I:.- ZFC ior 2"""""- FCfOf 2......,._ zFCior 3- • - FC!or 3-o- ZFCior •- • - FC!ct 4-<>- ZFCiof S- - FCfor S-4- ZFC1o1 6-- FC for 6--i>- ZFCior 7- -Metal-centered
MM4 tetrahedron

4

8

10

12

FC!or 7

14

Temperatu-e I K

Diamond framework

ZFC/FC for several
guestc[Mn3(HCOO)B] compounds

ReferencesG
Ferey, G. (2003) Nat. Mater.2, G36-G37.
2
Maspoch , D., Ruiz-Molina , D., Wurst, K., Domingo , N., Cavallini , M. , Biscarini , F. ,Tejada , J. , Rovira , C. and Veciana , J. (2003) Nat. Mater. 2 , G90-G95.
3
Halder, G. J., Kepert , C. J., Moubaraki , B., Murray, K. S. and Cashion , J. D. (2002)
Science 298 , G762-G765.
4
Wang , Z.-M ., Zhang , B., Fujiwara , H., Kobayashi , H., and Kurmoo , M. (2004) Chem.
Commun . DOI:GO.G039 I B3G422GC .

MS08-2
CUBIC PEROVSKITE-RELATED PHASES IN THE TERNARY Sr0-Cu0Nbp5 SYSTEM
Y. Liu , R. L. Withers, F. Brink, L. Noren, V. Ting
Research School of Chemistry, Australian National University, Canberra , ACT 0200 ,Australia (yliu@rsc.anu.edu .au8.
The ternary Sr0-Cu0-Nb 2 0 5 system has been carefully re-investigated via powder
XRD and electron probe micro-analysis to clarify contradictions regarding phaserelationships in the literature (1-5] . Three distinct cubic perovskite-related solid solution
phases have been found and their structural and vibrational characteristics investigated
via electron diffraction and Fourier Transform Infrared spectroscopy. Results on these
cubic perovskite-related compounds are as follows:
The first solid solution (SS 18, composition close to S ~ _ 00 Cu 0 .. 0 Nb0 _58 0 286 , was foundto be metrically cubic. Weak superstructure reflections requiring a doubling of the parent
perovskite cell dimension were detected by electron diffraction.
Compounds from the second solid solution , composition close to Sr 133 Nb067 0 3 , also
show cubic metric symmetry similar to that of SS1 but this is also accompanied by astrong , highly structured , diffuse intensity distribution arising from short range ordering andassociated structural relaxation . The presence of weak additional reflections , however,again necessitated a doubling of the parent perovskite cell dimension .
Compounds from the third solid solution are metrically tetragonal (presumably the
result of a strong John-Teller effect originating from the Cu 2• ions8 and exhibit a --J2X'12x2
supercell of the cubic perovskite parent structure. The true local symmetry, however, isactually monoclinic.

References
Y.N. Venevtsev, (19718 Mat. Res. Bull. ,6, 1085.
1
Z.Sun , X.H .Chen , R. Fan , X.G. Luo, L.Li , (20038 J.Phys . Chem . Solids , 64, 59 .
2
S. Tao , J. T .S. Irvine , (20028 Solid State lonics , 154-155, 659 .
3
E.G . Fesenko, V.G.Smotrakov, V.V. Eremkin , L.A . Shilkina , (19928 Inorganic
4
Materials, 28, 1751 .
A.L.Podkorytov, M.l. Pantyukhina , V.M. Zhukovskii , and V.V. Simonov, (19948
5
Russian J. lnorg. Chem ., 39, 1492.

MS08-3
NON-AMBIENT X-RAY DIFFRACTION ANALYSIS OF PHARMACEUTICALSOLIDS
A. Stefanovic, PANalytical, Singapore
31 Kaki Bukit Road 3, #06-04/05 Techlink Singapore 417818 ,Tel: +65 6741 2868 , Fax: +65 6741 2166
(Aieksandar.Stefanovic@panalytical.com)

For pharmaceutical substances , an unexpected phase transition at non-ambientconditions , for instance during storage or transport , can turn a powerful medicine into a
useless powder. Therefore there is an increasing concern to investigate the influence ofenvironmental conditions on the structure of pharmaceutical samples. Especially inpharmaceutical research there is an increasing need to investigate the influence of theseparameters on , for example , crystal structure, phase transitions or polymorphism of thesamples.
The production of the pure active pharmaceutical ingredients, excipients and drugs
in their final form is sensitive to the environmental conditions during the process andtherefore requires absolutely reproducible process parameters. Only X-ray diffraction cansolve the problem of adequately determining the precise conditions for obtaining thecompounds of constant composition .
The structural stability and phase transitions under various non-ambient conditions,especially temperature and humidity , will be discussed for different active ingredients ,excipients and functional stabilizers (bio-protectants). The structural and phase transitions
are investigated by using a non-ambient X-ray powder diffraction methods. The
comparison with other complementary methods , e.g. thermal methods (TGA I DSC) will
be discussed in details.

MSOB-4
CRYSTAL STRUCTURE OF POLY (3-HYDROXYBUTYRATE-C0-3HYDROXYHEXANOATE) CLOSE TO MELTING POINT
Katsuhito Mori ," Masayuki Nakamura ," Harumi Sato ," lsao Takahashi ," Hikaru Terauchi,"
Yukihiro Ozaki ," Fuminobu Hirose,b Kenichi Senda ,b and Isao Nodac•school of Science and Technology, Kwansei Gakuin University, Sanda , Hyogo 669-1337 ,Japan ; bKaneka Corporation , Japan; "The Procter and Gamble Company, U.S.A.
( scbcOO 1O@ksc. kwansei .ac.jp ).
Poly(3-hydroxybutyrate): PHB and the copolymer, Poly(hydroxyalkanoate): PHA are
biodegradable polymers , produced by a number of microorganisms . They are subjected
to degradation by bacteria in soil within some period , and therefore they are expected tocontribute to environmental preservation. These polymers are classified into biosynthesis
polyesters. However, only PHB and PHA have biodegradable and biocompatible
thermoplasticity. Therefore , as a substitute for petrochemical materials , the study ofbiodegradable polymer has attracted considerable attention.
In this study, we have investigated the thermal properties of PHB and a newbacterial copolyester, Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate): P(HB-co-HHx) , by
X-ray diffraction. P(HB-co-HHx) , one of the PHA polymer, is more flexible than PHB. BothPHB and P(HB-co-HHx) have a crystal structure based on a helix system . The crystallites
are distributed in a large amorphous matrix. Compared with PHB , as HHx increases P(HBof
degreelowashows
co-HHx)crystallization , and a low melting point.
MoKa radiation
Figure 1 shows a X-ray diffraction
pattern of P(HB-co-HHx), HHx=12mol%from room temperature to its melting point.
P(HB-co-HHx) changes from crystalline toamorphous as the temperature increases .
large
indicates
expansion
Thermalanisotropy: The a-axis length increases withincreasing temperature. However, the b-axis c:length keeps constant to temperature . It ~shows a sharp contrast with thermal~
13
12
11
10
9
8
7
6
behavior of PHB. The present results Z, 5
2theta/degree·strongly support a novel intermolecular :ginteraction between the carbonyl group and -E _the alkyl group along the a-axis direction , - ·which may be used for designing desirable biodegradable polymer with high flexibility and
Fig .1 Temperature dependence of X-ray
high melting temperature.
P(HB-co-HHx),of
diffraction(HHx=12mol %). For clarity, the data
are displayed vertically.

MS09-1
BLOCH WAVE DEGENERACIES IN NON-SYSTEMATIC CRITICAL
VOLTAGE EFFECT OBSERVED IN ELECTRON DIFFRACTION
Hirfumi Matsuhataa and Jon Gj0nnesb
aNational institute of Advanced Industrial Science and Technology (AIST) central 2
1-1 , Umezno, Tsukuba , lbaraki 305-8568 , Japan , (H . Matsuhata@aist.go.jp)
bCentre for Materials Research , University of Oslo , Gaustadalleen 0371 Oslo , Norway,

According to the Motto-relation , the scattering factors for electrons obtained byexperiments have an advantage in accuracy compared to that for x-ray, for reflections withlower scattering angles [1]. The accidental Bloch waves degeneracies observed inelectron diffraction patterns are one of the useful effect to obtain the accurate structure
factors at the low scattering angles. In this report, we show various non-systematic criticalvoltage effects, caused by the accidental Bloch wave degeneracies. Diffraction conditionsof the non-systematic critical voltage effects for three-beam case , four-beam case, andfive-beam case are explained and discussed. Application and analysis are shown for ZnS
as an example. Structure factors for 220 and 200 reflections are determined accurately,
and discussed in terms of the rearrangement of the outer electrons caused by ionization ..
References
1
H. Matsuhata and J. Gj0nnes (1996) Acta Cryst. A52 , 686-699 .

MS09-2
DIRECT IMAGING OF A LOCAL DEBYE-WALLER FACTOR ANOMALY IN
QUASICRYSTALS THROUGH ADF-STEM OBSERVATIONSNational Institute for Materials Science , 1-2-1 Sengen , Tsukuba 305-0047 Japan(abe.eiji@nims.go.jp)

A real-space imaging of a local thermal vibration anomaly in a solid has been
demonstrated for the first time , through atomic-resolution annular dark-field scanningtransmission electron microscope (ADF-STEM) observations of an AI 72 Ni 20 Co 8
quasicrystalline compound. Significant changes of ADF-contrast depending on theobservation temperature as well as the angle ranges of the annular-detector are found tobe obvious at some particular AI atomic sites. The origin of this anomalous ADF-contrast is
explained fairly well by concerning the thermal diffuse scattering (TDS) intensity change
due to different values of Debye-Waller factor, which is defined by mean-square thermal
vibration amplitude of the atoms. These localized atomic fluctuations presently observedin the quasicrystal provide an important hint on an issue of phason - the phason is an
extra elastic degree of freedom specific to the quasiperiodic order (in addition to the usualphonons in crystals) and has been theoretically predicted to cause localized fluctuations .
References
Abe , E, Pennycook , S. J. & Tsai. (2003) Nature (London) 421, 347-350 .
1

MS09-3
STRUCTURAL STUDIES OF THE A2lnNbOs1 :1 AND ~CoNb209 1:2
ORDERED PEROVSKITES (A= Ca 2+, Sr2•, Ba 2•)
V.Ting, Y. Liu , R. L Withers and L. Noren
Research School of Chemistry, Australian National University, Canberra , ACT 0200 ,Australia (vting@rsc.anu .edu .au)

Recent XRD investigations [1 , 2, 3] of these AzlnNbOB 1:1 perovskites and the
AJCoNbzOg so-called 1:2 ordered perovskites (A = Ca 2 +, Sr2• , Ba 2• ) reported random
distribution of ln 3•/ Nb 5 • and Co 2./Nb 5+ ions onto the respective perovskite B-site positionsof these compounds . Based on this assumption , the A= Ba , Sr compound s in the 1:1
series were assigned simple cubic Pm-3m space group symmetry and the A = Cacompound , the space group Pnma. Similarly, the 1:2 Ba and Sr materials were assigned
Pm3m symmetry, while the Ca 1:2 compound was not assigned a space group at all.
Therefore, a thorough investigation has been carried out on these AzlnNbOB and
AJCoNbzOgperovskites with a view to clarify the space group symmetries and structures ofthese materials and also to see if we could rationalise the structural distortions causing
those space groups .
A careful electron diffraction study showed that while the 1:1 BazlnNb06 compoundoccurs in the cubic Fm-3m , elpasolite structure type , both the A = Ca and Sr 1:1
compounds occur at room temperature in monoclinic P12 ,/n1 perovskite-related
superstructure phases. In the case of the 1:2 compounds , the observed extinctions allow
the Ba compound to be assigned the space group P-3m1 and the A=Sr and Ca
compounds to be definitively assigned to the space group P12 ,/c1.
The superstructure reflections are the combined result of B-site cation ordering andstructural distortions away from the ideal cubic perovskite parent . G ± 1/2<111 > p* satellite
reflections seen for each of the 1:1 compounds are the result of a rock salt-type ordering
scheme for the B-site cations , as well as a displacive modulation originating from theconcerted octahedral contraction of the nearest-neighbour oxygens around the B-site Nb
cation and the expansion of the oxygen octahedra around the In cation that this ordering
scheme necessitates. Correspondingly, the G ± 1/3<111 >p * satellite reflections seen ineach of the A3CoNbz0 9compounds results from the 1:2 ordering scheme along <111 > andthe associated displacive modulation . In addition , in the case of the strontium and calcium
compounds in both series , a need to satisfy bond valence sums for the A cations drives afurther distortion in the form of rotations of the rigid octahedra (manifesting as satellite
reflections at G ± 1/2<111 >p*).
References
1
J. Yin , Z. Zou and J . Ye , (2003) J . Phys. Chem . 8 , 107, 61-65.
J. Yin , Z. Zou and J. Ye , (2003) J . Phys. Chem . B, 107, 4936-4941.
2
3
R. Ratheesh , M. Wohlecke , B. Berge , Th . Wahlbrink , H. Haeuseler, E. Ruhl , R.
Blachnik , P. Balan , N. Santha and M.T. Sebastian , (2000) J . Applied Physics, 88 ,281 3-2818

MS09-4

UNUSUAL MAGNETIC BEHAVIOR IN Pr1_xSrxCo0 3 : A LORENTZ
MICROSCOPE STUDY
Masaya Uchida ,a.b Ramanathan Mahendiran ,a Yasuhide Tomioka ,c Yoshinori Tokura ,a.c.dandYoshio Matsuib•ERATO-SSS , Japan Science and Technology Agency (JST) , c/o AIST, Tsukuba
305-8562, Japan; bNational Institute for Materials Science (NIMS) , Tsukuba 305-0044 ,Japan; <CERC , National Institute of Advanced Industria l Science and Technology (AIST),
Tsukuba 305-8562 , Japan; dUniversity of Tokyo , Tokyo
113-8656, Japan(MATSUI. Yoshio@nims.go .jp ).

The Pr,_,Sr,Co0 3 (0 .3 :> x :> 0.5) series exhibit unusual magnetic behavior not foundin other rare earth cobaltites [1] . The de magnetization exhibits an anomalous downward
step in low fields (H< 0.01 T) at a temperature (TA- 120 K) much lower than the
ferromagnetic transition (Tc- 230 K).
Lorentz electron microscopy was used to investigate this unusual magnetic
behavior around TA in Pr0 _5 Sr0 _5 Co0 3 . The specimen is in a magnetic field-freeenvironment. Ferromagnetic domain walls started to appear just below T 0 • When further
cooling down , the magnetic domain walls disappeared below 90 K. The magnetization
patterns obtained by the so-ca lled transport of intensity equation method [2] indicate thatferromagnetic component decreases below 90 K. It is suggested that such behavior ispossibly due to a temperature induced spin-state change. We will discuss magnetic phase
diagram of Pr,_,Sr,Co0 3 (0 :> x :> 0.5) and compare with other cobaltites .
References
1
Mahendiran , R. and Schiffer, P. (2003) Phys . Rev. B 68 , 24427.
2
Paganin , D . and Nugent, K. (1998) Phys. Rev. Lett. 80 , 2586-2589.

MS09-5

ICOSAHEDRAL QUASICRYSTAL MISSING ICOSAHEDRAL SYMMETRY
Koh SAITOH•, Tadahiro YOKOSAWAb, Michiyoshi TANAKA< and An Pang TSAid•National Institute for Advanced Industrial Science and Technology, Tsukuba 305-0032 ,Japan; bArrhenius Laboratory, Stockholm University, S-1 06 91 Stockholm Sweden ;clnstitute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai
980-8577 , Japan; dNationallnstitute for Materials Science , Tsukuba 305-0007 , Japan(saitoh.koh@aist.go.jp)

Crystal symmetry is one of the fundamental properties , which is closely related tothe stability of the structure . Quasicrystals is considered to be stabilized by their highrotational symmetry, such as icosahedral or decagonal symmetries [1], despite that theperiodic translational symmetry is substituted by the quasiperiodic translational symmetry
instead . From this viewpoint, the high rotational symmetry of the quasicrystal seems to
be a requirement for the formation of the quasicrystalline structure. Actually, all the
icosahedral quasicrystals which have been discovered so far show icosahedral symmetry
without any exception . In the present paper, we report unique features of the structure of
Cd-based icosahedral quasicrystal [2] investigated by convergent-beam electron
diffraction (COED) .
The selected-area electron diffraction (SAED) patterns of Cd 65 _1 Yb 10 9 taken from anarea with 1OOnm in diameter along the five- , three- and two-fold axes are composed of
sharp spots and exhibits five- , three- and two-fold symmetries respectively with almost no
deviations from the regular positions. This indicates that the quasiperiodic lattice is of
icosahedral symmetry with negligible phason defects, confirming a long-range icosahedral
order of the lattice. It was found that the COED patterns of Cd65 , Yb 10_9 show clear
symmetry breaking of the five- , three- and two-fold symmetries. This indicates that the
icosahedral symmetry of the quasicrystal is lost in a definite range despite that thequasilattice has a long-range icosahedral order. A possible explanation of the symmetry
breaking is that Cd 65 ,Yb m. 9 is formed by an atom cluster missing icosahedral symmetry,
which is embedded to the regular icosahedral quasilattice points with the sameorientation . The results of the present COED study may be compatible with the structuralmodel of the atom cluster of the Cd-Yb alloy crystal , which was reported to exhibit the
breaking of icosahedral symmetry by Tsai et a/.[2] .
References
V. Elser and C. L. Henley, (1985) Phys. Rev. Lett. 55 2883.
A. P. Tsai et al. , (2000) Nature 408 537.
2

MS10-1
STRUCTURAL GENOMICS STUDY OF THE SARS CORONAVIRUS -THE
CRYSTAL STRUCTURES OF SARS VIRUS MAIN PROTEASE (MP'0 ) AND
ITS COMPLEX WITH AN INHIBITOR
Zihe Rao
Laboratory of Structural Biology, Tsinghua University & National Laboratory of
Biomacromolecules, Institute of Biophysics , Chinese Academy of Sciences , Beijing , China(raozh@xtal.tsinghua.edu.cn)

A newly identified coronavirus , SARS-CoV, is the etiological agent responsible
for the outbreak of severe acute respiratory syndrome (SARS). SARS-CoV Mpro , which isa 34.6 kDa protease (also called the 3C like Protease, 3CLpro) , plays a pivotal role inmediating viral replication and transcription functions through extensive proteolytic
processing two replicase polyproteins , pp1 a (486 kDa) and pp1 ab (790 kDa). Here we
report the crystal structures of the SARS coronavirus main protease , Mpro , at different pHvalues and in complex with a specific inhibitor. The protease structure has a fold that canbe described as an augmented serine-protease but with a Cys .. .His at the active site . This
series of crystal structures, the first of any protein from the SARS virus , reveal substantial
pH-dependent conformational changes , and an unexpected mode of inhibitor binding ,providing a structural basis for rational drug design.

MS10-2
A HIGH-THROUGHPUT APPROACH TO LINK THE BIOCHEMICAL AND
CELLULAR FUNCTIONS OF MACROPHAGE PROTEINS
Bostjan Kobe ,"·b Pawel Listwan ,"·b Nathan Cowieson ,b Anna Aagard ,b Thomas Huber,C
Timothy Ravasi ,b Christine Wells ,"·b David A. Humeb and Jennifer L. Martina.b
8
Department of Biochemistry and Molecular Biology; blnstitute for Molecular Bioscience ;cDepartment of Mathematics, University of Queensland, St. Lucia QLD 4072
(b.kobe@uq.edu.au) .

We have instituted a program for functional characterization of proteins involved inmacrophage function. Macrophages are special cells that represent the first line ofdefence by mammals against pathogens . They recognize pathogens , engulf and attempt
to destroy them . However, inappropriate macrophage activation leads to conditions suchas septicimea and toxic shock, arthritis , atherosclerosis and other chronic inflammatory
diseases.
Our program takes advantage of expression profiling by microarrays and structural
biology as two extremely powerful techniques for the characterization of the cellular andbiochemical functions of proteins , respectively. The combination of these two techniques
provides a unique opportunity to link the knowledge of molecular and cellular roles toachieve a complete functional characterization . Furthermore , the focus on macrophages
leads to the identification of therapeutic targets for two classes of therapeutics,
compounds that may amplify the immune function of macrophages , and compounds that
may treat inflammatory and other macrophage-associated diseases.
Our current approach involves the following experimental steps: target selection
using the combination of eDNA microarray technology and bioinformatics , PCR primer
design , ligation into bacterial expression vectors, trial protein expression of histidinetagged proteins and solubility and refolding tests, large scale expression and purification ,high throughput crystallisation trials and structure determination , and functional assays.
Most of these steps involve parallel experiments on a number of proteins using 96-wellplates and robotic automation .
Our program is to our knowledge the first high throughput structural biology
program in Australia. The approach is equally amenable to smaller groups and larger
consortia. The approach will be illustrated by the studies on one of our first successful
targets , mouse latexin (see Figure). The combination of expression profiling and structure
determination provides clues to the function of this sole carboxypeptidase inhibitor in
macrophage activation.

MS10-3
STRUCTURAL GENOMICS OF C. ELEGANS
Ming Luo. Ph .D.
Southeast Collaboratory for Structural Genomics, Center for Biophysical Sciences andEngineering , University of Alabama at Birmingham , Birmingham , AI 35294 , USA(mingluo@uab .edu )Several programs of structural genomics were initiated with bacterial genomes. Our group
selected the genome of C. elegans as a representative of higher eukaryotic genomes .
Funded by a new NIH program , Protein Structure Initiative, we originated this project as astructural proteomics approach to map out the function of each gene in C. e/egans.
Goals: To establish the high throughput capability to express , crystallize and solve thestructure of the predicted 22 ,000 genes in C. elegans. A production capability of 100-200
structures per year will be attempted .
Protein preparation : We are using the GATEWAY™ expression system from Invitrogenfor the high throughput protein production . The reaction conditions are ideal for parallel
performance . We currently are capable of processing 384 genes per three weeks using arobotic system. A novel strategy including a dynamic ELISA analysis method has beendeveloped for this efficient approach . For proteins that show soluble expression , largescale production is carried out for 10 proteins per week. We can express proteins in
multiple systems of prokaryotic and eukaryotic cells to maximize protein expression.
Crystal screen: A robotic crystal screen system using microplates is installed including
sitting drop setup , automatic imaging , and image analysis . Nanoliter samples were used
so each crystal screen could be performed with 100 IJI of purified protein samples .
X-ray structure: The X-ray analysis was carried out at a state-of-the-art synchrotron
facility (SERCAT) operating in Advanced Photon Source , Argonne National Laboratory.
This facility will allow automated operation to collect X-ray diffraction data in a timely
fashion . New phasing methods by single wavelength anomalous dispersion (SAD) were
implemented to solve structures using protein crystals from recombinant or natural
sources based on hetero-atoms such as Fe, Ca , or S without heavy atom isomorphous
phasing or selenium substitution .
Results : Over 6,500 genes from the C. elegans genome have been tested in the HTP
facility for protein expression . 3,000 proteins were expressed , among which 446 weresoluble . 63 proteins have been crystallized . The system met the basic criteria we designed
for. Structural studies are now in progress. Progress will be discussed at the conferenceMS10-4
AN INTEGRATED APPROACH FOR SYNCHROTRONBASEDSTRUCTURAL PROTEOMICS ON PROTEINGL YCOSYLATION AND TRANSPORT
Soichi Wakatsuki•, M. Kawasaki•, R. Kato•, M. Hiraki•, N. Matsugaki•, N.lgarashi•, &M. Suzuki••Structural Biology Research Center, Photon Factory, IMSS , KEK, Tsukuba , lbaraki ,Japan. (E-mail : soichi.wakatsuki@kek.jp)

Glycosylation is one of the most important post-translational modifications carriedout by an intricate network of glycosyltransferases, glycosidases , transporters , andtransport proteins in the endoplasmic reticulum (ER) and the Golgi apparatus . Here,vesicular transport machineries play crucial roles for protein glycosylation as well asprotein transport such as endocytosis, exocytosis, and autophagy. We are pursuing atarget-oriented structural proteomics project on the molecular mechanisms of protein
glycosylation and transport as part of the Japanese national project, Protein 3000 . The
project is benefiting from an integral approach which combines efforts in protein
overexpression , purification , crystallization , synchrotron beam line development and rapid
data collection , structure solution , and biological assays.
The structures of the three domains of GGA, a new class of adapter proteins ofvesicular transport [Nature 415 , 937 , 2002; Traffic in press ; Nature Structural Biology, 9,527 , 2002; ibid. 10, 386 , 2003] will be used to illustrate our approach . In addition , several
other examples of recent X-ray structures will be chosen from plant lectins responsible fortrafficking of glycosylated proteins , mammalian glycosyltransferases [J.Bioi.Chem. inpress] and glycosidases.
In the area of structure determination , we are developing a number of highthroughput technologies to assist not only our structural genomics projects but also
general users from Asia and Oceania . These include two new insertion-device MAD beamlines (PF BL-5 & PF-AR NW12) which can produce high quality data sets in 5 to 30
minutes with user-friendly software and highly accurate (1 to 2 microns rotational error)
diffractometers, an extremely large scale crystallization robot (200 ,000 conditions/day) androbotics for crystal harvesting and cryo-protectant exchange. We are also developing anext generation X-ray area detector called X-ray HARP which will enable continuous andsuper-fine phi slicing data collection (for example 180 degree oscillation in one rotation)from weakly diffracting crystals .

MS11-1
MAGNETIC STRUCTURE ANALYSIS OF ANTIFERROMAGNETIC ANDFERROELECTRIC COMPOUND ERMNp 5 AND YMNp 5
Y. Noda ,a S. Kobayashi , a T. Osawa , a Y. Fukuda , a H. Kimura , a I. Kagomiya b and K. Kahnb•institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai
980-8577 , Japan ; bDepartment of Physics , Waseda University, Shinjuku-ku , Tokyo
169-8555, Japan (ynoda@tagen. tohoku.ac.jp ).

The family of RMnp 5 compounds (R=Y and rare earth elements) was recently
payed much attention because magnetic order and ferroelectric order strongly couple
each other. For instance , in Y and Er compounds, the anti-ferromagnetic phase transition
occurs at about TN=44K with doubly modulated incommensurate magnetic phase (qM=(1 /2+x, 0, 1/4+z) ). On further cooling , the modulation wave vector locks-in thecommensurate ones sequentially, first lock-in on qz and then lock-in on q, at about T 0 =41 K
and TcM=40K , respectively. Simultaneously, electric spontaneous dipole moment shows
up and dielectric constant peaks at the lock-in transition of qz=1 /4[1-3].
We have performed crystal and magnetic structure analyses of YMn 2 0 5 andErMnp 5 at the commensurate magnetic phase , at 25K and 20K respectively. R-factors of
crystal and magnetic structure analyses are 4.5% and 8.6% for YMn 2 0 5 , and 2.8% and5.5% for ErMn 2 0 5 . W obtained the magnetic moment as each component of 8Mn 4 +, 8Mn 3+
and 8Er3 + independent atoms(Fig.1 ), but no magnetic moment in Y atoms. We found themagnetic moment on Mn•+ and Mn 3+ are sinusoidally modulated and the moment of Er3+
has mainly z-component (longitudinal wave character). The difference between Er and Y
compound is that the node of the sinusoidal wave is between Mn 4 + atoms (magnetic Er
atom layer) for Er compound , while it is on the Mn 4 + atom for Y compound.
References
1
I. Kagomiya , H. Kimura , Y. Noda and K. Kahn ,J. Phys. Soc. Jpn . 70 (2001) Suppl. pp.145-147
2
Y. Noda, Y . Fukuda , H. Kimura , I. Kagomiya , S. Matsumoto, K. Kohn ,T. Shobu and N. Ikeda , J. Korean Phys. Soc. 42(2003) S1192-1195.
3
S. Kobayashi , T. Osawa , H. Kimura , Y. Noda , I. Kagomiya and K. Kohn
J. Phys. Soc. Jpn. 73(2004 )N04 in press

MS11-2
RESONANT X-RAY SCATTERING FROM Fe304 SINGLE CRYSTAL: A
SCENARIO OF ELECTRONIC PHASE SEPARATION BELOW THE
VERWEY TRANSITION
Hsueh-Hsing Hung aaNational Synchrotron Radiation Research Center, Hsinchu Science Park, 30077, Taiwan(hhh@nsrrc.org .tw).

Origin of the Verwey transition in magnetite is unsolved for more than 60 years [1].
At the room temperature , magnetite forms a cubic lattice of inverse spinel structure:(FeA3. 0)(Fes3· Fes2·0 3) . As generally considered , the electronic fluctuation among theoctahedral B-site iron ions reasons out the metallic phase above the Verwey temperature ,Tv=122K. Regarding the unoccupied valence states and whether or not long-range chargeordering below Tv, there have been two recent letters of work at ESRF just standing up for
an opposite point of view [2 , 3]. One observation , based on single-crystal results ofresonant X-ray scattering (RXS) from "forbidden " (002) as well as (006) reflection , claimed
that no charge separation below Tv in magnetite because of neither change of the 1s to 3d
nor to 4p resonant electronic excitation been captured in their measurement. The otherone , derived from a best-fit model with two sets of Fes-0 bond length to match the data of
X-ray and neutron powder diffraction , however, supported a possible evidence of charge
separation below Tv.
In our RXS work at the BL 158 beamline of NSRRC, but under an exact way toaccess this problem , distinctive changes in feature of resonant electronic excitations
through the Verwey transition are disclosed without ambiguities. Particularly, as following
the in-plane (1-1 0) rhombohedral distortion , continuous structural transformation as well
as charge localization is initialized at 4 degrees above the expected Verwey temperature
and , thus , electronic phase separation is abruptly formed at Tv due to the bonddimerization .
References
1
E. J. W. Verwey, Nature (London) 144, 327 (1939).
J. Garcia , et al , PRL 85 , 578 (2000); PRB 63 , 054110 (2001 ).
2
3
J.P. Wright , J.P. Attfield , and P.G. Radaelli , PRL 87 , 266401 (2001 ); PRB 66 ,214422 (2002).

MS11-3
CORRELATIONSHIPBETWEEN
CRYSTAL
STRUCTUREPIEZOELECTRICITY IN LANGASITE WITH FOUR CATIONS

AND

H. Ohsato•, T. lwataki•, N. Araki•, H. Morikoshib and K. Kakimoto••Nagoya Institute of Technology, Gokiso-cho, Showa-ku , Nagoya 466-8555 , Japan ;bMaterials Research Center, TDK Co ., 570-2 , Matugashita, Minamihatori, Narita
286-8588 , Japan (ohsato.hitoshi@nitech .ac.jp).
Recently, one of promising piezoelectric materials for higher frequencies , wider
bandwidth and higher-bit rates digital communication is Lapa 5 Si0 14 (LGS) designated as
langasite applied SAW filter. It has larger electromechanical coupling factor than quartz
and also has nearly the same temperature stability as quartz. LGS crystal withCa 3 Ga 2 Ge 4 0 14 -type crystal structure was synthesized and the crystal structure is analyzed
by Mill [1]. It is also important feature that the growth of the single crystal is easy. In thecase of three-elements compounds such as [R3]A[Ga] 6 [Ga 3]c[GaSi] 0 0 14 (R=La , Pr andNd), the piezoelectric constant increases with the ionic radius of R [2-4]. In this study,
crystal structures of four-element compounds such as [A 3]A[B] 6 [Ga 3 lc [Si 2] 0 0 14 (A=Ca or Sr,
B=Ta or Nb) are analyzed by single crystal X-ray diffraction, and the mechanism andproperties of the piezoelectricity depend on the species of cation was clarified based on
the crystal structure.
This crystal structure with P321 space group belongs to trigonal crystal system withthree-hold axes in a primitive hexagonal lattice. The crystal structure formulae presented
in this paper are shown as [R3]A[Ga] 6 [Ga 3]c [GaSi] 0 0 14 for three-elements compounds
RGS and [A 3]A[B] 6 [Ga 3]c(Si 2] 0 0 14 for four-elements components ABGS. Here, A: Sr and
Ca , B: Ta and Nb. There are four independent cation sites: A-dodecahedron , Boctahedron , C-, and 0-tetrahedron. In the large cation layer with A- and 8-polyhedra , acharacteristic empty space locates , which play an important role in the mechanism ofpiezoelectricity.
When a force is added to the [1 00] direction , polarization occurred on the [1 00] dueto the destruction of charge balance . The space releases for repulsion of large cations .
We also measured the piezoelectric constants and electromechanical coupling factor for
RGS and ABGS. We found a parameter which these properties are depend on . These
properties are located on the line as a function to the parameter.
Acknowledgements
A part of this work was supported by a grant from the NITECH 21st Century COE
Program "World Ceramics Center for Environmental Harmony" from Japanese Ministry of
Education , Science , Sports and Culture and by a Grant-in Aid for Science Research (C)from Japan Society for the Promotion of Science .
References
1
B.V.Mill et a /., Doklady Akademii Nauk USSR, 264 (1982 ) 1385-89 .
2
J.Sato eta/., J. Crystal Growth , 191 (1998)746-53 .
3
T. lwataki , H. Ohsato, e t a /., J. Euro. Ceram . Soc. 21 , (2001)1409-1412 .
4
H. Ohsato , eta/. , Abstract for 4th Asian Meeting on Ferroelectrics, pp232, 12-15, Dec. 2003
Bangalore, India.

MS11-4
CRYSTAL STRUCTURES AND PHASE TRANSITIONS IN THE SYSTEM
SrTi0 3-La 213 Ti0 3
Christopher J. Howard ! A. Gregory R. Lumpkin ,ab Ronald I. Smith ,< and Zhaoming Zhanga•Australian Nuclear Science and Technology Organisation , Private Mail Bag 1, Menai ,NSW 2234 , Australia ; bDepartment of Earth Sciences, University of Cambridge , Downing
Street, Cambridge CB2 3EQ UK; <iSIS Facility, Rutherford Appleton Laboratory, Chilton ,Didcot, Oxfordshire OX11 OQX, UK (cjh@ansto.gov.au).

The distribution of A-site cations in the perovskite system La.sr, _3.,2Ti0 3 depends onthe concentration of La 3 • ions and associated vacancies. For smaller x (x $ 0.2) the
substitutions are random. For x ~ 0.55 , the cations are ordered in such a way thatsuccessive layers are occupied to a greater (close to fully occupied) and lesser (this layer
contains most of the vacancies) degree, and this ordering drives a tetragonal distortion.
For x from about 0.25 to 0.5 , the X-ray patterns show diffuse peaks indicative of similarordering , but this is not long range order and no tetragonal distortion results. The lower
temperature structures also exhibit out-of-phase tilting of the Ti0 6 octahedra , setting in attemperatures varying practically linearly with composition from 105 K for x = 0 to about
650 K at x = 2/3.

MS11-5
ANTIPHASE DOMAINS
5)03/SrTi03 THIN FILMS

AND

B-SITEORDERING

IN

Pb(Mg113Nb2tJ-

Seon Hee Seo," Suraj Yadav," Do Young Noh•* and Kiyotaka Wasab•Department of Materials Science and Engineering , Kwangju Institute of Science andTechnology, Kwangju , Korea 500-712 ; bFaculty of Science , Yokohama City University,
22-2 Seto Kanazawaku , Yokohama , Japan (dynoh@kjist.ac.kr)
Anti-phase domains and 'B-site' ordered nanoregions are found in Pb(Mg113Nb213-0)03(PMN) thin films in a synchrotron x-ray scattering experiment. Epitaxial PMN(001) thinfilms grown by radio frequency magnetron sputtering evolve from tetragonal to pseudo
cubic structure as the film thickness increases due to the strain relaxation . In films withintermediate thickness , antiphase domain boundaries (ADB) with 1/2[110] displacement
appear. The lattice in the B-site ordered regions in the films with ADBs is much more
distorted than average lattice. The ADB phase shares common features with themonoclinic phase observed in bulk relaxsor PMN.
Author to whom
dynoh@kjist.ac.kr

correspondence

shouldbe

addressed ;electronic

mail :

MS12&13-1
MULTIPLE OPEN READING FRAMES, CODON BIOS AND AMINO ACID
USE AND THE EVOLUTION OF THE GENETIC CODE.
W. L. Duax•.c, R. Huether•, L. Habegger•, S. Connare•, V. Pletnevb and J. Schaber••Structural Biology Dept. Hauptman-Woodward lnst., 73 High St. , Buffalo , NY 14203,
bShemyakin-Ovchinnikov In st. , Moscow, Russia Federation and cSUNY, Dept of Structural
Biology, Buffalo , NY. (duax@hwi.buffalo.edu)

Examination of the complete genome of S. coelicolor reveals that the antisense
strands of 70% of the 7555 genes (5277) contain no stop codons and could in principle beopen reading frames (ORFs). Furthermore 2174 genes have a third full length ORF , 228
have a fourth ORF and 56 have five ORFs (no stop frames). We previously detected
multiple ORFs (MORFs) and a bias in codon usage in the short chain oxido reductase(SCOR) enzyme family. Of 1651 predicted or known gene products in species frombacteria , archaea , and eukaryotes , 84 SCOR genes having triple ORFs (TORFs) were
found to be encoded almost exclusively by the 32 of the 64 codons that are GC-only or
GC-rich (2 out of 3 nucleic acids in a codon being G or C) in composition. Examination of
the MORFs in S. coelicolor revealed a similar bias in codon use and a DNA triple bias thatis most severe in the QORFs and PORFs. The 228 QORF genes vary in length from 28 to
464 amino acid, 87% of the coding is from the GC-rich half of the genetic code and 82%of the protein sequences are composed of 10 amino acids (GPASTDLVER). Only
eighteen of the expected gene products are characterized . These include two ABC
transport proteins, a cyclase , a kinase , a synthetase, a two component regulator, acarbohydrate transport protein , an oxidoreductase and the L12 ribosomal protein . Further
investigation reveals a high incidence of MORFs, codon bias and amino acid bias in mostprokaryotic ribosomal proteins. Regardless of overall GC content many ribosomal
proteins have genes containing DORFs and have no cysteines or tryptophans in theiramino acid composition . The MORFs in the SCOR enzymes and S. coe/icolor appear to
identify a subset of the codon system that evolved first , and a subset of amino acids that
may have constituted the earliest folded proteins. This work is supported by NIH Grant
No. DK26546.

MS12&13-2
STRUCTURE BASED 'PUNCTUTATION MARKS' IN GENOMIC DNA
Manju Bansal• and Aditi Kanhere•• Molecular Biophysics Unit, Indian Institute of Science , Bangalore-560012(mb@mbu.iisc.ernet.in)
Recognition of genomic signals by RNA polymerase is an important first step intranscription initiation but exactly how RNA polymerase locates these signals in the stretchof genomic sequence remains unclear. Are there any punctuation marks other than the
known hexameric sequence motifs at -10 and -35 positions? We have analyzed 279
Escherichia coli promoter sequences for various structural properties like curvature ,flexibility and stacking energy. Overall , the promoter sequences show presence of acurved region covering the -1 0 and -35 signals . Our study shows that the mean curvatureof upstream sequences is more than that of the downstream coding sequences and there
are also clear differences in stacking energy of the two regions. Thus , analysis ofcurvature and stacking energy in the promoter DNA sequences reveal certain signals ,which could be used to identify such regions in a genomic sequence.

MS12&13-3
BIOINFORMATICS IN STRUCTURAL GENOMICS OF C. ELEGANS
Jun Tsao . Ph .D. , David H. Johnson , and Mike Carson , Ph.D .
Southeast Collaboratory for Structural Genomics , Center for Biophysical Sciences andEngineering , University of Alabama at Birmingham , Birmingham , AI 35294 , USA
Uuntsao@uab.edu)

Our NIH funded program on Structural Genomics of C. e/egans is a part of theProtein Structure Initiative. A relational database has been developed to capture all
experimental data and to mine data with regard to target selection , protein expression
conditions , crystallization conditions and structural analyses(website: http://sgce.cbse.uab.edu). Over 16,000 Open Reading Frame (ORF) clones of
C. elegans have been stored and their experimental results are presented. Trends ofsuccessful protein production and crystallization could be observed. Our results could
serve as reference gages to avoid pitfalls in selecting other eukaryotic ORFs for structural
analysis.

MS12&13-4
SSEP: SECONDARY STRUCTURAL ELEMENTS OF PROTEINS
K. Sekar, V. Shanthi , P. Selvarani , Ch. Kiran Kumar and C.S.Mohire
Bioinformatics Centre and Supercomputer Education and Research Centre, Indian
Institute of Science , Bangalore 560 012 , INDIA (sekar@physics.iisc.ernet.in)

SSEP is a comprehensive resource for accessing information related to thesecondary structural elements present in the 25% and 90% non-redundant protein chains .
The current version provides information about the a-helical segments, b-strand
fragments , 310-helices, b and n-turns and hairpin loops of varying lengths. The freegraphics program RASMOL has been interfaced with the search engine to visualize thethree-dimensional structures of the user queried secondary structural fragment. In
addition , the package can be used to extract the three-dimensional atomic coordinates ofthe defined secondary structural elements . The database is updated regularly and isavailable through Bioinformatics web server at http://cluster.physics.iisc.ernet.in/ssep/ or
http:/1 144.16.71 .148/ssep/. The details and the newly added options will be presented .
Reference
V. Shanthi , P. Selvarani , Ch . Kiran Kumar, C.S. Mohire and K. Sekar. (2003) Nucl.
1
Acids. Res. 31(1) , 448-451.

MS12&13-5
THE ROLE OF DATA DICTIONARIES IN KNOWLEDGE RETENTION
Sydney R Hall• and Nick Spadacciniba School of Biomedical &Chemical Sciences , University of Western Australia , Nedlands
6009 ; b School of Computer Science & Software Engineering , University of Western
Australia, Nedlands 6009 , Australia . (syd@crystal.uwa.edu.au)

Data dictionaries are electronic files that contain precise computer-readable
information about data items used in a particular field. These dictionaries are ofincreasing importance in science as the basis for the seamless interchange of data
between laboratories, journals and databases.
In crystallography, data dictionaries exist for a number of sub-discipline areas, aswell as for the "core " data items common to many aspects of crystal structures and theiranalysis . CIF dictionaries are available for the discipline areas of structure analysis ,macromolecular structure , powder diffraction , symmetry, incommensurate structures , andprecision density studies. These are described in detail in the soon to be publishedInternational Tables Volume G 1 •The primary function of data dictionaries is to precisely identify and characterise
frequently used data items. This characterisation, which includes the definition of
attributes such as dependencies between data items; whether they are numbers or text;
and allowed enumeration , forms the basis for data validation processes critical to journals
and databases accepting deposited data.
Data attributes in the next generation of data dictionaries (generally referred to as'domain ontologies') provide much more semantic information about data items. This
information is usually expressed as 'methods' which determine the relationship ofderivative data items to primitive (i.e. measured or postulated) and other derivative data.
Methods scripts may be expressed in various ways , but their common purpose is toprovide functional algorithms that allow non-primitive information to be evaluated.
Methods may be applied to data classes as well as individual items , and are particularly
important because they preserve executable knowledge about the data items they
determine.
The 'ontology evaluation ' approach differs from conventional software
because methods only link items , or classes of items , to the next level of data higher in thederivation chain. The sequence of evaluation steps is not predetermined as it is incomputer programs.
This paper will describe an ontology approach to knowledge retention based on the
StarDDL and dREL languages 2 , and demonstrate how these are applied to data
evaluation and validation .
References
1
International Tables for Crystallography Volume G (2004) Eds. S R Hall and B
McMahon . Kluwer Academic Press: London .
2Spadaccini , N., Hall, S.R. and Castleden , I.R. (2000) J. Chern. Inform. & Computer
Sci. 40 , 1289-1301.

MS12&13-6
3D STRUCTURAL ANALYSIS OF PROSITE PATTERNS
Sukanta Mondal ,a Vasanthakumar.B,b S. P. Jaishankarb and S. Ramakumara.bab

Department of Physics, Indian Institute of Science , Bangalore-560 012 , India.
Bioinformatics Centre , Indian Institute of Science , Bangalore-560 012 ,lndia.(suku@physics.iisc.ernet.in)

True positive hits of PROSITE patterns are expected to have a characteristic threedimensional structure. The combined sequence-structure attributes of PROSITE patterns
can be used for function prediction of an uncharacterized protein with known primary andthree-dimensional structure , a situation that might arise in structural genomics projects.
We have analyzed the structural features of variable length sequence patterns as well as
fixed length sequence patterns from different categories of Enzyme classification in
PROSITE. The results of the analyses for the variable length patterns show thatconserved residues in the pattern can adopt well-defined backbone conformation. In
general , conserved residues in variable length patterns are likely to be completely buriedor partially solvent exposed . Key residues for metal binding are from conserved positionsin the variable length pattern and ligands are mostly interacting with conserved residues.
We have found specific examples of true hits of PROSITE fixed length patterns displaying
structural plasticity by assuming significantly different local conformation depending upon
the context. Our work highlights the importance of taking into account all the known
distinct conformations of PROSITE patterns while creating a sensitive 3D template for thepattern for use in functional annotation .

MS12&13-7
MATCHING STRUCTURE TO CELL DISTORTION IN TWINNEDCRYSTALS
A. David Rae•
Research School of Chemistry, The Australian National University, ACT 0200 , Australia(rae@rsc.anu.edu.au).

aWhen twin related reciprocal lattices coincide sufficiently well for all intensities to becollected as the sum of two components , there is the possibility that the wrong one of two
cells might be chosen to go with the fractional coordinates determined for the structure .
This is often recognised by obtaining a satisfactory refinement with the twin ratio reversed
compared to expectation. Demands of cell conventions and standard space groups may
require changing fractional coordinates and equivalent positions rather than the cell tocorrect such problems . The problem arises naturally when a structure is obtained byrelating it to an already known structure of higher symmetry rather than trying to untwin
intensities to obtain an initial solution (a procedure that is less reliable as 1:1 twinning isapproached).
Many structures can be described as an occupancy modulation of an idealised 1:1
disordered parent structure of higher symmetry corresponding to the Fourier transform ofa subset of the observed reflections or a symmetrised component of the observedreflections. Symmetry elements destroyed by ordering the structure may reappear as amechanism for polytypism , stacking faults or twinning. An example where all 3
phenomena can occur, sometimes in the same "crystal" , is 9,10 phenanthrenequinone [1] .
A 1:1 disordered parent structure of P2,1c symmetry can be ordered to form different
orientations of a Cc structure with a and b doubled or different orientations of a F-1
structure with a, band call doubled. In the triclinic case and are no longer exactly 90 °.
For the 100 K structure of Ag(bipy)N0 3 , bipy = 4,4'-bipyridine [2] the only extra reflections
occur from the loss of systematic absences when the symmetry is lowered from Fddd toF12/d1 and is no longer 90 o. In both compounds the use of standard settings of standard
space groups , viz P-1 and C2/c helps disguise the existence of an idealised parent
structure of higher symmetry .
Choices are made when these structures are ordered. The choice of cell can be
replaced by a choice between pseudo symmetry related sets of equivalent positions of theparent structure. The requirements of standard space group settings may complicate thischoice. Using no restraints or constraints refinements can be performed that are identical
except that the twin ratio is reversed. However a sensible use of constraints and restraints
produces a preference for one structure and helps explain the cell distortion. The above
compounds will be used to illustrate appropriate procedures .
References
1Rae, A. D. and Willis, A.C . (2003) Z. Kristallogr. 218 , 221-230 .
2
Somphon , W. , Hailer, K.J . and Rae , A. D. (2004) AsCA'04 Abstracts .

MS12&13-8
DATA BASE OF HYDROGEN AND HYDRATION IN PROTEINS
N. Niimura•, I.Tanakab, K.Kuriharab, T.Chatakeb and M.Maedab•Faculty of Engineering , lbaraki University, Naka-narusawa , 4-12-1 , Hitachi, lbaraki ,316-8511 , Japan. TEL +81-294-38-5254 (niimura@mx.ibaraki.ac.jp)
bNeutron Science Research Center, Japan Atomic Energy Research Institute, Tokai-mura ,lbaraki-ken , 319-1195, Japan. TEL : +81-29-282-5906 , FAX: +81-29-284-3822
Neutron diffraction provides an experimental method of directly locatinghydrogen atoms in proteins , and the development of the neutron imaging plate (NIP)
became a breakthrough event in neutron protein crystallography. Several high resolution
neutron diffractometers dedicated to biological macromolecules (BIX-2 , BIX-3 and BIX-4)
with the NIP have been constructed at the Japan Atomic Energy Research Institute andthese have enabled high resolution (such as from 1.5A to 2.0A) structural analyses ofseveral proteins to have been carried out. The crystal structures of myoglobin , rubredoxin(wild & mutant), hen egg-white lysozyme (at pH4.9 and 7.0) and , human lysozyme , cubic
insulin , DsrD and oligomer DNA have been determined using BIX . From these studies, all
the hydrogen and hydration in these proteins have been summarized as data base , andby using them , very interesting topics relevant to hydrogen and hydration in proteins , suchas hydrogen bonds (bifurcated H-bondings and very few example of co-linear H-bondings
arrangement of X-H ----Y) and dynamical behaviors of hydration structures includinghydrogen have been extracted from the analytical procedure of the Data Base .
The part of this work is supported by ORCS and JST data base promotion funding.

MS14-1
AB INITIO STRUCTURE DETERMINATION OF Co(dt)2 BY GENETIC
ALGORITHM
Makoto Sakataa. Yuichi Fujishiroa, Eiji Nishiboria, Masaki Takatab, Akiko Kobayashic,
Hayao Kobaya shid.
aoepartment of Applied Physics , Nagoya University, Nagoya 464-8603, Japan ; bJapan
Synchrotron Research Institute, Kouto , Mikazuki-cho, Sayo-gun , Hyougo 679-5198 ,Japan ; cResearch Centre for Spectro-chemistry, The University of Tokyo, Hongo , Bunkyoku , Tokyo 113-0033, Japan ; dlnstitute for Molecular Science and CREST, Myodaiji ,Okazaki 444-8585 , Japan(sakata@cc.nagoya-u.ac.jp).
As a related material to single compon ent molecular conductor Ni(tmdt)2 1 (tmdt= tetrathiafulvalene-trithiolate),a cobalt complex with extended-TTF ligand , Co(dt)2 (dt= tetrathiafulvalene-dithiolate ), was synthesized under the expectation of the magnetic
molecular conductor by changing central metal atom and ligand . Electrical resistivity ofCo(dt)2 pellet sample was 1 .9S em·' which showed fairly metallic at room temperature . The
magnetic susceptibility at room temperature was too small , 3.5 x 10 4 emu mol·' . The
crystal structure determination of this material was required for understanding very low
magnetic susceptibility. However, single crystal of Co(dt)2 has never been synthesized andonly small amount of powder sample was obtained . In this study, ab initio structure
determination of Co(dt)2 was successfully carried out by using third generation synchrotron
powder diffraction data. The structure was determined by genetic algorithm(GA) andrefined by MEM/Rietveld method 2.Eventually precise charge densities of was Co(dt)2
obtained .
The powder diffraction pattern of Co(dt)2 was measured at SPring-8, BL02B2 . The
wavelength of incident x-ray was 1.0A. The powder data was indexed using the program
DICVOL on the basis of the first 24 observable peaks , giving the tri clinic unit cell :a=11.7164(2)A, b=10.9496(1)A, c= 7.7319(7)A , a=79.731(1 )" , [3=96.481(2 )" ,y=113.9686(9) 0 . A planer molecular structure model of Co(dt)2. which is similar toNi(tmdt)2 were used in the process of structure determination by GA. The GA analysis was
carried out for both P1 and P-1 triclinic space group. The reliab ility factor of GA solutions
based on weighted profile , Rwp , was 14% for P1 and 15% for P-1 respectively. Eachsolution gave almost identical structure. Then , it is concluded that solution of P-1 spacegroup , which has higher symmetry, was the final result by GA.
The structure refinement by MEM/Rietveld analysis was carried out based on GA result.
The reliability factors of final Rietveld refinement based on Bragg intensities , Rl , andweighted profiles , Rwp , were Rl=6.4% and Rwp=3 .6%, respectively. Each of two extended
TTF-Iigands of Co(dt)2 molecule was distorted in opposite direction and inter moleculardistance from nearest neighbor molecule was as small as 3.12 from Rietveld refinement.
Furthermore , the MEM charge density of cobalt atom was connecting to not only four S
atoms which belong to same molecule but also S atom belonging to nearest neighbormolecule . It was concluded that Co(dt)2 forms a dimeric molecule that two molecules areparallel to each other. It is considered that the dimer formation suppress the magnetic
moment of Co ions by anti-ferromagnetic interactions of two Co(dt)2 molecules .
References
1. H. Tanaka. , et al. , (2001) Scien ce 291, 285-287.
2. M. Takata ., et al. , (1995) Nature 377 , 46 ., M. Takata, et al. , (2001) Z. Kristallogr. 216,
71.

MS14-2
APPLICATIONS OF LARGE 2D DETECTORS FOR NEUTRON POWDERDIFFRACTION.
Alan W. Hewat
lnstitut Laue-Langevin , BP 156X Grenoble Cedex 9, 38042 France (hewat@ill.fr).

1D electronic position sensitive detectors were first developed for neutron powder
diffraction in the late 1960's in Grenoble , and for the first time made it possible to study
very small samples , chemical kinetics etc. using Rietveld refinement. A few years later,
linear wire detectors became available for X-ray powder diffraction. Recently we have built
a large high-resolution 20 neutron detector (super-D2B) , and we have approval for a
project to build an even large high flux 20 neutron detector (DRACULA), with a prototype
already working (019).
In this presentation we will describe some of the new science that might be donewith such detectors, and show that they will allow powder diffractometers on high flux
reactors such as at ILL in France , or the new reactors FRM-11 in Germany and RRR in
Australia , to compete successfully with machines on the new American and Japanesepulsed neutron sources.

MS14-3
SCREENING STABILIZING POLYMERS FOR DRUG DEVELOPMENTUSING VARIABLE TEMPERATURE X-RAY DIFFRACTION
Z. Ping Wu , R. Hart, and D. Stirling
Pharmaceutical Sciences , Pfizer Global Research & Development, 10777 Science Center
Dr, San Diego , CA 92122, USA; (zhen .wu@pfizer.com).

The performance of pharmaceutical solid dosage forms often are affected by thesolid state form of the drug used in the formulation ' . Amorphous materials are often usedin drug formulation due to their higher solubility and absorbability. However thesematerials need to be stabilized with a polymer since they tend to be physically andchemically less stable. We report here a method to quickly screen polymers for use as astabilizer in drug formulation .
The method described here is the Non-ambient X-ray Diffraction (NA-XRD)
technique .2 This is a powerful new tool for identifying new solid forms and characterizing
their stability. This technique allows the x-ray powder pattern of a sample to be recorded
at selected temperatures and relative humidities, where physical or chemicaltransformations of the sample may occur. A commercially available drug lndomecathin
was used as a model in this study. Mixtures of lndomecathin with various polymers wereprepared and their stability was quickly determined under accelerated conditions using
NA-XRD. The results demonstrate that this technique allows rapid identification ofpotential polymers for further evaluation in drug development.
References
1
Chemburkar et al , (2000) Org. Proc. Res. Dev. , 4 , 417.
2
Fawcett et al , (1986) Adv. X-ray Anal. , 29 , 323.

MS14-4
STUDY OF CRYSTAL STRUCTURE IN LaMn 1 _xCux0 3 COMPOUNDS
S. Ravi and Manoranjan Kar
Department of Physics , Indian Institute of Technology Guwahati , Guwahati- 781039 ,India (sravi@iitg .ernet.in)

LaMn0 3 is an antiferromagnetic insulator with antiferromagnetic transition at around141 K [1]. The substitution of Cu in place of Mn can introduce the mixture of Mn 3• and Mn••ion in the compound . The ferromagnetic double exchange interaction between Mn 3• andMn•• in the Mn-0-Mn ( Mn3• - 0 2- - Mn••) network play the key role for ferromagnetic metal(FMM) to paramagnetic insulator (PMI) transition , and the colossal magneto-resistance(CMR) property in the vicinity of FMM to PMI transition temperature in mixed valence
manganite perovskites [2] . Simultaneously, the substitution of Cu in place of Mn will notaffect the crystal structure , as the size of Cu ion is comparable to that of Mn ions. Here wehave reported the crystal structure of LaMn ,_xCu.Q 3 by analyzing XRD patterns . LaMn ,.
xCu.Q 3 compounds were prepared for x =0, 0.1 0, 0.15 , 0.20 and 0.30 by solid-state route.
The final sintering in pellet form was carried out at 12oooc in air for over 60hrs withintermediate grindings. XRD patterns were recorded at room temperature using a Seifert
3003-TT XRD machine by employing CuKe radiation. The samples are mostly in single
phase form . XRD patterns were analyzed with the help of fullprof program by employing
rietveld refinement technique [3]. The patterns for all th e samples could be refined using
Pbnm space group . The typical lattice parameters are found to be a = 5.543A, b = 5.51 oA,
and c = 7.816A for x = 0.15. It has been found that the lattice parameters and unit cellvolume is almost constant for all the samples. It could be due to the two competing
effects, such as smaller ionic size of Mn•• ions compared to Mn 3• ions and larger ionic sizeof cu2• ions compared to Mn3• or Mn•• ions. The average Mn-0 bond lengths and Mn-0Mn bond angles have been calculated from the rietveld refined parameters . The particle
size has been calculated from XRD pattern using the Scherrer formulae [4] . It has beenfound that particle size increases with the increase of Cu concentration . DC electricalresistivity measurements down to low temperature show semiconducting behaviour for all
the samples. Temperature variations of ac susceptibility down to 30K were measured at
an ac field amplitude of 5.30e. The above Cu doped samples show paramagnetic toferromagnetic transitions . The paramagnetic to ferromagnetic transition temperature (Tc)decreases with the Cu concentration . It could be due to the increase of antiferromagnetic
superexchange interaction between the Cu and Mn ions . The reentrant spin glass likebehaviour has been observed at low temperature .
References
1
Wollan , J. E. 0 . and Koehler, W. C. (1955) Phys . Rev., 100 545 .
2Jin, S., Tiefel , T. H., McCormack , M., Fastnacht, R. A. , Ramesh , R. and Chen , L. H.
(1994) Science , 264 , 413 .
3Young , R. A. (1996) "The Rietveld Method" International Union of Crystallography,(New York , Oxford University Press) .
4Taylor, A. (1961) X- ray Metallography (Wiley, New York).

MS14-5
POWDER DIFFRACTION STUDIES OF BISMUTH DOUBLE PEROVSKITE
Ba2AJ+Bs+os
Qingdi Zhou•, Brendan J. Kennedy •• Centre for Structural Biology and Structural Chemistry and Centre for Heavy Metals
Research , School of Chemistry, The University of Sydney, Sydney, NSW , 2006 , Australia(q .zhou@chem.usyd .edu.au)

The double perovskite compounds of Ba 2AJ• B5•Q 6 (A = Bi , Sc, B = Ta , Sb , Bi) havebeen synthesized and their structures have been determined by synchrotron X-ray andneutron powder diffraction techniques. These studies seek to establish the effect of Bi
valence on the structures and phase transitions in these double perovskites. At room
temperature , the compound Ba 2 ScBi0 6 is cubic in space group Fm3m, whereas
Ba 2 BiSb0 6 and Ba 2 BiTa0 6 have a rhombohedral structure in space group R3 . Variabletemperature synchrotron powder diffraction studies show that heating Ba 2 BiTa0 6 result inan , apparently, continuous transition to the cubic structure near 250 °C (Figure 1).
Ba 2 BiSb0 6 becomes cubic above 300 °C. For both these compounds the Bi-0 bonddistances are indicative of trivalent Bi. In comparison , Ba 2 Bip 6 is monoclinic at room
temperature , /2/m, as a result of both BP 11 N charge ordering and tilting of the Bi0 6
octahedral. This undergoes a first order transition near 150 °C to the rhombohedral
structure. These experimental results are consistent with a group theoretical analysis of
the PT in rock-salt ordered double perovskites[1] .
References
1
Howard , C.J. ; Kennedy, N.J .; and Woodard , P.M. (2003) Acta Cryst. 859, 463-471.

MS15-1
MOLTEN SALT SYNTHESIS AND CRYSTALPALLADIUM PHOSPHATES AND ARSENATESSTRUCTURES

OF

Kwang-Hwa Lii ,"·b Ling-1 Hung ,< and Sue-Lein Wang<•Department of Chemistry, National Central University, Chungli ; blnstitute of Chemistry,
Academia Sinica, Taipei ; <Department of Chemistry, National Tsing Hua University,
Hsinchu , Taiwan , R.O.C. (liikh@cc. ncu .edu .tw)

All elements in the fi rst transition series and most elements in the second and third
series form crystalline phosphates. However, few phosphates of the platinum-groupmetals , namely Ru , Os , Rh , lr, Pd and Pt, have been reported . Solid phosphates of
osmium and iridium are actually not known . The structural chemistry of the corresponding
arsenates is even more limited. This presentation reports the results of our exploratory
synthesis of palladium phosphates and arsenates by molten flux reactions . Six
compounds with the general formula A2Pd 3(X20 1)2 (A= monovalent metal cations) and fivedifferent structural types have been characterized . For example , the structure of
Cs2Pd3(P20 7)2 co nsists of discrete Pd 11 0 . squares which are linked by P20 7 groups via
corner-sharing to generate a 3D framework containing 12-ring channels in which cs·
catons are located . Much to our surprise the arsenate analogue , Cs2Pd3(As20 7)2, with thesame general formula adopts a 2D layer structure with the interlayer space filled with cs•
cations. Within a layer there are PdO. squares and As20 1 groups fused together via
corner-sharing. Adjacent layers are stacked such that strings of Pd atoms are formed. The
PdO. squares show eclipsed and staggered stacks with alternate short and long Pd ·.. Pd
distances. The structure of Cs2Pd3(As20 7)2 is shown below.

MS15-2
SPIN DENSITY AND CHARGE DENSITY STUDIES ON AN ORGANICMAGNET
Jey-Jau Leea and Yu WangbaNational Synchrotron Radiation Research Center, Hsinchu 300 , Taiwan ; bOepartment ofChemistry, National Taiwan University, Taipei , Taiwan =jjlee@spring8 .or.jp)
Spin density and electron density studies of organic radical compound have been
carefully investigated by Polarized Neurton diffraction , Neurton diffraction and X-ray
diffraction method at very low temperature =2K, 20 K and 125 K respectively). Electron
density and spin density distribution based on multipole model will be presented .
The PND experiment data are actually measuring the flipping ratio, R, of bragg
reflections , =hkl) . This ratio is defined as the ratio of the diffracted intensities and withincident neutron beam polarized in spin up , lr=hkl) , and down , t=hkl), respectively. The
flipping ratios of a Bragg reflection , R=hkl ) is then given by=
R (hkl )= ..£.

F ;v
' 2 + Sln. ' a F';i + 2 s1. n-' a F N F·· M
1I1

r ;v+ si n2 a F;,, - 2si n2 a FN FM

A total of 585 such flipping ratios are collected up to sin =fl)/ ;1=0 .80 A- 1 . The magnetic
structure factor , FM, deduced from the flipping ratios , is the Fourier component of the spin
density S=r). After the analyses , there are significant spin density distribution =O .O?:e) at thehydrogen atom of the phenyl group .
According to the results of the PND and three MO calculations , Significant spin
density are located at the nitroxide group and they are perpendicular to the N-0 bonds but
directly point toward the hydrogen atom of the phenyl group. The DFT!Dmol calculationon the dimer of this radical also indicates significant spin density population on thehydrogen-bonded hydrogen atom . Based on the spin density measurement and the MO
calculations, the transmittance of the magnetic behavior of the title compound is believed
to be due to the intermolecular hydrogen bond , N-0 .. . H-C and can be well identified .

DFT calcul ati ons
Ex pt.
monomer dim er Xtal PNDFirst Molecule010.52640.5258 .446 .372 1
0.430 IN50.4308 .500 .32 11
H22( H8)0.
0.0025 .005 ·.02
H23( H7)0.
0.00 13 .003
.07
Second Molecule045
0.5045N49
0.4489H66( H8)0.
H67( H7)0.
Figure.spin dens ity distribution
on y= I/4 plan

Tab le. Theoreti ca l and experimental spin density
popul ation on se lected atoms.

MS15-3
A NOVEL ALUMINOBORATE MOLECULAR SIEVERS CONTAINING
OCTAHEDRAL FRAMEWORKS OF 3D TUNNEL STRUCTURE
Jianhua Lin and Jing Ju
State Key Laboratory of Rare Earth Materials Chemistry and Applications, College ofChemistry and Molecular Engineering , Peking University, Beijing 100871 , P. R. China
Qhlin@chem.pku.edu.cn)

A new microporous aluminoborate family , i.e., HAI 3 B6 0 15 (0H) 4 (PKU-1 ), AI 5Bp9 (0H) 3(PKU-5), A1 4 B6 0 15 (PKU-5) and HAI 5 Bp8 (PKU-6), have been synthesized in the boric acid
flux by direct reactions with aluminum salts in a closed system at the temperatures slightly
above the melting point of boric acid . The structures of these aluminoborates were
established by using powder X-ray diffraction techniques . PKU-1 , PKU-5 and PKU-5
crystallize in trigonal structures consisting of borate groups and porous octahedral
frameworks with 18-, 54-and 10-membered octahedral tunnels. In the structures , the Aloctahedra share edges , respectively, in cis- and trans-fashions , forming the octahedral
frameworks . The borate groups , all in triangular geometry, share oxygens with theoctahedral frameworks thus to compensate the negative charge of the frameworks. The
structure principle of PKU-6 is different from that of other members of PKU family. The
aluminum atoms are all 5-coordinated with pyramid geometry. The Al-polyhedra shareedges forming one-dimensional chains that are linked to one-dimensional pore framework
via triangular borate (Bp 7 ) . Two structure units are fundamental in the PKUs structures ,i.e., the 3-membered ring units 5AI+B and AI+5B , which , as we believe , are crucial tostabilize these unusual octahedral frameworks. PKU-5 is stable up to 800°C; while theframeworks of PKU-1 and PKU-5 collapse at about 600 and 400°C respectively. PKU-6
discomposes at about 650 °C. These compounds exhibit typical microporous behavior.
References
1 Jing Ju, Jianhua Lin* , Guobao Li, Tao Yang , Hongmei Li , Fuhui Liao, Chun-K. Loong ,and Liping You , Octahedra-based Molecular Sieves with 18-0ctahedral-atom
Frameworks , Angew. Chern . tnt. Ed. 42 , 5607 (5003); Angew. Chern. , 115, 5765(5003)

MS15-4
MODULATED STRUCTURES IN THE Ta 2 0 5 -W0 3 SYSTEM FROM X-RAY
AND NEUTRON POWDER DIFFRACTION DATA
Siegbert Schmida and Anja Binderb
aschool of Chemistry, The University of Sydney, NSW 2006 , Australia ; blnstitute forInorganic Chemistry, University of Tubingen , Germany (s.schmid@chem .usyd.edu.au-.

Systems that form modulated structures are a fascinating class of materials , whichlack lattice periodicity but may still be perfectly long-range ordered [1] . Such systems exist
across the whole range of chemical disciplines from organic conductors to high-Tc
superconductors and minerals. The importance of modulated structures has beenrecognised , but there have been few systematic studies across composition ranges ofsolid solutions that form modulated structures. Such a systematic investigation is expected
to further our understanding of crystal chemical and structural aspects of modulated
structures as well as the reasons for their existence .
One example for a modulated structure , the wide-range, non-stoichiometric solid
solution (1-x-Ta,O.-xWO,, 0 :<=: x :<=: 0.267 , has been subject to intensive investigation overmany years [2] . Owing to the phase transition at 1360 oc, large single-crystals of L- Ta,O,
were impossible to grow. Thus , attempts were made to stabilise the phase by the additionof other oxides . For WO,, a series of anion-deficient a-UO,-related 'line phases' with basic
structure dimensions very similar to those of L-Ta,O, was found within the compo sition
range (1-x-Ta,o ,.xW0 3 , 0 :<=: x :<=: 0.267 .
As part of a systematic study X-ray and neutron powder diffraction data for anumber of compositions were collected at the Australian National Beamline Facility,
Tsukuba , Japan and at the HIFAR facility , Lucas Heights, Australia , respectively. The
results of the structure refinements using JANA [3] will be presented.
References
1
Withers , R. L., Schmid , S. & Thompson , J. G. (1998-. Prog. Solid State Ch em.
26, 1.
2
Schmid , S., Futterer, K. & Thompson , J. G. (1996-. Acta Cryst. 852, 223 .
3
Petricek, V. & Dusek, M. (2000-. JANA2000, Programs for ModulatedandComposite Crystals , Institute of Physics , Praha , Czech Republ ic.

MS15-5

A CHIRAL METAL ZINCOBOROPHOSPHATE TEMPLATED BY ACHIRALTRIAMINE: SYNTHESIS AND CHARACTERIZATION OF(C 4 N 3H16 )[Zn 3 B 3 P6 0 24 ]'H20
Wei Liu . Hao-Hong Chen , Xin-Xin Yang , Man-Rong Li , Ming-Hui Ge and Jing-Tai Zhao
The State Key Laboratory of High Performance Ceramics and Superfine Microstructure,
Shanghai Institute of Ceramics, Chinese Academy of Science , Shanghai 200050 , P. R.
China (lw@mail.sic.ac.cn)
Organically templated metal borophosphates are of great current interest becauseof their novel structures and potential applications. ' The first example of an organotemplated chiral zincoborophosphate, (C 4 N3 H,6 )[Zn 3 B3 Pp 24 ]·H20 has been hydrothermallysynthesized in the presence of structure-directing agent, DET A. It crystallizes in the
hexagonal system , space group P6 522 , a= 9.6677(14) A, c = 14.860(3) A, y = 120", V =1202.8(3) A3 , Z = 2. The structure is an infinite three-dimensional zeolite-analogous openframework structure built from corner-sharing Zn0 4 , B0 4 and P0 4 tetrahedra. Two types ofchannel systems exist in the structure along the c axis. Besides the large channels built
from the borophophate chains ~ ' {[B 3 Pp 24 ] 9 ·} , the other one-dimensional opening is madeup of two twisted corner-sharing tetrahedral helices connecting through Zn0 4 tetrahedra.
Protoned DET A molecules are arranged along 61 or 65 axis and are located in the freespaces of borophosphate helical chains to form a novel chiral organic-inorganic channel
system. It is the first example of an organically templated borophosphate derivative havingsuch a chiral arrangement of organic molecules in the crystal. The terminal (HpETA) 3•
groups connect adjacent borophosphate helical ribbons via N-H ... O hydrogen bonds
while water molecules are also supported by hydrogen bonds with the organic molecules.
Thermal investigations show that this compound can lose the water molecules in thechannels up to 200oC and obtain a dehydrated microporous phase. The crystalline
dehydration product is a microporous borophosphates with helical hollow channel
structure and can be stable up to 450°C in air, which have a potential application as acatalyst.
References
1 Anthony, K. C ; Gerard, F.; Thierry, L. (1999)Angew. Chem., Int. Ed. Engl., 38 , 3268-?.

\

P01
ANALYSES OF HYDROGEN BONDS IN AMINO ACID- INORGANIC ACID

2:1 COMPLEXES
B.Sridhar • , K.Anitha and R.K.Rajaram••School of Physics ,(ssh iya@yahoo.com)

Madurai

Kama raj

University,

Madurai-625

021 ,

India

In an Amino acid-inorganic acid complex, when the number of hydrogen atoms
attached to the inorganic acid is less than the number of amino acids , the hydrogen atom
liberated from the inorganic acid is shared by the two amino acids through a short 0-H .. . 0hydrogen bond. The following crystal structures , L-methionine, L-aspartic acid , Lphenylalanine , L-proline , L-lysine hydrochloride , L-valine and j3-alanine were grown in a
stoichiometric ratio 2:1 with the inorganic acids like perchloric acid and nitric acid . In thecase of hydrogen bis (L-phenylalanine) perchlorate , bis (L-proline) hydrogen perchlorate ,L-valine L-valinium perchlorate monohydrate , D-serinium D-serine nitrate and bis (Lproline) hydrogen nitrate , the hydrogen bond linking the aminoacid residues may betermed as a nearly symmetric hydrogen bond , from the donor-hydrogen and hydrogenacceptor distances. In the crystal structures of hydrogen bis(L-Iysinium(+))dichloride
perchlorate, hydrogen bis(L-Iysinium(+))dichloride nitrate, hydrogen bis(L-phenylalanine)
nitrate L-methionine L-methioninium perchlorate monohydrate and L-aspartic acid nitrateL-aspartic acid , the hydrogen atoms may be termed as asymmetric bond , since hydrogen
atom is closer to the donor carboxyl group. The structural details of the above complexes
will be presented. A survey of similar compounds, in relation to the geometry of the
carboxylate and carboxylic acid groups, will also be discussed

P02
BONDING AND AGGREGATIONS OF SOME AMINO ACID- INORGANICACID COMPLEXES
B.Sridhar a , K.Anitha and R.K .Rajaram••School of Physics,(sshiya@yahoo .com)

Madurai

Kama raj

University,

Madurai-625

021 ,

India

When the number of amino acid and hydrogen atoms liberated from theinorganic acids is equal , then these free hydrogen atoms , in general , link the aminoacid and the inorganic acid through rather strong 0 -H .. . 0 hydrogen bonding (0 .. . 0
distance - 2.6 A) . In thi s conte xt, the crystal structures of L-threonine , L-tyrosine ,DL-aspartic acid , L-methionine , L-phenylalanine , L-glutamic acid and L-isoleucine
were grown in stoichiometric ratio of 1:1 with inorgani c acids like sulfuri c acid andortho phosphoric acid . The crystal structures were solved using standard
crystallographic methods . The packing diagram of the crystal structure reveals theaggregation pattern in the unit cell. Generally, hydrophobic a-amino acid like valine ,leucine , phenylalanine and norleucine , aggregates as two-dimensional ordered layers.
The examination of the packing diagram of tri (L-isoleucinium) sulfate bisulfate reveals theaggregation of hydrophilic zone interconnected by 0-H .. .0 and N-H ... 0 hydrogen bonds
in a cage like structure . The crystallographic features of the above structures will bepresented.

P03
ELECTRONIC STRUCTURES OF La 1_.sr.Co0 3 EXAMINED BY XMCDMEASUREMENS AT THE Co K ABSORPTION EDGE
Takayasu Hanashima ,a Satoshi Sasaki ,a Norio Shimizu ,a Kouji Yamawaki ,a Takeharu Mori,band Masahiko Tanakab
aMaterials and Structure Laboratory, Tokyo Institute of Technology, Nagatsuta 4259 ,Midori, Yokohama 226-8503, Japan ; blnstitute of Materials Structure Science , HighEnergy Accelerator Research Organization , Oho 1-1 , Tsukuba 305-0801 , Japan(sasaki@n .cc. titech .ac.jp)
The end-member compound LaCo0 3 is considered to be a nonmagnetic
semiconductor in the low-spin state of Co 3 • at low temperature . Magnetic susceptibility
slowly increases with temperature and reaches a maximum of a broad peak at T- 100 K[1] . The nonmagnetic LaCo0 3 is considered to transform to paramagnetic with the spincrossover phenomenon around the temperature. Also, an intermediate-spin ground state
has been proposed to be stabilized for a Co 3• (cf') system in LaCo0 3 or Co4 • (d5 ) in SrCo0 3[2 ,3]. When holes can be doped into LaCo0 3 by substituting Sr for La , the transition of
La 1_xSrxCo0 3 compounds changes from nonmagnetic semiconductor to ferromagnetic
metal for x 2! 0.2 up to the other end-member of SrCo0 3 [4].
We have studied the effect of Sr doping on the magnetic structure of La,_xSrxCo0 3(x =0, 0.2, 0.3, 0.4 , 0.5 and 0.6) by X-ray magnetic circular dichroism (XMCD) at the Co K
absorption edge .
A negative peak of XMCD was clearly observed for pure LaCo0 3 atE= 7.719 keVwithin the threshold region , suggesting the existence of the intermediate-spin state of Co 3•.
A positive peak appeared at E = 7.723 keV of the main edge by Sr substitution for La in
LaCo0 3 (x 2! 0.2) , which is in accord with the observation of Co 4• on X-ray absorption nearedge structure . A negative peak observed at the pre-edge suggests the hybridization andsuper-exchange interaction between Co 4 • and neighboring Co 4• with the positive mainedge peak. The dispersion-type XMCD signals at the main edge can be rationalized withthe double-exchange interaction between Co 3• and Co 4 •.

References
1
Yamaguchi , S. , Okimoto , Y. , Taniguchi , H. and Tokura , Y. (1996) Phys. Rev. B 53 ,R2926-R2929 .
2Goodenough , J.B. (1971) Mater. Res. Bull. 6, 967-976.
3
Potze , R.H. , Sawatzky, G.A. and Abbate , M. (1995) Phys. Rev. B 51 , 11501-11506.
4
Jonker, G.H. and van Santen , J.H. (1953) Physica (Amsterdam) 19, 120-130.

P04
COW FORMATION IN AN INCOMMENSURATE PHASE OF 1T-TaS2
STUDIED BY X-RAY THERMAL DIFFUSE SCATTERINGYo Machida ,a Satoshi Sasaki ,ab Takayasu Hanashima ,a Kouichi Ohkubo ,a Kouji Yamawaki ,a and Masahiko Tanakac•Department of Materials Science and Engineering , Tokyo Institute of Technology,
Nagatsuta, Yokohama 226-8503 , Japan; bMaterials and Structures Laboratory, Tokyo
Institute of Technology, Nagatsuta, Yokohama 226-8503 , Japan ; clnstitute of Materials
Structure Science , KEK , Oho , Tsukuba 305-0801 , Japan (sasaki@n.cc.titech.ac.jp)
Charge-density-wave (CDW) formation is considered as the consequence ofthe electron-phonon interaction. The layered transition-metal dichalcogenides such as
TaS 2 have attracted much interest because of their unique electron properties associatedwith quasi-two-dimensional characters and phase transitions related to the CDW
formation. 1 T-TaS 2 has three stable phases , which are an incommensurate phase (IC), a
nearly commensurate phase (NC) and a commensurate phase (C) with phase-transition
temperatures of 350 K (IC to NC) and 190 K (NC to C) [1 ,2] .
We have studied the dispersion curves of phonons by means of synchrotron xray thermal diffuse scattering (TDS), which relates quantitatively to the frequency andwavelength of traveling elastic waves in a crystal. Since the thermal vibration of the lattice
can be described by a linear superposition of these waves , the TDS intensity gives thephonon dispersion curves (3] . The TDS intensity of the IC phase was measured at theBL-10A station of Photon Factory. Single crystals of 1 T-TaS 2 were synthesized by thechemical vapor-transport method (4] . A single crystal in dimensions of 5 x 5 x 0.2 mm 3
was mounted with a small furnace in a vertical-type four-circle diffractometer. A satellite
reflection was observed at q = 0.28a* + c*/3. The TDS intensity around the 1 -1 0
reciprocal lattice point was measured within the temperature range between 300 and 460
K.
Least-squares analyses in terms of lattice dynamics yielded the dispersion
curves of phonons, which revealed the Kahn anomaly both in the longitudinal acoustic(LA) and transverse acoustic (TA11 ) modes. It is suggested that the rotation of the orderingvector in the nearly commensurate phase at low temperature is triggered by the softened(TA11 ) modes .
References1
Wilson , J.A. , DiSalvo , F.J. and Mahajan , S. (1974) Phys. Rev. Lett. 32, 882-885 .
2Scruby, C.B. , Williams , P.M. and Parry, G.S. (1974 ) Phil. Mag. 31 , 235-274
3Holt, M., Wu , Z., Hong , H., Zschack, P. , Jemian, P., Tischler, J. , Chen , H. , andChiang , T.-C. (1999) Phys. Rev. Lett. 83 , 3317-3319 .
4Endo, T. , Nakao, S. , Yamaguchi , W ., Hasegawa , T. and Kitazawa , K. (2000) Solid
State Commun . 116, 47-50 .

P05
CRYSTAL STRUCTURE OF ETHYL 4-(2,5-DIOX0-2,5-DIHYDR0-1HPYRROL-1-YL)BENZOATE
Vasu•, K.A.Nirmala * b , M.Vishwasc, Deepak Choprad• vivekananda degree college Malleshwaram west Bangalore-560055 ,b Reader in physics, Bangalore University, Bangalore-560056 ,cGovernment college of Pharmacy Bangalore-560027 ,d Indian Institute of Science , Solid State Chemistry Unit, Bangalore-560012 ,(vasusriranga@rediffmail .com)
Succinimides are important medicinal agents in the therapy of diseases such as
tuberculosis , convulsions and hypertension[1 ,2] . This application of the compound
attracted us to take up the crystal and molecular structural work by X-ray diffraction
method to know the conformational aspects. The title compound Ethyl 4-(2 ,5-dioxo-2 ,5dihydro-1 H-pyrrol-1-yl)benzoate is a derivative with an ester-substituted aryl maleimide.
The yellow compound crystallizes in monoclinic system of space group P2,/c with numberof molecules per unit cell four. The X-ray data was collected on SMART AXX ceo
detector. The structure was solved using WINGX(1.64 ). The lattice parameters are
a=12 .028(6)A, b=7.358(4 )A, c=13 .561 (7)A, ~=96.364(7) 0 • The refinement gave a final Rvalue 0.044 for 2328 unique reflections.
The angle between the mean planes passing through the benzene ring and themaleimide ring is 41 .4(1 )0 , indicating the steric repulsion between the carbonyl groups andthe benzene ring. The dihedral angle is small [2 .5(2) 0 ] in a similar structure withoutcarbonyl groups[3] .
Molecular chains are observed , via two different C-H ... O hydrogen bonds runningalong the a and c-axes , respectively. The C-H ... O hydrogen-bonded chain down the aaxis involves the ester carbonyl group , whereas the other down the c-axis employs one of
the carbonyl groups of the maleimide ring.
We acknowledge DST(IRHPA) and Prof.T.N .Guru Row IISc., (SSCU) for providing
diffraction data. One of the authors Vasu acknowledges Vivekananda Degree College
principal for the support.

Fig : Molecular structure of the compound with 50% probability ellipsoid
References1
Pandey, U.K. , Lohani ,H.C.&Agrawai .,A.K.(1984. 1ndian Drugs , 21 ,135-138
2
Crider,M. &Edward0.M.(1977)J.Med.Chem.20,405-409.
3Paulus ,E.F .&Rivo ,E.(1988) Acta Cryst C44 1242-1244.

P06
X-RAY DIFFRACTION, XANES AND XMCD STUDIES ON THE SITE
PREFERENCE AND VALENCE STATE OF Co AND Fe IONS IN IRON
COBALTITE
Kouji Yamawaki ,a Norio Shimizu ," Satoshi Sasaki ," Takayasu Hanashima ,a Tomoaki
Watanabe ,• Masahiro Yoshimura ," and Masahiko Tanakab•Materials and Structures Laboratory, Tokyo Institute of Technology, Nagatsuta 4259 ,Midori-ku, Yokohama 226-8503 , Japan ; blnstitute of Materials Structure Science , HighEnergy Accelerator Research Organization , Oho 1-1 , Tsukuba 305-0801 , Japan(shimizu@lipro.msl .titech.ac.jp).
Iron cobaltite , Fe 12 Co1.80 4, is a mixed-valence compound with the spinel structure.
The cation distribution between tetrahedral A and octahedral B sites as well as thevalence states of Co and Fe ions are indispensable to the interpretation of the magnetic
properties of cobaltites.
The site occupancy of Fe and Co ions was determined with the anomalous
scattering effects of synchrotron X-rays. Although it is generally difficult to grow single
crystals of cobaltites, fortunately single crystals of Fe 12Co 1p 4 could be synthesized by thehydrothermal reaction . Diffraction data were collected at A = 1.6182 A, by using a verticaltype four-circle diffractometer at BL-10A in the Photon Factory. The chemical formulaobtained in site-occupancy refinements is [Fe 0_72 (4po 028 ]A[Fe 0..8Co 152] 9 0 4.
In order to determine the valence states of Fe and Co ions, the measurements of
X-ray absorption near edge structure (XANES) and X-ray magnetic circular dichroism(XMCD) spectra were performed at Fe K and Co K edges at BL-3A. The Fe K XANES
spectra indicate that all Fe ions exist as trivalent ones. On the other hand , a ratio ofdivalent and trivalent Co ions was estimated to be Co 2• : Co 3• = 1 : 8 from the Co K
XANES data. The intensity variation of XMCD signals was used to determine the valencesof Co ions on individual sites . Since the main-edge peak of XMCD spectra has beenreported to originate Co 2• ions in the B sites for a series of iron-cobaltite studies [1], theoccupation of Co 2• in Fe 12 Co 1.p 4 was determined from the estimation of the peak height.
The results shows that only Co 2• ions occupy the A sites.
Thus , it is finally suggested that the most plausible chemical formula is[Fe3•o72(4)Co2•o.2sJA[Fe3• o..aCo2•o.n CoJ• o.soJBO4.
References
1
Kita , N. , Shibuichi , N. and Sasaki , S. (2001) J. Synchrotron Rad., 8, 446-448.

P07
FERROMAGNETIC ORDERING MODEL OF A Cox Ti 1_p 2 THIN FILM (x =0.07)
Norio Shimizu ,• Satoshi Sasaki ,a Takayasu Hanashima ,a and Kouji Yamawaki••Materials and Structures Laboratory, Tokyo Institute of Technology, Nagatsuta 4259 ,Yokohama 226-8503 , Japan (shimizu@lipro.msl.titech .ac.jp).
A Co-doped Ti0 2 (anatase) thin film was discovered as a ferromagnetic andtransparent semiconductor having Tc above 400 K [1] . The ferromagnetic properties wereconfirmed by hysteresis on the M-H loop from magnetic response measurements ,hysteresis of Kerr loops or vibrating sample magnetometry.
Recently, fluorescence X-ray magnetic circular dichroism (XMCD) and absorption
spectra at the Co K absorption edge were measured for a Co-doped anatase thin film on a
LaAI0 3 (001) substrate [2]. Negative-to-positive dispersion-type XMCD spectra wereclearly observed at E = 7.725 keV, suggesting the ferromagnetism at room temperatureand unlikelihood on the existence of Co-metal clusters. XANES spectra support the Co 2•
oxidation state and participation of a partial structure of ilmenite-type CoTi0 3 .
We have proposed a crystal structure of Co-doped anatase films and theferromagnetic order scheme by Co-Ti-0 polysynthetic twin lamellae. A (012) CoTi0 3 layerinterstitially distributes parallel to the (001) plane of anatase and replaces a quarter of theanatase cell at intervals of three and half times of the cell along the c axis. Thus , oursample has a Co01Ti0 2 ratio of 1/(4n+1) (n = 3) and c = (2n+1 )c.n/2, which gave the best
magnetic property as a result of the combinatorial crystal growth. The cell dimensions are
a = 7.6 , b = 3.8 and c' = 33 A (c = 66 A). The thin film forms an antiphase domain (APD),
having (1) a repetition of 3.5 unit cells of Ti0 2 toward the can axis , (2) an antiphaserelationship by 2 1 screw rotation and (3) an out-of-step of a.n/2 for the APD boundary.
The above geometrical relationship is known as the polysynthetic twinning or
tropochemical cell-twinning (TCT) [3]. The magnetic moments of Co 2 • in CoTi0 3 areferromagnetically coupled within a layer, where the direction of the magnetic moment lies
along the c axis perpendicular to the plane of the Co-Ti-0 layer. The adjacent Co-Ti-0
layers are far enough to prevent the antiferromagnetic interaction . The isolated Co-Ti-0
layer characterizes the magnetic moments of Co 2• by in-plane ferromagnetic ordering andis defined as the "ferromagnetic lamella".
References
1
Matsumoto, Y. eta/ (2001) Science 291 , 854-856 .
2
Shimizu , N. eta/. (2004) J. Phys. Soc. Jpn , 73 , in press.
3
Takeuchi , Y. (1997) Tropochemical Cell- Twinning , MSMR Monographs, Terra
Scientific Publishing Co ., Tokyo.

P08
CRYSTAL STRUCTURE OF 2-AMINO-N-(2-CHLOROPHENYL)-5,6DIHYDR0-4H-CYCLOPENTA[b]THIOPHENE-3-CARBOXAMIDE.
K.A.Nirmala ! Vasu ,b S.Mohan ,c J.Saravanan ,d Deepak Chopra••professor, dept. physics, Bangalore University, Bangalore-560056 , bVivekananda degreecollege Malleshwaram west , Bangalore-560055 , cP.E.S college of Pharmacy
Hanumanthanagar Bangalore-560050 , dM.S.Ramaiah college of pharmacy,
Bangalore-560054 , •indian Institute of Science , Solid State Chemistry Unit,
Bangalore-560012 , (nirmalaka47@yahoo .com)
Schiff bases and their derivatives of thiophene possess antibacterial , antitubercularand antifungal properties(1 ,2,3]. Sulphur containing Schiff bases are most effective. The
title compound shows the above mentioned properties. In view of this application of thecompound , crystal and molecular structure work by X-ray diffraction method was taken up
to understand the conformational aspects. The title compound synthesised by refluxing
cyclopentanone and o-chloroacetanilide with diethylamine, sulphur powder with ethanol.
Pale green crystals of the compound were grown by slow evaporation method using N,Ndimethyl Formam ide and ethanol (1 :1) as the solvents. The single crystal X-ray data wascollected on a SMART AXX CCD detector. The crystals are in monoclinic system ofspace group P21/c with two crystallographically independent molecules . The structure wassolved using WINGX(1.64).
The lattice parameters a =9.939(3)A, b=29.449(8) A,
c=9.747(3) A, f3=111 .912(4) 0 • The refinement gave a R-value 0.0568 for 5215 uniquereflections.
The torsional angles between the thiophene moiety and the chlorophenyl ring inthe 2 molelcules is -178.9(3) 0 and 173.3(3) o respectively, thus indicating extensive
electron delocalization over the entire molecule. There exists strong
and highly
directional intra and inter-molecular N-H ... O hydrogen bonds which is responsible for thepacking of molecules leading to needle crystals.
We kindly acknowledge DST(IRPHA) and Prof.T.N .Guru Row IISc. ,(SSCU) in
helping the data collection .

Referecnes
1
Csaszar,J ., &Morvay,J.(1983). Acta Pharmaceutica . Hungarica. 53(5), 121-128.
2
Lakshmi ,V .V. , Sridhar, P.& Polasa ,H.(1985). Indian J. of Pharmaceutical Sciences.
47 ,202-204.
3
Cohen ,V.I. , Rist,N.& Duponchei ,C.(1977) J. of Pharmaceutical Sciences. 66 , 13221334.

P09
DEGREE OF DISORDER IN SPINEL-TYPE (Mn,Zn,Fe)p 4 EXAMINED BY
THE TWO-WAVELENGTH ANOMALOUS DISPERSION METHOD
Syoichi Sakurai ,• Satoshi Sasaki ,a Kouji Yamawaki ,a Takayasu Hanashima ,a and Norio
Shimizu••Materials and Structure Laboratory, Tokyo Institute of Technology, Nagatsuta 4259 ,Yokohama 226-8503 , Japan (sasaki@n .cc.titech .ac.jp)
The spinel structure is divided into two extreme types in cation distribution
between tetrahedral A and octahedral B sites. One is normal-spinel type of [Y]A[ZZ] 8 0 4
and the other is inverse-spinel of [Z]A[YZ] 8 0 4 , where Y and Z are different kinds of cations .
There are some reports on the existence of temperature dependence on the cation
distribution in Mn ferrites [1 ,2] . It is an obvious result that the Mn-Zn-Fe ferrite synthesized
by the Bridgman method and used for videotape recorder 's heads belongs to a normalspinel type of [Mn 054 Zn 034 Fe 0 , 2]A[Zn 0 _0 ,Fe , 99 ] 8 0 4 [3]. However, recent EXAFS analyses
have reported different cation distributions such as [Mn 025Zn 0 _36 Fe 040 ]A[Mn 040 Fe, 59] 8 0 4(aqueous solution ; heating at 500oC) and [Mn 021 Zn 052 Fe 027 ]A[Mn 034 Fe , 66] 8 0 4 (solid
reaction) [4].
Since the cation distribution attracts our interest in understanding the magnetic
properties of ferrites , it has been investigated with the two-wavelengths anomalous
dispersion (TWAD) method of synchrotron x-rays [5] . Single crystals were grown inevacuated silica tubes at 1373 K for 180 hours. The chemical formula was obtained fromthe EDX analysis . The cell dimension and u parameter are a = 8.5000(5) A and u =0.261 0(2) , respectively. Diffraction experiments for Mn 0 _80Zn 0 _, 8 Fe 20 p 4 were performed
using a spherical single crystal of 0.1 mm in diameter. Synchrotron experiments werecarried out in a four-circle diffractometry at BL-10A of the Photon Factory.
The
wavelengths used in this study are 1.7535 and 1.2934 A. which are 0.01 A longer than
The TWAD method isthose at Fe K and Zn K absorption edges , respectively.
indispensable to a ternary Mn-Zn-Fe system and allowed us to determine the cation
distribution accurately with a large difference in atomic scattering factors . Least-squares
refinements gave a final chemical formula of [Mn 0 _7 ,Zn 0 _, 0 Fe 0 19 ]A[Mn 009 Zn 008 Fe, d 8 0 4 ,showing that about 17% of Mn and Zn ions exists as the inverse-spinel ingredient.
References
1
Yasuoka , H., Hirai , A. , Shinjo, T. , Kiyama , M. , Bando, Y. and Takada , T . (1967) J.
Phys. Soc. Jpn . 22 , 174-180.
2
Ohara , H. , Mizobuchi , T. , Matsumoto, K. and Sasaki , S. (2000) Ferrite : Proc. of 8thIntern . Conf. Ferrite (ICF-8) , 223-225
3Okita , A ., Saito , F., Sasaki , S. Toyoda , T. and Koinuma , H. (1998) Jpn. J. Appl.
Phys. 37 (6A), 3441-3445.
4
Calvin , S. , Carpenter, E.E., Harris, V.G. and Morrison , S.A. (2002) Appl. Phys. Lett.
81 (20) , 3828-3830 .
5Tsukimura , K. and Sasaki , S. (2000) Phys. Chem. Minerals 27 , 234-241.

P010
X-RAY STRUCTURAL STUDY OF IN-PLANE ATOMIC ARRANGEMENTS
IN THE LAYERED COMPOUNDS MxTiS2 (M=Cu, Ni, Co)
Ken-ichi Ohshima, Yoshinobu Kasuga, Tomoko Kusawake , Makoto Yasuda and Hiraki
Uratani
Institute of Materials Science , University of Tsukuba , Tsukuba 305-8573 , Japan(ohshima@bk.tsukuba.ac.jp)
The layered disulphides of transition metals are intercalated with various ions andmolecules between the sulphur layers which are normally separated throughout the Van
der Waals interaction. These intercalation compounds are of interest because of their
quasi-two-dimensional (20) properties and because of their application as electrodes incell.
We have performed the X-ray diffraction study to measure composition dependencesof diffuse or superlattice scattering for single crystals of MxTiS2 (M=Cu , Ni , Co) compounds
for understanding the local or ordered arrangements of the intercalated M atoms at room
temperature.
1) CuxTiS2 (x<0.37) : Two types of diffuse maximum due to the different in-plane
correlations of Cu atoms appeared , depending on the composition. The maxima
appeared at 1/2,0,1/2, 0,1/2,1/2 & equivalent positions and at 1/3,1/3,1/2,2/3 ,2/3 ,1/2
and equivalent positions for the lower content and for the highest composition ,respectively. For the intermediate composition , the types of diffuse scattering coexist,
with intensities depending on the composition. We expect the following in-paneordered phases : 2x2 and (3 112x3 112)R30° structures in Wood notation , whose
stoichiometric composition x corresponds to 1/4 and 1/3, respectively [1 ,2].
2) NixTiS2 (x<0.37): One type of diffuse maximum appeared at 1/3,1/3, 1/2, 2/3, 2/3 ,1/2
and equivalent positions at around x=0.33. There is no extra scattering at lower
content.
3) CoxTiS 2 (x<0.33) : Two types of superlattice reflection due to the atomic orderedarrangements of Co atoms appeared at 1/2,0, 1/2, 0, 1/2, 1/2 & equivalent positions
and 1/3, 1/3, 1/2, 2/3,2/3 ,1/2 & equivalent positions for x= 1/4 and 1/3, respectively. As
expected in the compounds Cu xTiS2, in-pane ordered phases, 2x2 and (3 112x3 112 )R30°
structures, are confirmed to exist in the compounds CoxTiS2 at x=1/4 and 1/3.
Observed in-plane diffuse intensities are compared with the calculated ones , using alinearized mean-field approximation for the correlations of a binary Ising system welldeveloped above Tc developed by Class and Moss [3] .
References
1 Kusawake , T. , Takahashi , Y., Ohshima , K. and Wey, M.-Y. (1999) J. Phys.:
Condens. Matter 11 , 6121-6128 .
2
Kusawake , T. and Ohshima , K. (2003) J. Phys. Soc. Jpn . 72 , 2829-2831.
3
Moss , S.C. and Clapp , P. C. (1966) Phys. Rev. 142, 418-427.

P011
CRYSTAL STRUCTURE OF 7-METHYL 6, 8-DINITRO 4-BROMOMETHYLCOUMARIN
K.V.Ajuna Gowda•·c, T.N .Guru Rowb, N.C.Shivaprakashc and M.V. Kulkarnid•Department of Physics, S.J.C.I.T. ,Chickballapur, Kolar-562 101 , India , bSolid State andStructural Chemistry Unit, Indian Institute of Science , Bangalore-560 012 , India,
coepartment of Instrumentation , Indian Institute of Science , Bangalore-560 012 , India,
dDepartmentof Chemistry, Karnataka
University, Dharwad-580
003 , India(shiv@isu .iisc.ernet. in).

Attempted nitration of 7-methyl-4-bromomethyl coumarin has resulted in theformation of 6 ,8-nitro product which has been confirmed by spectral methods[1]. The
compound crystallizes as colourless plates in orthorhombic with space group Pbac andcell dimensions a =8.122(2), b = 11 .091 (4 ), c =27 .723(6) A. The Structure was solved by
SHELX97 program (Sheldrick 1997) and refined to a R factor of 0.059 . We have noticed
that the allylic bromine is not in the plane of coumarine but is oriented at an angle of 104°
with respect to the pyrone ring . The compound stabilzes with presence of four Br ... Br
weak interactions. The details of weak interactions are discussed in this paper.

References
1
Clayton A, (191 0), J Chern Soc , 97 , 1397- 1399.

P012
CRYSTALLOGRAPHIC ANALYSIS OF HYDROGEN BONDING IN SERIESOF CHOLEST -BASED STEROIDAL MOLECULES
Dinesh* and Rajnikant
Condensed Matter Physics Group , Department of Physics , University of Jammu,
Jammu Tawi 180 006 , INDIA. (dine_nesh@rediffmail.com)
The work reported in this paper is based on a comparative analysis of C-H ... O, NH . .0 and N-H .. . N hydrogen bonded interactions which play an indispensable role inorganic molecular assemblies. Both intra and intermolecular interactions have been
examined in case of a series of cholest-based steroidal molecules . In view of some recent
spurt in literature on weak interactions and their role in organic molecular assemblies , wehave selected the C-H ... 0 hydrogen bond as a prototype of the entire interaction type andhave analysed it in case of series cholest-based steroids whose three-dimensional
molecular and crystal structures have been elucidated by us. Taking into account thegeneralized distance and angle cut-off criterion for the intra and intermolecularinteractions , as proposed by Desiraju and Stenier (1999) , we have found that both thesekinds of interactions in cholest-based steroids fall in the range of "intermediate to strong
and weak interactions". Graphical projection of interaction data further authenticate ourfindings . Details will be presented.
References
Desiraju , G.R. & Steiner, T. (1999) The weak hydrogen bond in structural
1
chemistry and biology, IUCr, Oxford Press, 10-11 .

P013
NEUTRON STUDIES OF CLUSTER BEHAVIOUR OF Pd 40 Ni 22 _5 Fe 175 P20
SPIN GLASS
E.P. Gilbert,a R. Woodward ,b D.H . Yu ,a and R. A. Robinson••Bragg Institute, Australian Nuclear Science and Technology Organisation , Lucas Heights,
NSW , 2234 , Australia ;bSchool of Physics , University of Western Australia , Perth , 6009 , Australia.
Magnetic metallic glasses have enormous technological importance in , for example ,magnetic recording , magnetic refrigeration and the construction of electrical transformers
and motors. Traditionally these amorphous materials were prepared by melt spinning (1 06
K s·' ) to form ribbons.
Bulk magnetic metallic glasses based on the quaternary alloy Pd-Ni-Fe-P exhibit
interesting phase behaviour depending on temperature and applied magnetic field . For thealloy of Pd 40 Ni 225 Fe 175 P20 , paramagnetic, superparamagnetic, ferromagnetic and spinglass regions are all evidenced [1] . It is proposed that the complex phase transitions inthese kinds of materials may be due to the materials not being truly amorphous. The
possible large-scale chemical inhomogeneities within the alloy may lead to clustering ofmagnetic ions. On cooling , frustration due to competing interactions between clusters may
result in the observed spin glass-like behaviour.
We will present our first neutron-studies , employing small-angle neutron scattering ,with polarised incident beam , on the alloy of Pd 40 Ni 225 Fe 175 P20 as a function of temperature(RT to 5K) and applied magnetic field (0 to 5T).

References
1
Shen T. D., Schwarz R. B. and Thompson J.D., J. Appl. Phys. 85 , 4110-4119 ,
1999.

P014
AB-INITIO PHASING AT 1.7A RESOLUTION OF A PROTEINFERREDOXIN I BY COMBINED REAL SPACE- RECIPROCAL SPACEAPPROACH
Krishna Chowdhury," Soma Bhattacharya , band Monika Mukherjee a
80epartment of Solid State Physics , Indian Association for the Cultivation of Science ,Kolkata 700 032 , India; bOepartment of Physics , St. Xavier's College , Kolkata 700 016.
(sspmm@iacs.res.in)Ferredoxin I, an iron containing protein , is capable to interact and form electrontransfer complexes with many different proteins and it's three dimensional structure is offundamental importance to help these interactions. The structure of Ferredoxin I has beensuccessfully redetermined ab-initio from a single native data set by a combined real
space- reciprocal space approach. The protein contains 97 amino acid residues (733 nonH atoms) and a (2Fe-2S] cluster with 81 solvent water molecules. The complex crystallizes
in space group P2,2,2, with cell parameters a=31.0 , b=39.2 , c=83 .5A and Z=4 . X-ray
diffraction data (1] extending to 1.7A was obtained from protein data bank (PDB code :1a70).
The direct method approach of MUL TAN88 generated several thousand phase sets
at 1.7A with 1000, 1500, 2000 largest lEI values. The phase set with lowest mean phaseerror (MPE) of 68 .91 o gave an E-map that indicated positions of two Fe atoms.
Successive weighted Fourier maps could reveal (2Fe-2S] bridge and few small fragments
but not the entire protein model. The initial phase estimates using (Fe+4S) and (Fe+6S)
coordinates obtained from the Fourier maps were subjected to 400 - 500 cycles ofrefinement with options fo r low density elimination and histogram matching using the
program PERP (2]. MPE dropped from 62 .2° to 45.5" and the map correlation coefficient(MCC) increased from 0.421 to 0.651 for 3922 reflections with IEI>1 .0. The resultant
phase set could yield an interpretable electron density map. The study reveals that evenwith knowledge of phases for 2% of the scattering material the real space - reciprocal
space phasing approach can lead to proper model building for proteins diffracting at low
resolution of 1.7A.
References
1
Binda , C., Code , A. , Aliverti , A. , Zanetti , G. , and Mattevi , A. (1998) Acta Cryst .
054 , 1353 - 1358.
2
Refaat, L.S ., Tate, C ., Woolfson , M.M. (1996) Acta Cryst. 052 , 1119- 1124.

P015
DIFFUSE NEUTRON SCATTERING FROM d-BENZIL, C1P 10 0 2 , USING
TIME-OF-FLIGHT LAUE DIFFRACTION
T. R. Welberrya D. J. Goossensa W. I. F. Davidb M. J. Gutmannb M. J. Bullb and A. P.
Heerdegena
aResearch School of Chemistry, Australian National University, Canberra ACT 0200 ,Australia; biSIS , Rutherford Appleton Laboratory, Milton , Didcot, Oxfordshire , UK(goossens@rsc.anu.edu.au).

Diffuse neutron scattering data have been recorded for the molecular crystal dbenzil , C 14 D,p 2 , using time-of-Flight Laue diffraction on SXD and PRISMA at ISIS. Using
SXD it was possible to access a large fraction of the total three-dimensional reciprocal
space out to a Q value of 15 A-1 , using only four individual exposures and by making useof the -3m Laue symmetry of the crystal. By binning the scattered data according toincident neutron energy, patterns were obtained using neutrons in the range of -20 meV
to 150 meV, which showed little sign of inelastic effects and so could be compared withpreviously analysed X-ray data. For neutron energies of <20 meV, inelastic effects we reobserved , which have been used to obtain an estimate for the energy of phonons
associated with a particular vibrational mode . A model previously derived from analysis of
X-ray data observed over a limited range of Q has been used to calculate neutron patterns
over the full Q range . Comparison with the neutron data showed that while the modelfrom X-ray data gives a good description of the form of the diffuse patterns , themagnitudes of the atomic displacements are underestimated by a factor of -2.25.
We will discuss our latest results which test our model by using SXD to explore thetemperature dependence of the diffuse scattering. Further, PRISMA has been used tomeasure phonon energies directly, allowing comparison with those energies inferred fromthe diffuse scattering .

P016
S-SAD PHASING BY OASIS2004
J. W . Wang , Y. X Gu , C. D . Zheng , F. Jiang , and H. F. FanChinese Academy of Sciences, Institute of Physics, Beijing , 100080, P. R. China
Uwwang@cryst.iphy.ac.cn) .

OASIS [1] is a direct-method program in the CCP4 suite [2] for resolving the phaseambiguity in single-wavelength anomalous diffraction and in single isomorphous
replacement of proteins. It has recently been modified in order to make the phasing
procedure more efficient and automatic. The main modifications include : (1) automaticallyadjust the standard deviation D in the expression of lack-of-closure error; (2) fitting thedirect-method figures-of-merit to a uniform distribution before they are output to density
modification.
The new version of OASIS has been tested with sulphur single-wavelength
anomalous diffraction (S-SAD) data from the protein Glucose isomerase and the protein
Xylanase [3] . Diffraction data sets used in the following test were kindly provided by Dr. Z.
Dauter.
Glucose isomerase crystallizes in space group 1222 with unit cell a=92 .90 , b=97 .95
c=1 02 .71 . Diffraction data at 2A resolution were collected with synchrotron radiation at-1.=1.54A. The Bijvoet ratio (<l:IF>/<F>) is 0.60%, which is a rather low value among theothers . S atoms were located by the program SHELXD , then the phases of the whole setof reflections were derived by OASIS. After density modification using the program DM in
the CCP4 suite , the average phase error was decreased to 44°. The automatic modelbuilding program ARPiwARP found 386 residues of the total of 388.
Xylanase crystallizes in space group P2, with unit cell a=41 .19, b=67 .18 c=50 .88.
beta=113 .5°. Diffraction data at 1.63A resolution were collected with synchrotron radiation
at -1.=1 .743A. The Bijvoet ratio (<l:IF>I<F>} is 0.69%. The 5 independent S atoms werelocated by SHELXD. OASIS phasing followed by OM led to an average phase error of 55°.
The resultant map is easily interpreted .
The new version of OASIS will be released in due course , presumably first on the
webpage http://cryst. iphy. a c.en .
References
1
Hao, Q , Gu , Y X , Zheng , C. D. & Fan , H. F. (2000) J Appl. Cryst. 33 , 980-981 .
2Collaborative Computational Project, Number 4. (1994). Acta Cryst. 050 , 760-763 .
3
Ramagopal. U. A ., Dauter, M., Dauter Z. (2003) Acta Cryst. 094, 1020-1027.

P017
TREATMENT OF EXPERIMENTAL ERRORS IN DIRECT-METHOD SAD
PHASING
S. Huang•, J . W. Wangb, Y. X. Gub, D. C. Xian•, H. F. Fanb & M. M. Woolfson c•institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100039, China .
blnstitute of Physics, Chinese Academy of Sciences , Beijing 100080, China. cDepartmentof Physics , University of York, Y01 5DD , UK(shuang@cryst.iphy.ac.cn)
In treating experimental errors in the magnitude of normalized structure factors , aweighting function is given to the three phase structure invariants IE.h·Eh. ·Eh·h·l· The
function is expressed as.!.

W= exp (- kV 2 )where
V= ( a,E,. )'+ ( £,_,.
~ E,, )'+(0" E,)'* (~)'£ "_,.

E h.
and k is a constant to be determined in each test case.
Experi mental single-wavelength anomalous diffraction (SAD) data from two proteins
were used in our test:
Azurin [1] crystallizes in space group P4 1 22 with unit cell a=b=52.65, c=1 00.63A.
There is one Cu atom (anomalous scatterer) in the asymmetric unit. The Bijvoet ration<LJF>I< F> at .-t=0.97 A is 1.44%.
Rusticyanin [2] crystallizes in space group P2 1 with unit cell a=32.34 , b=60.68,
c=38.01A, fr-=1 07.82° There is one Cu atom (anomalous scatterer) in the asymmetric unit.
The Bijvoet ration <LJF>/< F > at .-t=1 .376A is 2.36%.
Phases were derived by the program OASIS and improved by the program DM , bothare supported programs of the CCP4 suite [3]. Test for each SAD data set was performedby comparing results of two identical phasing processes , one with and the other without
the weighting fun ction. Preliminary results showed that the use of the weighting function
led to smaller averaged phase error and better electron density maps.
£ ,.

References
1 Dodd , F. , Hasnain , S. S. , Abraham , Z. H. , Eady, R. R. & Smith, B. E. (1995). Acta
Cryst. D51, 1052-1064.
2 Harvey, 1. , Hao,Q. , Duke , E.M. H., lngledew,W. J. & Hasnain , S. S. (1998). Acta Cryst.
D54 , 629-635.
3 Collaborative Computational Project, Number 4. (1994 ). Acta Cryst. 050 , 760-763.

P018
EFFECT OF SULFUR-ANOMALOUS SCATTERING SIGNAL ON SAD
PHASING IN THE PRESENCE OF IRON ATOMS
D. Q. Yaoa, J. R. Chenb, J. W. Wangb, C. D. Zhengb, Y. X. Gub, F. Jiangb, H. F. Fanb & D. C.
Xi anaa Institute of High Energy Physics , Chinese Academy of Sciences , Beijing 100039, China .

Institute of Physics , Chinese Academy of Sciences , Beijing 100080, China.
(dqyao@cryst.iphy.ac.cn)bRecently there is a revival of single-wavelength anomalous diffraction (SAD) phasing
in protein crystallography. So far in practice, successful SAD phasing accompanied with aBijvoet ratio (<IDFI >/< F>) greater than 0.6%. The present work is to examine the effect of
weak sulfur-anomalous scattering signals on SAD phasing in the presence of muchstronger anomalous scattering atoms Fe. Test was performed with SAD data of the protein
CAUFD . The experimental diffraction data was kindly provided by Dr. Z. Dauter.
CAUFD [1] crystallizes in space group P4 3 2 12 with unit cell a=b=33.95 , c=74 .82A.
Diffraction data at 0.94A resolution were collected with the synchrotron radiation at/=0 .88A. There are 8 Fe and 8 S atoms in the asymmetric unit. The Bijvoet ratio
contributed from the Fe-substructure is 3.6%, while that from the S-substructure is 0.55% .
Phases were derived based on the known substructure of anomalous scatterers by the
program OASIS and improved by the program DM , both are supported programs in the
CCP4 suite [2] . The result of SAD phasing based on Fe-anomalous scattering signals andthat based on "Fe+S"-anomalous scattering signals were compared. Although either result
led to nearly the complete structure, the electron density map of the latter contains
evidently fewer spurious peaks . This implies that the contribution of sulfur-anomalous
scattering signals with Bijvoet ratio as low as 0.55% is not negligible even in the presenceof much higher anomalous scattering signals from Fe with the Bijvoet ratio as large as
3.6%.
Comparison of phase errors , correlation coefficients and electron density maps will beshown.

References
1 Dauter, Z., Wilson , K. S. , Sieker, L. C., Meyer, J. & Moulis , J. -M. (1997) . Biochemistry,
36 , 14493-14502.
2 Collaborative Computational Project, Number4. (1994). Acta Cryst. 050 , 760-763.

P019
SYNCHROTRON X-RAY POWDER DIFFRACTION STUDY OF THE
STRUCTURAL PHASE TRANSITION IN CaBr2
Brendan J. Kennedy • and Christopher J. Howard b•school of Chemistry, The University of Sydney, Sydney, NSW 2006 Australia ; bAustralian
Nuclear Science and Technology Organisation , Private Mail Bag 1, Menai , NSW 2234 ,Australia (cjh@ansto.gov.au).

The structures of CaBr2 have been investigated using high resolution powder
synchrotron X-ray diffraction methods between room temperature and 800 °C. At room
temperature CaBr2 has an orthorhombic CaCI 2-type structure (Pnnm Z = 2) with a =6.8847(1) b = 6.5806(1) and c = 4.3477(1) A.
Heating above 560 oc results in acontinuous transition to a tetragonal rutile type structure (P42 /mnm Z = 2) with a =6.81 095(7) and c = 4.41770(5) A at 650 °C. Investigation, through either spontaneous
strain or octahedral tilt angle, suggests that the transition is close to second order innature , although the contribution from the sixth order term in the Landau potential cannot
be neglected.

P020
CHARACTERIZATION OF THE!).' PHASE- MATRIX INTERFACE IN 1420
ALUMINIUM ALLOYS BY SAXSChai Zhi-Gang
Beijing Aeronautical Technology Research Center, Beijing 100076
People's Republic of China (chaizg@sina.com.cn)

The interface between the 8' phase and matrix in 1420 aluminium alloys , whichwere treated by 1) aging or 2) retrogression and re-aging (RRA) methods , have beencharacterized by means of the small angle X-ray scattering (SAXS) technique . The results
indicate that a transition zone exists between the o' phase and matrix for both treatment
methods. The existence of a transition zone implies that the 8' phase is precipitated byspinoidal decomposition. The results also show that the RRA treatment can effect rapid
disappearance of the interfacial transition zone.

P021
CATION ORDERING IN PENTLANDITE (Fe,Ni)(Fe,Ni) 8 S8Kia S. Wallwork•, Allan Pringband Christophe Tenailleaub•ANSTO , PMB 1, Menai , NSW, 2234; bSouth Australian Museum , North Terrace,
Adelaide , SA , 5000 (kiw@ansto .gov.au)

Pentlandite is the primary nickel mineral in nearly all Ni-sulphide deposits and is thusof enormous economic importance.
Pentlandite adopts a cubic structure based on a ccp array of S atoms with metals in
1/ the tetrahedral
sites and in 1/ 8 of the octahedral sites . Thus the formula can be written
201
as M M 8 S8 where M' is the metal in tetrahedral sites and M0 is a metal in the octahedral
site. The structure consists of cubic clusters of tetrahedral metal ions [M 8 S6] that are linked
to MS 2 octahedra. Natural pentlandite contains roughly equal amounts of Fe and Ni,
together with small amounts of Co and Cu , but pure Fe and Ni end-members are notstable.
Single crystal X-ray diffraction studies of two natural samples indicate that Fe can bepreferentially ordered into the octahedral site , a process that occurs at lower temperatures[1 ,2] . Tsukimura (1] showed that the ordering was destroyed by annealing at 250 oc.
Strain is associated with ordering of Fe/Ni between octahedral and tetrahedral sites andleads to an increase in the cell parameter. Etschmann eta/. [3] and Wang eta/. (4]annealed a number of synthetic pentlandite samples at low temperature (150- 200 °C} forperiods of up to five months and noted changes in the cell parameters that indicate somecation ordering may have occurred.
Using this collection of low temperature anneal/quench samples we have determinedthe cation distribution between the octahedral and tetrahedral sites and thus be able todetermine the kinetics of cation ordering and the activation energy . This
pentlandite/pyrrhotite system is one of the few sulphide systems in which cation orderinghas been investigated . The low temperature (250 °C) at which the cation ordering is
destroyed is indicative of the high metal mobility in sulphides at low temperatures . Thiscan be compared with the rock forming silicates were cation ordering is destroyed attemperatures around 600 °C .
Due to the similarity of the Fe and Ni scattering curves for X-rays high resolution
powder diffraction data were collected at a number of different energies in order to exploit
anomalous dispersion effects .
References
1
Tsukimura , K. (1989) Mineralogical Journal, 14, 323-337.
2
Tsukimura , K. and Nakazawa, H. (1984) Acta Crysatallographica , B40 , 364-367 .
3Etschmann B., Pring , A. , PutnisA. , Grguric, B.A ., and Studer, A . (2004) American
Mineralogist, 89 , 39-50 .
4Wang , H., Ngothia, Y., O'Neill , B., Etschmann , B. and Pring A. (2003) Chemeca
2003 , Proceedings Volume.
5
Zhang , Y., Wilkinson , A. , Nolas, G. , Lee, P. and Hodges, J. (2003) Journal ofApplied Crystallography, 36 , 1182-1189.

P022
THREE-BEAM DIFFRACTION ANOMALOUS FINE STRUCTURE OF THIN
FILMS
Hsueh-Hung Wu ," Yen-Ru Lee ," Hsin-Hung Chen ," Wen-Shien Sun ," and Shih-Lin Chang••Department of Physics , National Tsing Hua University, Hsinchu , Taiwan , 300 , R.O.C.
(d893308@oz.nthu.edu.tw)
Different from the usual two-beam OAFS (diffraction anomalous fine structure), we
have recently developed the multi-beam OAFS (MDAFS) for observing the local structuralenvironment of resonant atoms. With three-beam diffraction data for different photon
energies , the visibility Rv of the intensity asymmetry related to the phases of structurefactor triplets involved in the three-beam diffraction can be determined. Analysis based on
the dynamical diffraction theory and XAFS gives fine structures of OAFS spectra . In thispaper, the three-wave diffractions of (1 00) CdTe thin films epitaxially grown on the (1 00)
lnSb substrates are measured for different photon energies covering all the Ledges of theconstituent atoms. The crystallographic phase of structure-factor triplets and theresonance phase shifts influenced by the substrate could be analyzed to give the interface
structures in relation to the CdTe and lnSb. Using this MDAFS technique, we have also
extracted the information about the fine structures of Cd and Te around the interface.

P023
CRYSTAL STRUCTURES OF ANHYDROBARAKOL AND
ANHYDROBARAKOL HYDROCHLORIDE; AN EVIDENCE OF
EXCEPTIONAL C=O/C-OH QUINONE CHARACTERISTIC
P. Chimsook•, N. Ngamrojnavanich•, C. Chaichantipyuthb, N. Chaich i\C, P. Kongsaereed, A.
Petsom•, N. Muangsin•*•Research Centre for Bioorganic Chemistry, Department of Chemistry, Faculty of Science ,Chulalongkorn University, Bangkok 10330, Thailand , "Department of Pharmacognosy, Faculty of
Pharmaceutical Sciences , Chulalongkorn University, Bangkok 10330, Thailand , <Department of
Physics, Faculty of Science and Technology, Thammasart University, Bangkok 12121 , Thailand ,"Department of Chemistry, Faculty of Science, Mahidol
University, Bangkok 10400, Thailand(44723304@Student.chula .ac.th , Ch_Piti@hotmail.com)
Barakol(1 ), (3a,4-dihydro-3a ,8-dihydroxy-2 ,5-dimethyl-1 ,4-dioxaphenalene) [1 a, 1 b] ,is an active component extracted from Cassia siamea. It is used in traditional medicines
for treating insomnia and other medicinal conditions [2] . Barakol is unstable and easily
converted to anhydrobarakol(2). In order to study their physiochemical , physiological andpharmacological properties , anhydrobarakol hydrochloride (3) , a stable salt form , isprepared. However, these properties are not clearly understood [3a , 3b , 3c, 3d] . The
spectroscopic data including NMR and IR are unusual and ambiguous [1 b] . The
absorption band of C=O stretching at 1676 em·' was significantly red shifted from that of atypical C=O frequency (-1710 em·' ). Moreover, the IR spectrum of 3 also shows
unexpected n(C=O) stretching at 1671 cm-1 , similar to that of 2. Therefore, it is necessary
to obtain pure forms of 1 and 2, and also their crystal structures in order to explain theirproperties.
We present a preparation method to obtain a pure form of 2 and the first successful
crystal structures determination of 2 and 3. They were crystallized in a monoclinic system ,with space group P2,1c and P2 ,1n , respectively. Their crystal structures reveal aninteresting C=O and C-OH characteristic. As a consequence , the NMR and IR
spectroscopic data can be explained. The molecular structure of 2 , shows the elongated
C=O bond distance of 1.285(3) A, which is longer than a normal carbonyl bond of 1.22 A.
For the crystal structure of 3, it is interesting that C-OH bond distance of 1.3351 (6) A issignificant shorter than that of a normal C-OH of hydroquinone (1.40 A) [4], and dramatic
longer than that of C=O in 2 .
Referrences
1(a) Hassanali-walji , A. , King , T.J. , Wallwork , S.C. (1969) J.Chem.Soc. ChemCommun .12 ,678. (b) Bycroft, B.W ., Hassanali-walji , A., Johnson , A.W ., King , T.J. (1970) J.Chem .Soc.
12, 1686-1689.
2
Kinghorn , A.D., Balandrin , M.F. (1992) Human Medicinal Agents from Plants (American
Chemical Society , Washington , DC).
3(a) Thongsaard , W., Deachapunya, C., Pongsakorn , S., Boyd , E.A. , Bennett, G.W.,
Marsden , C.A. (1995) Br.J.Pharmacol. 114, 284p. (b) Thongsaard , W., Deachapunya, C.,
Pongsakorn ,S.,
Boyd ,
E.A. ,
Bennett,
G.W .,
Marsden ,C.A.
(1996a)Pharmacoi.Biochem.Behav. 53 , 753-758. (c) Fiorino , D. , Treit, D., Menard , D., Lermer, L.
and Phillips , A. (1998) Behavioural Pharmacology 9, 375-378. (d) Sukma , M. ,Chaichantipyuth C., Murakami Y. , Tohda M. , Matsumoto K. , Watanable H. (2002) Journalof Ethnopharmacology. 83 , 87-94.
Gilesdie, R.J ., Popelier, P.L.A. Oxford New York : Oxford University Press , 2001 .
4

P024
THE CLEAVAGE OF DIPEPTIDE$ BY Co(lll) COORDINATIONCOMPOUNDS
Ivan Bernal*, Manas Saha and Uday Mukhopadhyay
Chemistry Department, University of Houston , Houston , Tx 77204-5003 .
(chem4m@pop .uh.edu)
Cleavage of peptide bonds occurs when [Co(tren)CI2]+ or [Co(trien)CI2]+ (tren =tris(2-aminoethyl)amine , trien = 1,4,7 ,10 tetraaza- decane) are allowed to react with
dipeptide molecules such as b-alanyi-L-histidine (carnosine) , glycyi-DL-methionine and Lalanyi-L-alanine at pH -7 .5. The cationic complexes that contain a fragmented amino-acidresidue were isolated as the perchlorate salt or the mixed chloride perchlorate salt. balanyi-L-histidine (carnosine) reacts with [Co(tren)CI2]+ to give the [Co(tren)(histidine)]2+1
and [Co(tren)(b-alanine)]2+ 2. Glycyi-DL-methionine reacts with [Co(tren)CI2]+ or[Co(trien )CI2]+ to produce [Co(tren)(methionine)]2+ 3, [Co(tren)glycine]2+ 4 or[Co(trien)(methionine)]2+ 5 and [Co(trien)(glycine)]2+ 6. Reaction between [Co(trien)CI2]+and b-alanyi-L-histidine produces [Co(trien)(histidine)]2+7 and a free b-alanyl molecule.
to
yield
or
[Co(trien)CI2]+
reactswith
L-alanyi-L-alanine[Co(tren)CI2]+[Co(tren)(alanine)]2+ 8 or [Co(trien)(alanine)]2+ 9. All these cationic complexes werecharactersied by a nalytical data , spectral studies and crystal structures . The structural
illustrations provide important information regarding the mechanism and the streochemical
aspects of such reactions . [Co(tren )(histidine)]2+ 1 crystallizes in the enantiomorphic
space group P212121 . The circular dichromism spectrum for 1 suggests that a very small
extent of racemization of the amino acid takes place during the cleavage reaction between[Co(tren)CI2]+ and b-alanyi-L-histidine. 2 and 5 crystallize in P21 /c and 3, 8 in P21 /nspace groups , respectively. 7 and 9 crystalize P212121 and P21 , respectively. Circulardichroism spectral studies suggest that appreciable racemization of the amino acid takes
place during the reaction between [Co(trien)CI2]+ and b-alanyi-L-histidine and complete
racemization was observed in case of reaction between [Co(tren)CI2]+ and/or[Co(trien)CI2]+ and L-alanyi -L-alanine .

P0025
STRUCTURAL AND CONFORMATIONAL STUDIES OFDIHYDROPYRIMIDINES
G.Y.S.K. Swamy and K.Ravikumar
Laboratory of X-ray Crystallography, Indian Institute of Chemical Technology, Hyderabad
500 007 , India (swamygundimella@yahoo.com)
Quinazolin-4(1 H)-ones commonly known as benzpyrimidones , form an importantclass of heterocyclic compounds. Substituted quinazolin-4(1 H)-ones possess a wide rangeof pharmacological activities , such as antibacterial [1] and anti cancer[2]. Reported herearecrystalstructureof2-(4-Dimethylamino-phenyl)-1-phenethyl-2 ,3-dihydro-1 Hquinazolin-4-one and 1-Phenethyl-2p-tolyl-2,3-dihydro-1 H-quinazolin-4-one . The structural
analysis provides an opportunity to study biological activity and its implication in the
structural requirement needed for binding to the receptors.
The most important aspect of the molecules concern from the pharmacological pointof view is the disposition of the key functional group, which in turn depends on
conformation of the central pyrimidine ring. The central dihydropyrimidine ring in both thestructures are affected by conjugation. The sum of the valance angles around the nitrogenatoms N1 ,N2 & N3 is 360°, indicating that the state of hybridization of these is sp 2 . The
DHP ring is puckered in such a manner that the atoms N1 ,C6,C5,C3, & N2 are coplanarwith the sixth atom C1 is displaced 0.605 A(0.18A for compound II ) above the leastsquares plane . The conformation of pyridine ring can be described as a sofa withasymmetric parameters 6.C 1= 6.09(compound I) & 4.73(compound II). Ring planarity withrespect to torsion angles was correlated to pharmacological activity. The results werecompared with related structural data. The phenethyl group has a fully extended
conformation with respect to the central pyrimidine ring(N2-C11-C17-C13 174.95(3)0 &179.3(2)0 for compounds I & II respectively). The dimethyl amino group of compound I is
coplanar wth the phenyl ring with which it is attached and positioned equatorially at C1 ofthe dihydropyrimidine ring . This is defined by the average magnitude of C3-N2-C1-C12
and C6-N1-C1-C12 torsion angles(175 .34(2)0 ). In the crystal packing, pseudo dimmers
are forming along the a-axis through N-H-... 0 hydrogen bonding. Other ring
conformations along with correlations with other similar structures will be presented.
References1
Ager, I.R., Harrison , D.R. , Kennewell , P.O . & Taylor, J.B. (1977). J. Med. Chem.
20 , 379-386.
2
Skula, S.K ., Agnihotri , A.K. & Chowdhary, B.L. (1981). Indian Drugs ,19, 59-60.

P026
TWO- AND THREE- DIMENSIONAL ORGANICALLY TEMPLATED OPENFRAMEWORK LANTHANIDE SULFATES: EFFECTS OF "LANTHANIDECONTRACTION" ON THE FRAMEWORK ARCHITECTURES**
Jianq-Gao Mao and Yan-Ping Yuan
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of
Matter, Chinese Academy of Sciences , Fuzhou 350002 , P. R. China (mjg@ms.fjirsm.ac.cn)
Materials with open-framework and microporous structures are promising candidates forhybrid composite materials in electro-optical and sensing applications in addition to theirpotential applications in the areas of catalysis, ion exchange, intercalation chemistry,
photochemistry, and materials chemistry.1 1· 21 The study of metal open architectures making use ofother oxy-anions such as group 16 elements has started to be flourishing since the pioneering
works of Rao et al. on the preparation of organicall y templated open-framework cadmium
sulfates.1 31 The exploration for the organically templated metal sulfates has been expended tolanthanide and actinide metals recently, which exhibit different coordination chemistry from thatof transition metals. An open framework solid of scandium sulfate-phosphate was reported by
W right's group.14 1One-, two- and three-dimensional org anically templated lanthanum(lll)) sulfateshave also been structurally characterized , the open frameworks isolated are closely related tothe "structure directing" template cations as well as the reaction conditions .1 51 Herein we report
two Nd(lll) sulfates with layered and 3D open frameworks , and a layered Er( lll ) sulfate, namely,
three-d imensional {C 2 H10 N2},Nd 2(S0 4 ) 5 (H,0) 2 1, {C 2 H10 N2}3 Er2 (S0 4 ) 6 (H 2 0) 2 2 and {C 4 H16 N3 }Nd(S0 4 ) 3(H,0) 3 with a layered stru cture.
All three lanthanide sulfates we re synthesized by a similar method . A mixture ofla nthanide(( lll ) oxide, sulfuric acid, organic amine and 10 ml of water with a molar ratio of Ln :amine : sulfate= 1: 3 : 14 was sealed into an autoclave equipped with a Teflon liner (25 ml) andheated at 110 °C for 2 days. Needle shaped crysta ls of 1, 2 and 3 were obtained as pure phases
based on XRD powder diffraction and element analysis. Their structures have been establishedby sing le crystal diffraction.JBJ
References

A. K. Cheetham , G. Ferey, T. Loiseau , Angew. Chern. Int. Ed. 1999 , 38, 3268.
J. Zhu, X. Bu , P. Feng , G. D. Stucky, J. Am. Chern. Soc. 2000 , 122, 11563.
(a) A. Choudhury, J. Krishnamoorthy, C. N. R. Rao , Chern. Cornrnun. 2001 , 2610 ; (b) G.
Paul, A. Choudhury, C. N. R. Rao , J. Chern. Soc. Dalton Trans. 2002 , 3859 .
I. Bull , P. S. Wheatley, P. Lightfoot, R. E. Morris, E. Sastre, P. A. Wright, Chern . Commun.
42002 , 1180.
(a) Y. Xing , Y. Liu , Z. Shi , H. Meng , W. Pang , J. Solid State Chern. 2003 , 174, 381 ; (b) Y.
5
Xing , Z. Sh i, G. Li , W. Pang , Dalton Trans. 2003 , 940; (c) T. Bataille, D. Louer, J. Mater.
Chern. 2002 , 12, 3487.
Crystal data : C 4 H24 N4 Nd 2 0 22 S'i, 1, Mr = 929.05, monoclinic, P2 ,fc with a = 6.6051 (2) A, b =6
17.0238(7) A, c = 20.4648(8) A, {3 = 94.921 (2) V = 2292.66(15) A3, Z = 4, f.1 = 5.045 mm-1 ,P calo = 2.692 g em·'- C 6 H 34 N ~ E r 2 0 26 S 6 , 2, Mr = 1133.27 , orthorhombic, Pbca with a =9.6460(1) A, b = 19.9459(4) A, c = 30.3455(6) A, V = 5838.42(18) A3, Z = 8, f.l = 6.254
mm-1 , P calo = 2.579 g em·'- C 4 H 18 N 3 Nd0, 3 S ~, 3, Mr = 556.63 , monoclinic, P2 , with a =V = 758.2(1) A3, Z = 2, f.l =6.6380(1) A, b = 10.361 (1) A, c = 11 .050(1) A, {3 = 93.808(4)3.913 mm·', P cald = 2.438 g cm·3 . Unique reflections: 1, 3988(R,,1 = 4.72%); 2 , 5158(R 1, 1 =6.65%); 3, 3519(R1, 1 = 2.07%). Observed reflections (1>2cr(l)): 1, 3102 ; 2, 4386 ; 3, 3389.
Final R1 , wR2 for observed data : 1, 0.0589 , 0.1031 ; 2 , 0.0437 , 0.0817; 3, 0.0244, 0.052 1.
GOF : 1, 1.155; 2, 1.184; 3, 1.046.
**This work was supported by National Natural Science Foundation of China (No . 20371047)
1
2
3

0

,

0

,

P027
THE CRYSTAL STRUCTURES OF HYDRAZINIUM 2,3PYRAZINEDICARBOXYLATES, N2 H5 Hpyz(C00) 2 , (N 2 H5 ) 2 pyz(C00) 2 andN2 H 5 Hpyz(C00) 2 .H 2 pyz(C00) 2
T . Premkumar,a S. Govindarajan ,"* and Nigam P. Rathb•Department of Chemistry, Bharathiar University, Coimbatore 641 046 , India; bOepartmentof Chemistry, University of Missouri-St. Louis , MO 63121 , USA(premsrf@yahoo.co.in)Thecrystalstructuresofhydraziniumhydrogen-2,3-pyrazinedicarboxylate
N2 H5 Hpyz(C00)2 (1 ), dihydrazinium 2,3-pyrazinedicarboxylate, (N 2 H 5 ) 2 pyz(C00) 2 (2) andhydraziniumhydrogen-2 ,3-pyrazinedicarboxylate
2,3-pyrazinedicarboxylic
acid ,
N2 H5 Hpyz(C00) 2 . H2 pyz(C00) 2 (3), where H2 pyz(C00) 2 = 2,3-pyrazinedicarboxylic acid , havebeen investigated by three-dimensional single-crystal X-ray data , collected at -25, -50 and-130°C, respectively. While Crystallographic data for salt 1 are orthorhombic, space group
P2 ,2,2, witha = 6.8321 (2), b = 19.2716(4 ), c = 25.6913(6) A, Z = 16 and final R factorof 0.1688 based on 8141 independent reflections, 2 are monoclinic, space group P2 ,fc with
a= 8.0171 (3), b = 15.3659 (7), c = 8.1431 (4) A, ~ = 94.952 (3) 0 , Z = 4 and final R factor of
0.0892 (!, = 0.071073 A) based on 1968 independent reflections. The salt 3 crystallizes in thetriclinic space group P-1 with a = 7.3542 (9), b = 7.9617 (9),c = 8.3895 (1 0) A, Z = 2 andfinal R factor of 0.0621 based on 1727 independent reflections. The structures of all the salts
suggest that each contains N 2 H 5• cation and a residue of Hpyz(C00) 2·/pyz(COO)/ anion. In
addition to the above, the salt 3 contains one molecule of parent acid. Though it has been
speculated, such a type of acid rich hydrazinium salts has not been isolated so far. For the firsttime , we have not only isolated the same in the solid state but also studied crystallographically.
Further, it is worth to mention here that, for the first time a successful attempt has been madeto synthesize aforesaid all the three types of hydrazinium salts with
2,3-pyrazinedicarboxylic
acid and proved crystallographically. It is observed that, in all these salts, there is a common
arrangement of molecular packing. In all , there is an anionic chain running along one of thecrystallographic axes formed through0-H ... 0 and/or N-H .. .0 hydrogen bonds. The
hydrazinium ions sit at the space between the pyrazinedicarboxylic moieties in the crystal latticeso as to form multiple-hydrogen bonds leading to molecular network. The results will bepresented .

P028
NEW TEN COORDINATED LANTHANUM 2-PYRAZINECARBOXYLATEDIHYDRATE CONTAINING HYDRAZINIUM CATION
S. Govindarajan •*, T. Premkumar •, V. Manivannan b, K.R. Radhakrishnan c and Jonathan
W . Steed d•Department of Chemistry, Bharathiar University, Coimbatore 641 046 , India; bDepartmentof Physics, Presidency College , Chennai , 600 005 , India; <Department of Physics ,Government Arts College , Kumbakonam 612001 ,India ; dDepartment of Chemistry , Kings
College , Strand , London , WC2 R2LS , UK.
(drsgovind@yahoo.co.in)New
dihydrazinium
lanthanum
2-pyrazinecarboxylate
dihydrate ,(N 2 H5 ) 2 [La(pyzC00) 5 ].2Hp, (pyzCOO = 2-pyrazinecarboxylate) has been synthesized and its
solid state structure determined from single crystal X-ray study. The crystals are monoclinic,
space group P2 ,fn with a = 16.401 8 (4 ), b =22.8727 (6), c = 14.9608 (9) A, ~ = 102.660 (2 t, Z
= 8 and R = 0.0592 . The structure analysis shows that the crystals consists of N2H5• cations,water molecules and the [La(pyzC00) 5)2· anions. The asymmetric part contains two
crystallographically independent lanthanum atoms having similar coordination . Interestingly,
each lanthanum atom has ten coordination formed by five 2-pyrazinecarboxylate (bidentate
chelate) ligands, via its N, 0 bonding moieties. The other pyrazine N atom present in the ring is
not involved in coordination. The N2 H5• ions and the water molecules are not coordinated to themetal. Coordination numbers from six to twelve have been established in lanthanide
compounds but ten coordination appears rarely. It is worthwhile to mention here that, the ten
coordination of hydrazinium lanthanide complexes with carboxylate anions have been observed
for the first time. The structure is built up by lanthanum ions joined by 2-pyrazinecarboxylategroups forming two-dimensional sheets parallel to (001) plane . The space between the sheets
is occupied by hydrazinium ions and lattice water molecules. The sheets are held together by
the network of hydrogen bonds involving N2 H5 • ions, lattice water and 2-pyrazinecarboxylate
oxygens. The complex anions are stacked one above the other along c-axis. As a whole theN-H ... 0 and Ow-H ... 0 hydrogen bonds.
structure is stabilized by N-H .. .Ow, N-H ... N,
Further, from the X-ray powder patterns, it is evident that the corresponding Ce complex isisostructural with the titled compound. The results from the IR and thermoanalytical studies arein accordance with these isostructural groupings.

P029
LADDER NETWORKS IN INCLUSION COMPLEXES OF 4,4-BIS(4HYDROXYPHENYWCYCLOHEXANONE
Srinivasulu Aitipamula ,a Ashwini Nangia ,a Mariusz Jask61ski ,b and Ram Thaimattamb
aSchool of Chemistry, University of Hyderabad, Hyderabad 500 046 , India ; bCenter for
Biocrystallographic Research , IBCh , Polish Academy of Sciences and Department of
Crystallography, Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780
Poznan , Poland . (che078s@uohyd.ernet.in).

Molecules with symmetrical molecular scaffold , a degree of rigidity, and goodhydrogen bonding groups (OH , COOH , C=O) form open framework structures . For
example , 1,1-bis(4-hydroxyphenyl)cyclohexane includes a variety of guest molecules [1].
We have undertaken a systematic study of 4,4-bis(4-hydroxyphenyl)cyclohexanone , 1,
and its inclusion complexes . The crystal structure of 1 has two independent molecules in
the crystallographic asymmetric unit and the network associated with one of the symmetry
independent molecules encircles the other molecule through 0 - H· ··O and C- H···Ohydrogen bonds [2] . Inclusion complexes of 1 form two types of ladder networks
assembled from the T-shaped leeton. In one case , molecules of 1 form the ladder networkand the guesUsolvent molecules bind to the host framework (G ,). In the second type ,water expands the host framework along the ladder rungs and guesUsolvent molecules
are included in the voids (G 2 ) . These structures represent two variants of ladder hostguest adducts built from a T-shaped leeton [3] . TGA/DSC measurements confirm thethermal stability and host-guest stoichiometry.

OH@ 1 = anilin e, phenol@ 2 = o-creso l+water, m-creso l+wa ter,p -creso l+water, 2-chl o ropheno l+wa ter
References
1
Caira , M. R. , Horne, A. , Nassimbeni , L. R. and Toda , F. (1997) J. Mater.
Chem. 7 , 2145-2149 .
2
Aitipamula , S. , Desiraju , G. R., Jaskolski, M., Nangia , A. andThaimattam , R. (2003) CrystEngComm , 5, 447-450.
3Kumar, V. S. S., Nangia , A ., Kirchner, M. T. and Boese , R. (2003) New
J. Chem. , 27, 224-226.

P030

rr-STACKING IN NOVEL FLUORESCENT NAPHTHALIMIDE SYSTEMSJim Simpson , C. John McAdam , Joy, L Morgan and Brian H Robinson
Department of Chemistry, University of Otago , P.O. Box 56 , Dunedin , NEW ZEALAND
Usimpson@alkali.otago.ac.nz)

Efficient energy transfer between redox and/or photoactive centres is an important
goal for new materials incorporating both organic and organometallic species because of
their potential technological applications. 1,8-naphthalimides are excellent candidates ascomponents of donor acceptor arrays and , with appropriate substitution of thenaphthalimide moiety, offer the possibility of significant charge separation in the excitedstate [1 ,2].
In the course of this work we have obtained the crystal and molecular structures ofseveral naphthalimide derivatives with the general formula shown in the diagram [R = Me ,C6 H4 CN , CH 2 Fc (Fe = (11 5 -C 5 H4 Fe(11 5-C 5 H5 ) , R = H, piperidine , E-CH=CH-piperidine , -C=CFc, -C= C-2 , 3,4 , 6-tetra-0-acetate-~-0-glucopyranoside , R . = H, N0 2 ] . A common threadis the stabilisation of these solid state structures by offset rr-stacking interactions involving
the naphthalimide rings , with substituents on the dicarboximide N-atoms and thenaphthalene rings oriented to optimise the stacking interactions.
Interestingly, while the corresponding naphthaldiimides with R = Fe or Fc-CH 2 substituents on the imide N atoms can be prepared , the products are found to be totally
intractable green solids that are insoluble in a wide range of solvents. It is postulated thatstrong rr-stacking interactions promote aggregation in these materials.
References
1
McAdam , C.J ., Robinson , B. H. and Simpson , J. (2000) Organometallics 19 ,3644-3653
2
McAdam , C.J. , Morgan , J.L. Robinson , B.H. , Simpson , J., Rieger, P.H. , andRieger, A.L. (2003) Organometallics 22 , 5126-5136

P031
DL-THREONINE AND DL-PHENYLALANINE COMPLEXES WITH
TRICHLOROACETIC ACID
K.Rajagopal•, R.V.Krishnakumar", K.Ravikuma r" and S.Natarajand•Department of Physics, Saraswathi Narayanan College , Madurai-625 022 , India, "Department of
Physics, Thiagarajar College , Madurai- 625 009 , cLaboratory of Crystallography, Indian Instituteof Chemical Technology, Hydrabad-500 007 , India , dQepartment of Physics, Madurai Kamaraj
University, Madurai-625 021 , India (s_natarajan50@yahoo.com)
Amino acids and their complexes are of great chemical and biological interest. Hence, wehave undertaken systematic and precise X-ray crystallographic investigations on several
complexes of amino acids involving carboxylic acids with a view to study the geometry of aminoacid molecules in different crystalline environments. This paper describes the crystal andmolecular structures of DL-Threonine and DL- Phenylalanine with trichloroacetic acid.
Trichloroacetic acid represents a class of simple organic molecules of the type R-CO, H(monocarboxylic acids) and assumes importance in the formation of hydrogen bonds with aminoacids owing to the presence of a highly 'participating ' carboxylic acid group and a relatively'passive' R group (CI 3 , in the present case). Crystal structure elucidation of trichloroacetic aciditself was carried out in our laboratory recently (1]. The crystal structure elucidation of complexesof amino acids viz. , DL-valine , DL-methionine , L-Proline , 13-alanine and L-Phenylalanine, withtrichloroacetic acid were also reported [2-6]. Interestingly, these complexes may also be depicted
as proton transfer complexes of the type A.B. where A is a amino acid and B is a carboxylic acid.
Single crystals of the compounds were grown from saturated aqueous solution containing
respective amino acids and trichloroacetic acid in a 1:1 stoichiometric ratio. DL-Threoninium
trichloroacetate (C 4 H10 N o; . C2 Cl 3 O,-) crystallizes in the monoclinic system , Space group P2 1with a = 10.329(1) A. b = 10.427(1) A, c = 10.780( 1) A, 13 = 103.12(1)0 and Z = 4. DLPhenylalaninium trichloroacetate (C 9 H12 N o; . C2 Cl 3 O,-) crystallizes in the monoclinic system ,space group C2/c with a = 18.820(4) A, b = 16.511 (3) A, c = 10.053(2) A, 13 = 111 .27(3) 0 and Z =8. The structures were solved by direct methods and refined by full-matrix least squares on F2 with
R values 0.033 and 0.056 , respectively. In both the structures , amino acid molecules exist as
cations and trichloroacetic acid molecules as anions. The symmetry related amino acid cations
and trichloroacetate anions are held together by N---H ... O and 0---H ... O hydrogen bonds inaddition to van der Waals interactions . The details of molecular aggregation and hydrogenbonding pattern will be presented .
References
1
Rajagopal , K. , Mostad , A. , Krishnakumar , R. V., Subha Nandhini , M. &Natarajan , S. (2003) Acta Cryst. E59 , o316-o318.
Rajagopal , K., Krishnakumar, R. V. , Subha Nandhini, M , Mostad , A. &2
Natarajan , S. (2002) Acta Cryst. E58 , o279-o281 .
Rajagopal , K., Krishnakumar, R. V., Mostad, A. & Natarajan , S. (2003) Acta
3
Cryst. E59 , o31-o33.
Rajagopal , K. , Krishnakumar, R. V. , Mostad, A. & Natarajan , S. (2003) Acta
4
Cryst. E59 , o277-o279.
Rajagopal , K. , Krishnakumar, R. V. , Subha Nandhini , M. , Mostad, A. &5
Natarajan , S. (2003) Acta Cryst. E59 , o206-o208.
6
Rajagopal , K. , Krishnakumar, R. V. , Subha Nandhini , M. , Cameron , T. S. &Natarajan , S. (2003) Acta Cryst. E59, o1084-o1086.

P032
COMPARATIVE INVESTIGATION FOR THE CRYSTAL STRUCTURE OF
THE COORDINATION COMPOUNDS OF THE RARE EARTH AND SHORTCHAIN ETHER E02 , E03
Jianming Gu andXiurong Hu

Analysis Center of Zhejiang University , Hangzhou 310028 , P.R.China(gujianming@zjuem.zju.edu .cn)

Aggregative glycol have more general character of crown ether and cryptate ether,composing easy and low toxicant, so they can be comprehensive studied because theirimportant function in the field of chemistry and biology[1 ,2].
The crystal structure of Nd(E02)3 and La(E03) 3 are investigated andcompared[3,4]. The crystal Nd(E02)3 belongs to monoclinic system with space group P
2,/n and the cell are a=14 .124(1 ), b=13 .990(1 ), c=15.265(1 )A,~=96 . 78(1 )", V=3001 .1(6) A 3 , All Oxygen on chain ether of the three groups wereparticipate in coordinated , formed nine-coordination , and it's coordinating polyhedron
showed tricapped trigonal prism , the ether link round the bond of C--C arrange into
sr f S (Symmetry, Trans).
The crystal La(E03) 3 belongs to monoclinic system with space group
P 2,/c and the cell are a=15.474(2) , b=11.386(1) , c=20.481(4)A,~=99 . 82(1 )", V=3618(1) A 3 , ten-coordination , it's coordinating polyhedron is biscapped
tetrahedron antiprism , the arrangement of ether link round the bond of C--0 are shown
err G r r Gauche , Trans .
The negative ion CI0 4 does not take part in coordination .
References1
Pedersen C.J. , (1967) J.Am.Chem., 89 , 2495
2
Hirashima , et al , (1986) Bull. Chern . Soc. Jpn ., 59 , 25
3
Gu Jianming , Hu Xiurong , (1998) (Chinese)J Inorganic Chern , 3, 313-317
4
Gu Jianming , Hu Xiurong , (1996) Chinese J Structural Chern , 3, 239-242

P033
REVERSIBLE SOLID-VAPOR SUBSTITUTION REACTIONS OF LAYEREDCADMIUM ORGANOSULFONATES
Jinsen Zhou , Li Wang ,_Jiwen Cai
School of Chemistry and Chemical Engineering , Sun Yat-Sen (Zhongshan) University,
Guangzhou 510275 , P. R. China (puscjw@zsu.edu.cn)(1)and{Cd(~h-p-N , OLayered[Cd(1 ,5-naphthalenedisulfonate)(H20 h ]n
NH2CsH. S03)2( H20 h}n (2) can uptake amine quantitatively without dehydration , via solidvapor reaction. The substitution reaction process is selective and reversible at room
temperature . Remarkably, single crystals of the C2HsNH2 and C3H1NH2adducts (3,4) grew
into single crystal suitable for X-ray structure analysis , in situ of the solid-vapor reaction .
The resulting adducts were also characterized by elemental analyses, IR and TGA. The
reversible process was recorded by PXRD. The result represents the first crystalline metal
sulfonate complex undergoing reversible solid-vapor substitution rea ction with amines atroom conditions . The difference in the physical properties , especially the conductivity of 2
as a neutral polymer and 3 as a salt, could be used to explore the potential application of
the air-stable and easy-to-make crystalline material 2 as a chemical sensor or switch forvolatile amines. We thank the financial support from the National Natural Science
Foundation of China (Grand No. 20271053).

Figure 1. The 2-dimensional coordination network of 1 and 2.

'"'P.
' .

,.,...
"'"-~ ~"~-

ru ~

~

~

Figure 2. The coordination structure of 3 and 4.
References1
2

Jiwen Cai , Jin-sen Zhou and Mu-liang Lin . (2003) J. Mater. Chem. 13 , 1806-1811.
Jin-Sen Zhou , Jiwen Cai , Li Wang and Seik Weng Ng , (2004) Dalton Tran s. ,submitted.

P034
CONSTRUCTION OF SLVER(I) COLUMN WITH ENCAPSULATEDACETYLENEDIIDE AND A HYDROPHOBIC SHEATH PROVIDED BY
ANIONIC AND ZWITTERIONIC CARBOXYLATE LIGATION
Xiao-Li Zhao and Thomas C. W. Mak
Department of Chemistry, The Chinese University of Hong Kong , New Territories, Shatin ,Hong Kong SAR , P. R. China(tcwmak@cuhk.edu .hk)
Betaines are zwitterions having a carboxylate group and a quaternary ammonium
group , with the presence of the carboxylate group , they belong to the family of carboxylatecompounds and exhibit most of the common coordination modes . Owing to theirpermanent bipolarity and overall charge neutrality, betaine ligands are expected to beadvantageous in the study of coordination polymers in several respects : 1) synthetic
access to water-soluble polymeric metal carboxylates; 2) new structural varieties , such ascomplexes with metal centers bearing additional anionic ligands , and those with variable
metal to carboxylate molar ratios ; 3) easy synthetic modification of carboxylate ligands byvarying the substituents on the quaternary nitrogen atom and the link between the twopolar terminals.
In the course of our investigation on silver salts containing silver acetylide , twodouble salts of silver acetylide containing both anionic and zwitterionic carboxylate
ligands, [(Ag 2C2 )(AgCF 3 C0 2 ) 4 (Hp)L 1)·2Hp(1) and [(Ag 2C2 ) 3 (AgCF 3 C0 2 ) 14 (L 2 ) 4) (2) (L 1 =pridinioacetate; L2 = pyridiniopropionate) have been synthesized and structurally characterized. Each has
a columnar structure generated from the fusion of silver cages with C2 2• species
embedded in its inner core and an exterior coat comprising anionic and zwitterioniccarboxyla,.,t,
es:..·~~-.,

This work is supported by Hong Kong Research Grant Council Earmarked Grant Ref. No.
CUHK 4268/00P .

P035
STUDIES ON IRON(III) COMPLEXES OF
2-PYRI DYL-6-(2-PYRI DYLCARBONYL )-2-PYRI DYLM ETHAN ONE
Xu-Dong Chen and Thomas C. W. Mak
Department of Chemistry , The Chinese University of Hong Kong , New Territories , Shatin ,Hong Kong SAR , P. R. China (tcwmak@cuhk.edu .hk)
The structure diversity displayed by the metal complexes of di-2-pyridyl ketone , whichstems from the ability of the doubly and singly deprotonated forms of the gem-diol form , or
the monoanion of the hemiacetal form of this ligand , to adopt a variety of coordination
modes, has drawn a great deal of interest of chemists in recent years.[1]During our systematic studies of metal complexes of a new ligand , 2-pyridyl-6-(2pyridylcarbonyl)-2-pyridylmethanone (L), it was found that reaction of L with FeCI 3 can besolvent-controlled , giving four crystalline compounds exhibiting two kinds of structures ,among which is a linear tri-iron complex assembled with two deprotonated hemiacetals of
L (L"). The three iron(lll) atoms are bridged by oxygen atoms from both L" and ~-OCH 3
and the linear structure is terminated by two chloro ligands; the Fe2 ··· Fe1 ··· Fe3 angle is152.6°, and the distance between Fe1 and Fe2 , Fe3 are 2.897 A and 2.916A, respectively.
The other three crystals have the same structure containing a mononuclear iron(lll) cation
with only one carbonyl group taking the gem-dial form while the other remains intact.

C3

C9This work is supported by HongKong Research Grants Council Earmarked grant Ref. No.
CUHK 402003.
Reference:
1
Papaefstathiou , G.S. and Perlepes , S.P., (2002), Comments on Inorganic
Chemistry, 23(4) , 249-274 .

P036
SUPRAMOLECULAR STABILIZATION OF OXOCARBON ANIONS IN
UREA HOST FRAMEWORKS
Chi-Keung Lam , Thomas C. W . Mak
Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories,
Hong Kong SAR , P. R. China (tcwmak@cuhk.edu.hk).
Our current interest is to generate new inclusion compounds [1] with oxocarbon
anions [2] and urea derivatives plus other molecular species as the building blocks ofvarious host lattices, using different types of quaternary ammonium cations as guest
templates. In the course of our systematic studies , we found that an elusive species suchas allophanate NH 2 CONHC0 2- [3] or dihydrogen borate BO(OH) 2- [4] can be generated insitu and stabilized in a hydrogen-bonded urea host framework . Guided by this design
strategy, the C2v valence tautomeric structures of croconate [5] and the relatively unstablerhodizonate species [6] are subsequently stabilized in two novel crystalline inclusioncompounds .

il lJ9(l)126.11 (8) CJ

02~208<~2J~Q2A~ C\
2l 26A(l )107. 5( 1)/

C2A

I.W (2)

1.469(2)108.59(7)125.3( 111

C1~C1A~ u;;\ 'J -

126.08(7 )

-o,

01A

Hydrogen-bonding environment of the croconate dianion in the crystal structure of[(C 2 H5 ) 4 N+] 2C5 0 52-·3(CH 3 NH) 2 CO (left); bond lengths (A) and anglesof the C2 v valencetautomer of the croconate dianion with standard deviations enclosed in parentheses(right).

nThis work is supported by Hong Kong Research Grants Council Earmarked Grants
CUHK 4268/00P and 402003 .
References
1
Mak , T. C. W. and Li , Q. (1998) in Advances in Molecular Structure and Research(Eds. : M. Hargittai, I. Hargittai), JAI Press , Stamford, Connecticut, Vol. 4, pp.
151-225.
2
Lam , C. -K. and Mak , T . C. W . (1999) Zh. Strukt. Khim. , 40 , 883-891; (2000) Cryst.
Engng ., 3, 33-40 , 225-226 ; (2000) Tetrahedron , 56 , 6657-6665.
3
Mak, T. C. W ., Yip , W . -H . and Li, Q. (1995) J. Am. Chem. Soc. , 117, 11995-11996.
4
Li , Q ., Xue , F. and Mak, T. C. W . (1999) lnorg. Chem. , 38 , 4142-4145.
5
Lam , C. -K., Cheng , M. F., Li , C. L., Zhang , J. P., Chen , X. M. , Li , W . K. and Mak,
T. C. W. (2004) Chem. Commun. , 448-449.
6
Lam , C. -K. and Mak , T. C. W. (2001)Angew. Chem.lnt. Ed. , 40 , 3453-3455.

P037
SYNTHESIS, STRUCTURE, AND DNA CLEAVAGE OF AN OPTICALREACTIVE SPIROPENTACOPPER CLUSTER
Szu-Miao Chen ," Yu Wang ,a· and Kuan-Jiuh Linb'•Department of Chemistry, National Taiwan University, No.1 , Sec. 4, Roosevelt Road ,Taipei , Taiwan ; bDepartment of Chemistry, National Chung-Hsing University, 250 ,Kuo
Kuang Road ,Taichung , Taiwan. (d92223013@ntu .edu.tw)
Nature uses a self-assembly principle to build a supermolecular envelope around themetal center, therefore, metal ions are often found at the active site of many
metalloenzymes to exhibit distinctive spectral and chemical features. Here we describe aself-assembly methodology to synthesize a spiropentacopper(ll) cluster self-enclosed bypyroglutamic acid ligands, K2CUs(pGiu)s(OH )2. 1OH20 , namely Spiro-Cus.
Spiro-Cus, synthesized by one-step solvothermal method , contains square planar,
square pyramidal , and distorted octahedral configurations which are present
simultaneously in three distinct Cu 11 (d 9 ) ions in the asymmetric unit. The three mixed
coordination geometries represent an entire spectra of nature Jahn-Teller distortion ofCu(ll) electronic configuration for the first time . The intra-cluster metal-metal separations
are of 2.992(2) , 3.185(2), and 3.549(3) A. Interestingly, it is found for the first time that thechiral pyroglutamic acid ligands appear to be in three different coordination types toencompass the novel spiropentacopper cluster with a center of symmetry(]) in the middle.
In the presence of H20 2, we propose that Spiro-Cus would initiate hydroxy radicals(·OH) and transfer electron(s) to the phosphate backbone of nucleic acids , consequently
cleave DNA. To our best knowledge , the spiropentacopper cluster is the first polynuclear
species (M>3) capable of mediating DNA cleavage.

P038
CHARGE DENSITY STUDY AND ROLE OF HYDROGEN BOND IN TRAN[Ni(cyan-kN)2(NH3)4] : COMPARISON BETWEEN EXPERIMENT AND
THEORYHsin-Hui. Shen , Yu-Wang*
Department of Chemistry, National Taiwan University, Taipei 106, Taiwan(r91223026@ntu .edu.tw)
The six-coordinated complex trans-[Ni(cyan-kN M NH 3 ) 4 ] has been characterized in thesolid state by X-ray diffraction at 100 K and 298 K. The space group at room temperature
is Fmmm with a site symmetry of mmm . While lowering the temperature , the space groupchanges to Ccmm at 100K and the molecule is located at a site symmetry of 2mm. The
main difference that involves phase transition at low temperature is the change ofhydrogen-bonding patterns. In order to understand the chemical bonding of the nickel
complex and various hydrogen-bonding in this complex , the electron density distribution of
the complex is derived using both the single crystal X-ray diffraction and OFT calculations
with different kinds of hydrogen bonds . The comparisons are made in d-orbital
occupancies at the nickel center and the topological properties associated with the BCP.
The pi-delocalization of the ligand will be discussed with reference to the bond ellipticity
and Fermi-hole distribution. Results on the electron density distribution will be presented in
the form of deformation density, Laplacian maps and the topological properties. The
Laplacian maps derived from the experiments agree well with the maps derived
theoretically.

R.T. (Fmmm)

100K (Ccmm)

P039
PHOTOCHROMISM OF SALICYLIDENEANILINES DEDUCED BY THE
ACID-BASE COMPLEX FORMATION
Kohei Johmoto. Hidehiro Uekusa, Yuji Ohashi
Department of Chemistry and Materials Science , Graduate School of Science andEngineering , Tokyo Institute of Technology, Tokyo 152-8551 , Japan(kjomoto@chem .titech .ac.jp)
Light-induced reversible color change of substances is known as photochromism
and has attracted attention due to their potential applications such as optical data storage
etc.
Salicylideneaniline (SA) derivatives have the property of photochromism or
thermochromism , which is reversible color change with variation of temperature . The
color change from stable yellow to unstable red is brought about by the change ofmolecular conformation. The planar conformation leads to thermochromism whereas nonplanar one to photochromism . Moreover, the large cavity around the imine group makes
the red form stable upon heating. Since SA has a non-planar conformation and large
cavity , its red form has long lifetime.
N-salicylidene-4-carboxyaniline (4C-SA) has a planar conformation and showsthermochromism . It was found that 4C-SA formed an acid-base complex withdibenzylamine and that the complex crystal shows photochromism. The structure wasanalyzed by X-rays. The molecular conformation of 4C-SA in the complex crystal ischanged to non-planar as shown in the Figure . Similar change was observed for thecompound of 3C-SA and its complex with dibenzylamine. The complex formation is a
powerful tool to obtain photochromism for the SA derivatives.

Figure . Molecular structures of (a) 4C-SA and (b) 4C-SA in the complex withdibenzylamine

P040
SOLVOTHERMAL INDUCED TRANS-CIS ISOMERIZATION OF[Fe(tzpyh(NCS)2] (tzpy=3-(2-PYRIDYL)[1 ,2,3]TRIAZOL0[1 ,5-A]PYRIDINE)
K. W . Chen , C. F. Sheu , G. H. Lee ,Y. Wang*
Department of Chemistry, National Taiwan University, Taipei 106, Taiwan(r90223020@ntu .ed. tw)

The novel complex Cis-[Fe(tzpy)2(NCS)2](1) has been synthesized successfully fromspin crossover trans-[Fe(tzpy)2(NCS )2](2) isomer by solvothermal induced isomerization
method . Single-crystal diffraction data was collected at 293 K by CAD-4 diffractometer.
Complex (1) crystallizes in the monoclinic space group C 2/c with Z=4 , a=14 .828(4) ,b=11.485(5) A ,c=15.071(2) A, beta= 110.081(15) deg. The bond lengths of Fe-N are
2.249(4) A, 2.197(4) A, and 2.056(5) A for complex 1 and 2.019(1) A, 1.971 (2) A, and1.933(1) A for complex 2 at LS state. Both complexes have a similar pseudo-octahedral[FeN6] core with the NCS- groups in the cis arrangement in 1 but trans in 2. Variabletemperature magnetic susceptibility measurement reveals that 1 staying in a high-spinstate in the observed temperature range of 5-300 K. It is interesting to note that thedifferences of the crystal packing between the isomeric iron (II) complexes result in a
dramatic change in their magnetic properties . Further studies on the origin of thediscrepancy in the crystal field responsible for this result are currently in progress.

ORTEP diagram of cis-[Fe(tzpy)2(NCS)2] (30%, 273 K )P041
A UNPRECEDENTED HOMOCHIRAL OLEFIN-COPPER(!) 2D
COORDINATION POLYMER
Ren-Gen Xiong , Xi-Sen Wang
Coordination Chemistry Institute, The State Key Laboratory of Coordination Chemistry,
Nanjing University, 210093 Nanjing, P. R. China , (xiongrg@netra.nju .edu.cn)
The reaction of 4-Vinylbenzylcinchonidinium chloride ([VB-N-CIN]CI (1 ), a chiralphase transfer catalyst (CPTC), prepared from the corresponding cinchona alkaloid and 4vinylbenzyl chloride in refluxing acetone and N,N-dimethylformamide, solvothermallyreacts with CuCI to afford the unprecedented 20 layered homochiral copper(l)-olefin
coordination polymer CusCI6(VB-N-CIN)2-C2H50H (2•Et0H) , in which The five Cu(l)centers connect together by four 112-CI and two J13-CI linkers to result in the formation of
two clusters composed of two triangles (Cu1-Cu2-Cu3 and Cu3-Cu1A-Cu2A), while two
triangles share a corner of Cu3 . Cu1 and Cu1 A and Cu2 and Cu2A are all three coordinated and coordinate to the N atom of the quinoline ring and olefin moiety of thequinuclidine ring to result in the formation of a 20 square-grid network . The remaining Cu3
only coordinates to four Cl atoms with a tetrahedral geometry. It is noteworthy that two
adjacent layers are in an AA type arrangement and one ethanol molecule is intercalated
between two layers of 2 as the framework. A preliminary enantioseparation investigationshows that the 20 layered network in 2 is capable of selectively intercalating (R)-2butanol.

fig1 a: the molecular for 1

fig1 b an asymmetric unit of compound 2

Sea led Tube

70 ;re2- NetworkOH( R )--CH 3-• CH
I - CH2- CH J

/755 7

Scheme 1: Proposed resolution process by intercalation
Reference
1 Xie, Y.-R. , Wang , X.-S. , Xiong , R.-G. , et.al. , (2003) , Organometallics , 22 , 4396

P042
FERROELECTRIC COPPER QUININE COMPLEXES
Ren-Gen Xiong , Hong Zhao
Coordination Chemistry Institute, The State Key Laboratory of Coordination Chemistry,
Nanjing University, 210093 Nanjing , P. R. China(xiongrg@netra .nju .edu .cn)

The reactions of quinine with Cu(I)CI and Cu(I)Br afford CusCig(H20uinine )2 (1) andCu3Br7(H20uinine h(H20) (2) , respectively, with 1D polymeric structures. The anionic chainin (1) contains Cu. CI62· adamantane-type aggregates that are linked to two identical units
by CuCil· bridges , and the Cu(l) centers in (2) have a distorted tetrahedral environment
formed by bridging and terminal bromide ions . Given that the products (1) and (2)crystallize in a chiral space group (C2) which belong to a polar point group (C2), their
optical properties were studied. Reliminary examinations of a powdered sample indicatethat both (1) and (2) are SHG-active with approximate responses 4 .0 times that of KDP.
Th e space group C2 is associated with the point group C2, one of the 10 polar point
groups (C,, C2, Cm, C2,, c •. c.,, C3, C3,, C6, C6,) required for ferroelectric behavior.
Experimental results indicate that (1) does indeed display good ferroelectric behavior while(2) shows relatively low ferroelectric responses. There is an electric hysteresis loop in (1 ),which is a typical ferroelectric feature with a remanent polarization (Pr) of 0.28 ~~C-cm · 2 andcoercive field (Ec) of 16 kVcm·' .8 . The saturation spontaneous polarization (Ps) of (1) is
ca . 2.0 f.!C·cm·2 compared to ferroelectric KDP which is 5.0 ~tC - cm ·2 (1) is the firsthomochiral metal-organic coordination polymer exhibiting ferroelectric behavior.

Figure 1. The structure of 1

Figure 2. The structure of 2

Figure 3. The electric hysteresis loop of a pellet of
powdered 1 observed by Virtual Ground Mode using
an RT6000 ferroelec- !ric tester at room temperature .

-2.0 L·1"'-50~-1oo:;;;--;;_so,---!;-o~50;;--,:0ooo;-"-;-1;;;-'50
Applied Field (kV/cm)

Reference
1 Zhao , H. ; Qu , Z.-R. ; Xiong , R.-G ., et al. (2003)Chem. Mater.15 , 4166-4168 .

P043
STRUCTURE OF AN COMPLEX COMPOSED OF METHACRYLIC ACID
AND PYRIDINE
K. YOSHIDA, H. UEKUSA, Y OHASHI
Department of Chemistry, Tokyo Institute of Technology, Tokyo 152-8551 , Japan:kyoshida@chem .titech.ac.jp)
Molecular complexes composed of low-molecular-weight acids and bases are goodmodels to understand intermolecular acid-base interaction in crystalline state . Since thecomponent molecules and the complex are liquid at room temperature , the complex
crystal should be prepared on the diffractometer using the cooling equipment and then the
In this work, the structure
intensity data should be collected with the diffractometer.
composed of methacrylic acid and pyridine , 1, was analysed at three temperatures toinvestigate the effect of pKa on intermolecular interaction.
Equimolar amount of methacrylic acid and pyridine was sealed in a capillary and thecapillary was mounted on the Rigaku R-AXIS RAPID diffractometer. Using the coolingequipment, a single crystal of 1 :m.p. 250K) was grown in the capillary. The intensity data
were collected with the diffractometer at 223, 173 and 123K. The complex crystal belongs
to the monoclinic system and the space group is P2 ,/n.
The methacrylic acid and pyridine molecules make the 1:1 complex with the 0-H ... Nhydrogen bond . However, the structure is disordered as shown in Fig. 1. The disorderedstructure is composed of two modes as shown in Fig . 2. At 223 K, the ratio of mode I to II
is 7:3 and the 01-H ...N and 02-H ...N distances in mode I and II are 2.69 and 3.14A,
respectively. At 123 K, the ratio comes close to 5:5 and the two 0-H ... N bonds have thesimilar distances. This indicates that the disorder is a dynamic one and that the pyridine
molecule shows the in-plane flip-flop motion to make the hydrogen bonds with both of 01
and 02. The crystal structure is shown in Fig . 3.

Figure 1

Figure 3. Crystal structure~, JlCOl

co

Figure 2. minor compound

P044
X-RAY ANALYSIS OF REACTION PROCESS THROUGH ARYLNITRENE
Takahiro Mitsumori, Hidehiro Uekusa, Yuji Ohashi
Department of Chemistry and Materials Science ,Graduate School of Science andEngineering , Tokyo Institute of Technology, Tokyo 152-8551 ,Japan(tmitsumo@chem .titech .ac.jp)
When arylazide is irradiated with UV light, it is dimerized to azo compound througharylnitrene as shown in the Scheme . When the crystal of the acid-base complex
composed of m-carboxyphenylazide and dibenzylamine was irradiated with UV light, thestructure of the intermediate nitrene was analyzed by X-rays at 80 K. ' l For the crystal of 1azide-2-nitrobenzene , the produced nitrene made a bond with the oxygen atom of the nitro
group to form benzofroxane. 2l In the present work, two crystals were prepared and theirreaction intermediates or products were analyzed by X-rays ; (I) an acid-base complex of
m-carboxyphenylazide and dicyclohexylamine , and (II) an acid-base complex of ocarboxyphenylazide and dibenzylamine.
Each crystal was irradiated with the high-pressure Hg lamp at 80 K on the X-ray
diffractometer and the intensity data were collected. The structure was refined with the
SHELXL-97 program.
Figure1 (a) shows the molecular structure of the complex (I) after photoirradiation .
A nitrogen molecule , whose occupancy is 13% is clearly observed . However, the nitrene is
obscure since it is too close to the original azide molecule. For the complex (II) after
irradiation , on the other hand , not only a nitrogen molecule but also 2, 1-benzisoxazolone
were observed , their occupancy factor being 10%, as shown in Figure1(b) . The produced
nitrene should make a bond with the oxygen atom of the carboxyl group. The
circumstance around the produced nitrene determines the reaction process after thenitrene formation in the reaction process .
References
1 M. Kawano , et al. , Chem. Lett. , 32 , 922 (2003).
2 T. Takayama et al. , Helv. Chim . Acta , 86 , 1352 (2003)

P045
X-RAY
DIFFRACTION
STUDY
OF
THE
CRYSTALLINE-STATEPHOTORACEMIZATION OF A BULKY ALKYL CROUP IN A COBALOXIMECOMPLEX
H. Takeoka , H. Uekusa , Y. Ohashi
Department of Chemistry and Materials Science , Tokyo Institute of Technology, 12-1 , 0okayama 2-chome , Meguro-ku, Tokyo 152-8551 , Japan(htakeoka@chem .titech.ac.jp)

The chira\ bulky alkyl group in some (buthoxycarbonyl)ethyl cobaloxime complexes
are known to be racemized by exposure to visible light with retension of single crystal
form. The mechanism of this reaction has been interested because the structural changeof such a bulky alkyl group in crystalline lattice is thought to be a model of enzymatic or
catalytic reactions which also proceed in restrained environments .
In
thiswork ,
weprepared[(R)-1-(buthoxycarbony\)ethy\)[(R)-1cyc\ohexylethy\amine]cobaloxime complex and carried out single crystal X-ray diffraction
measurement before irradiation and after 72 hours exposure to visible light. The result
showed that the 40% of the chiral bulky alkyl group was inverted to the opposite
configuration .

P046
IONIZATION STATES, STOICHIOMETRY AND HYDROGEN BONDING
PATTERNS IN COMPLEXES OF AMINO ACIDS WITH CARBOXYLIC
ACIDS
R.V.Krishnakumar• and S.Natarajanb•Department of Physics , Thiagarajar College , Madurai- 625 009 , bOepartment of Physics,
Madurai Kama raj University, Madurai-625 021 , India (mailtorvkk@yahoo.co.in)

Amino acids are known to exhibit specific characteristic aggregation patterns intheir crystal structures. Carboxylic acids , believed to have existed in the pre-biotic earth ,form proton transfer complexes of the type A.B , where A is an amino acid and B is acarboxylic acid . In our laboratory, systematic and precise X-ray investigations on morethan 25 amino acid - carboxylic acid complexes have been carried out with a view tounderstand the modes of interaction between these two distinct chemical species and alsocharacteristic aggregation patterns and specific interactions among them. Dicarboxylic
acids viz. oxalic, maleic, fumaric , tartaric and trichloroacetic acids were used in preparing
complexes with L- and DL- amino acids. Single crystals of the compounds were grownfrom saturated aqueous solution containing respective amino acids and carboxylic acids ina 1:1 stoichiometric ratio. In all the complexes, the amino acid molecule adopts a cationicform and the carboxylic acids exist as semi-anions i.e . with a carboxylic acid group and acarboxylate group. Though the stoichiometry remains 1:1 for a majority of complexes ,deviations were observed in the cases of oxalic acid with DL-aspartic acid and DL-serine
where the stoichiometry is 2:1. There exists a variety of intermolecular aggregation
patterns and the results of a detailed analysis of the ionization states, stoichiometry andmolecular aggregation patterns will be presented.

P047
SYNTHESES AND STRUCTURES OF NaCd(Hp) 2 [BPp 8]•0.8Hp AND
NaZn(H 2 0) 2 [BPp 8 ]•H 2 0 AT ROOM TEMPERATURE AND AMBIENT
PRESSURE
Minq-Hui Ge , Wei Liu , Hao-Hong Chen , Xin-Xin Yang and Jing-Tai Zhao
The State Key Lab of High Performance Ceramics and Superfine Microstructure,
Shanghai Institute of Ceramics , Chinese Academy of Sciences, Shanghai 200050 , China(gmh@mail .sic.ac.cn)

Botophosphates have attracted many scientists in the recent year for their promisingproperties and potential applications. So far almost all the borophosphates reported havebeen synthesized by hydrothermal methods . Mix M 11 y(Hp) 2[BP 2 0 8]• zH 2 0 (MI= Li , Na , K,
Rb , Cs ; M 11 = Mg , Mn, Fe , Co , Ni, Zn , Cu ,Cd ; x = 0.35-1 , y = 1-1.3, z = 0.2-1) is a big family
in borophosphates. A chiral octahedral-tetrahedral framework related to the CZP topology
is present in the crystal structures of these compounds which also show a very interesting
reversible dehydration (or hydration) process[1] The two title compounds were firstprepared using hydrothermal method and were characterized by X-ray single crystal
investigations [2] . We have now succeeded in their syntheses at room temperature andambient pressure and the reaction procedure was monitored by X-ray diffraction methods
for the reactants in capillary micro-reactors . It is the first time using normal chemical
reactions to synthesize borophosphates in this family, and so far only one borophosphate(NH.)5 [V 3 BPp , 9]·Hp was reported at room temperature to our knowledge[3]. This
success at room temperature and ambient pressure provided us many possibilities forsynthesizing new borophosphates in other systems. It also widely opened our mind for
exploring compounds at different conditions and helping us to understand the mechanismof borophosphate formation.
References
1 Boy, 1. ; Stowasser, F.; Schafer, G.; Kniep, R. (2001) Chem. Eur. J. 7, 834-839 .
2
Ge M.H.; Mi J.X. ; Huang Y.X .; Zhao J.T. ; Schafer G. Kniep R. (2003) Z. Kristallogr.
NCS 218, 1-2.
3
Bontchev, R.P. , Do , J. and Jacobson , A .J. (2000) lnorg. Chem, 39,4179-4181 .

P048
A MIXED CATIONS NICKEL DIPHOSPHATE WITH A LAYEREDINTERGROWTH STRUCTURE: SYNTHESIS, STRUCTURAL AND
MAGNETIC CHARACTERIZATION OF Na(NH 4 )[Ni 3(P 2 0 7 ) 2 (H 2 0) 2 ]Wei Liu .a Xin-Xin Yang ,a Hao-Hong Chen ,a Ya-Xi Huang ,b Walter Schnelle ,b Jing-Tai
Zhao•• The State Key Laboratory of High Performance Ceramics and Superfine Microstructure,
Shanghai Institute of Ceramics , Chinese Academy of Science , Shanghai , 200050 , P. R.
China (lw@mail.sic.ac.cn)
b Max-Pianck-lnstitut flir Chemische Physik fester Stoffe , Nothnitzer Strasse 40 , 011 FF
Dresden , Germany.

A mixed cations nickel diphosphate , Na(NH 4 )[Ni 3(PpF)2 (Hp) 2 ] with a layered
structure , has been synthesized hydrothermally in the presence of imidazole andcharacterized by single crystal X-ray diffraction , IR spectrum and magnetisation. The
structure consists of cis- and tans-edge sharing Ni0 6 octahedral chains linked via PpF
units to form [Ni 3 P40 16)2· layers. The ammonium and sodium cations locate alternately in
the interlayer spaces. A network of inter-layer and ammonium-layer based hydrogenbonds holds the structure togethher. Similar two-dimensional topological structure can beaslo found in the previously reported diphosphates K3Co 3(P p F)·HP and(NH 4 MMn 3 (PPFMHPM '.2 Compared to these layered cobalt and manganesediphosphates , the title compound reported here is different in several aspects. The crucial
distinguishing point is that the title compound has a different layer-stacking , which lead toessential structural differences such as different space group and crystal lattice. The
studies show that the presence of mixed cations has an important effect on the structuralformation of this layered compound , leading to a new layer stacking variants . Magnetic
measurement indicates that the magnetic susceptibility obeys almost a Curie-law over thewhole measured temperature range with IJ en of 3.32 1J 8 , showing Ni 2• character and very
weak antiferromagnetic interactions.
References
1 Lightfoot, P., Cheetham , A . K. J. (1990) Solid State Chern. 85, 2F5.
2 Chippindale , A. M. , Gaslain , F. 0 . M. , Bond , A. D. , Powell , A. V. (2003) J. Mater.
Chern. 13 ,1950.

P049
NH 4 [BP0 4 F]: A NOVEL OPEN-FRAMEWORK AMMONIUM FLUORINATED
BOROPHOSPHATE WITH A ZEOLITE-LIKE STRUCTURE RELATED TO
GISMONDINE TOPOLOGY
Man-Rong Li. Wei Liu , Ming-Hui Ge , Hao-Hong Chen , Xin-Xin Yang and Jing-Tai Zhao
The State Key Laboratory of High Performance and Superfine Microstructure,
Shanghai Institute of Ceramics , Chinese Academy of Science , Shanghai 200050 ,China .(mrli@mail.sic.ac.cn)
Organically templated metal borophosphates are of great current interest because of
their novel structures and potential applications. 4 Comparing to silicates and phosphates ,borophosphates containing halogen anions are very few 2 Here we report a novelcompound containing fluorine anion . Colorless crystals of NH 4 BP0 4 F were synthesizedunder mild conditions in Teflon-lined stainless steel autoclaves . Its structure wasdetermined by single crystal methods. The crystal structure of the title compound reveals
a new type of three-dimensional anionic structure . The condensation of B0 3 F and P0 4
1
tetrahedra through vertices leads to tetrahedral ribbons of OC! ([BPOJ
n ' which are.
arranged around 24 screw axes to form helical chains , which is the first example ofborophosphate compounds with such tetrahedral helical chains to our knowledge . The
chains are connected to each other by sharing common vertexes leading to the openframework with four- and eight-membered ring channels along the cubic axes to form athree-dimensional channel system. In the three-dimensional structure of NH 4 BP0 4 F, thenon-coplanar sequence of up (U) and down (D) linkages of four-memered rings lead to
double crankshaft (cc) chains around the eight-mememberd rings; and the coplanar
linkages of four-membered rings and adjacent parts of eight-membered rings result inchains including bifurcated square (bs). The condensed connection of these chains gives
a framework related to the gismondine (GIS) topology of 14.famd Symmetry. This more
open zeolite-like structure with channels along three directions instead one direction in
GIS could be considered as a new member of GIS family with cubic space group P2 4 3.
References
4
Anthony, K. C; Gerard , F. ; Thierry, L. (4999) Angew. Chem. , Int. Ed. Engl., 38 ,3268 .
2
Huang, Y. X. ; Schafer, G.; Carrillo-Cabrera , W. ; Borrmann , H.; Gil , R. C. ; Kniep ,R. (2003) Chem. Mater. 45 , 4930.

POSO
TAILORING OF BOROPHOSPHATE STRUCTURES BY HALOGENANIONS AND/OR ORGANIC TEMPLATES
Jing-Tai Zhao Wei Liu , Man-Rang Li , Ya-Xi Huang , Ming-Hui Ge ,Hao-Hong Chen and XinXin Yang
The State Key Lab of High Performance Ceramics and Superfine Microstructure,
Shanghai Institute of Ceramics , Chinese Academy of Sciences , Shanghai 200050 , China
Utzhao@mail.sic.ac.cn)

Organically templated metal borophosphates are of great current interest because of
their novel structures and potential applications .1 Surprisingly, despite intensive
researches carried out in many chemical systems , organically templated borophosphates
are still to be explored and compounds containing both organic templates and halogen
anions are very few. 2 Very recently we have successfully synthesized a few novel
borophosphate compounds which contain both halogen anions , amine templates or both ,(C2H10N2)[BP04F2],
NH4[BP04F],(C4H1sN3)[CdCIB2P30 12(0H)],
namely(C4H1sN3)[Zn3B3Ps0 24]·H20 . In these structures , the halogen anions and organic templates
both play important roles in constructing the structures. The tailoring effect of both canlead to novel structures with different dimensions.
B04 CdOSCIReferences
1 Anthony, K. C ; Gerard , F. ; Thierry, L. (1999) Angew. Chem. , Int. Ed. Engl. , 38 , 3268 .
2 Huang, Y. X.; Schafer, G.; Carrillo-Cabrera , W. ; Borrmann , H.; Gil , R. C. ; Kniep , R.
(2003) Chern. Mater. 15, 4930 .

P0 51SYNTHESISAND
CHARACTERIZATIONOF
BUTADIYNEDIIDE AND ITS RELATED SILVER(I)CONTAINING THE C/- DIANIONSILVER(I)1,3DOUBLE SALTS

Liang Zhao and Thomas C. W . Mak*
Department of Chemistry, The Chinese University of Hong Kong , Shatin ,New Territories , Hong Kong SAR , P. R. China (tcwmak@cuhk.edu.hk)
We have carried out a systematic investigation on the synthesis and structuralcharacterization of a series of double , triple and quadruple salts of the highly explosive
silver acetylide , Ag 2C2 .1 11 As an extension of the research in this field , the higher
homologue Ag 2 C4 , which is the second silver carbide to be full y characterized , has beensynthesized as a light gray powder that is explosive when heated (130°C) and sensitive tomechanical shock. In the pair of hydrated double salts Ag 2C 4 · 6AgN0 3 • nHp [n = 2, 3],
the nearly linear, centrosymmetric 1,3-butadiyne-1 ,4-diyl dianion exhibits anunprecedented p8-coordination mode , each terminal being capped by four cr-bonded
silver(!) atoms with rr-interaction to one of them (Figure (a)). Compared with the known
coordination modes of a naked tetracarbon chain in transitional metal complexes (Figure(b) I-VIII), this new mode IX is stabilized by ionic as well as argentophilic interactions andto date.
exhibits the highest ligation numberl 21 for

c.z-

·[I"

"
("

M --~!

'I

("

~

<"

1'1-· M

Lt

("

II

"

Ill

"Ill
("

I

"
("

II

M
IX

(a) Perspective drawing of aagg regate in Ag 2 C,. 6AgN0 3 . 2H,O.

[Ag, C,Ag,](b) Coordination modes of the naked linear
tetraca rbon (C, ) ligand in metal complexes .

This work is supported by Hong Kong Research Grant Council Earmarked Grant Ref.
No. CUHK 4268/00P.
References
1(a) Guo , G.-C. , Zhou , G.-D., 0.-G. Wang , Mak, T. C. W. (1998) Angew. Chem. , Int.
Ed. 37 , 630-632. (b) Guo, G.-C. , Zhou , G -D , Mak, T. C. W. (1999) J. Am. Chem.
Soc. 121 , 3136-3141. (c) Wang , 0.-M. , Mak, T. C. W. (2001) J. Am. Chem. Soc.
123, 1501-1502. (d) Zhao , X.-L. , Wang , 0.-M., Mak , T. C. W. (2003) lnorg. Chem.
42 , 7872-7876.
2
Guo , G.-C ., Mak, T. C. W . (1999) Chem. Commun. 813-814 .

P0 52
STRUCTURAL CHARACTERIZATION OF SPIN CROSSOVER COMPLEX
TRANS-[Fe(tzpy) 2 (NCSU (tzpy = 3-(2-PYRIDYL)[1 ,2,3]TRIAZOL0[1 ,SA] PYRIDINE)
C. F. Sheu•, J. J. Leeb, G. H. Lee•, I. J. Hsu•, Y. C. Lin•, K. Toriumic, Y. Ozawac, Y. Wang•*•Department of Chemistry, National Taiwan University, Taipei 106, Taiwan(fu@xtal.ch.ntu.edu .tw)bNational Synchrotron Radiation Research Center, Hsinchu 30077, Taiwan
cspring-8 , Hyogo 679-5198 , JapanThe spin crossover complex trans-[Fe(tzpyMNCS) 2 ] has been synthesized and thetemperature dependent magnetic susceptibility measurement shows that it is in the highspin state (S = 2) at room temperature and low spin state (S = 0) below 75 K. Single
crystal diffraction data were collected and solved at 293 K using in-house Kappa CCD
diffractometer and at 40 K using the low temperature vacuum camera facilities at beamline BL02B1 in sping8 . Complex trans-[Fe(tzpy) 2 (NCS) 2] crystallizes in monoclinic spacegroup P2 ,fc with cell constants a = 8.760(1 ), b = 17.476 (2), c = 8.367 (1) A, 13 =103.78(1 r at 293 K (HS state) and a= 8.531(2), b = 17.215 (3) , c = 8.213 (2) A, 13 =105.57(3r at 40 K (LS state), respectively. The iron(ll) atom is located at the inversion
center in a distorted octahedron environment, it is coordinated to two tzpy ligands in theequatorial positions and two NCS- groups in the axial positions (shown in Fig . 1 ). As
expected , the coordination geometry of iron center is strongly dependent upon the spinstate of Fe(ll). The bond length difference of the two spin states is -0.19 A in Fe-N. The
bond lengths of Fe-N are 2.217(2), 2.181 (2) , and 2.097(3) A at HS state and 2.019(1 ),1.971 (2), and 1.933(1) A at LS state . The distortion parameter 2 , defined as the sum of
the absolute values of the deviation from 90 " of the 12 cis angels in octahedronenvironment, are 74.8" at HS state and 51.8" at LS state . The preliminary light-induced
excited spin state trapping (LIESST) effect was investigated by the Fe K-edge and L-edge
x-ray absorption spectroscopy at 30 K using a green light (532 nm) laser irradiation.

Figure 1. ORTEP diagram of trans-[Fe(tzpyMNCS) 2 ] with atomic numbering scheme with
30% thermal ellipsoids at 273 K

P0 53
CHARGE DENSITY INVESTIGATION OF A NON-CENTROSYMMETRICMN COMPLEX : Mn(mai)(H20)2
Yen-Chen Lin ," 1-Jui Hsu ," Gene-Hsiang Leeb and Yu wang•·•National Taiwan University, Taiwan ; blnstrumentation Center, National Taiwan University,
Taiwan (sirius@xtal.ch .ntu .edu.tw)

Charge density distribution of the non-centrosymmetric malonate (mal = C30 . H/· )complex, Mn(mai)(H20)2 , has been studied by multipole model refinement. In the title
compound each Mn atom is coordinated by six oxygen atoms (four from three different
malonate ligands and the other two from the binding water molecules) and each malonate
anion coordinates to three Mn atoms to form two-dimensional layers perpendicular to caxis. Neighboring layers are connected by intermolecular hydrogen bonding of the axial
water ligands. The Mn- 0 bond distances are in the range of 2.1280(5) to 2.2315 (9) A.
The 0 ···· 0 distances involving the hydrogen bond are 2.762- 3.002 A.
Topological analysis provides a numerical comparison of the bond character.
Electron densities on the Mn-0 bond critical points are in the range of 0.27 to 0.36 e/N
which are compa rable to those of metal-oxygen bonds in metal squarate complexes 121.
AIM (atom in molecule) charge obtained from integration over the atomic basin and the dorbital population of Mn atom will be presented . Results from p-DFT (periodic Density
Functional Theory) performed by CRYSTAL98 will also be shown and the comparison
between experiment and theory will be given .
References
1
T . Lis and J. Matuszewski , (1979) Acta Cryst., 835 , 2212
2
C.-R. Lee , C.-C. Wang, K.-C. Chen, G.-H . Lee andY. Wang , (1999) J. Phys. Chem.
A103, 156

P0 54
CRYSTAL ENGINEERING WITH SCORPIONATE LIGANDS
Stuart R. Batten , and Martin B. Duriska
School of Chemistry, Monash University 3800 , Australia(stuart. batten@sci. monash. edu .au)

We have synthesised a range of scorpionate ligands with peripheral coordinationsites . The ligands are tris(pyrazolyl)borates with pyridyl or benzonitrile groups attached tothe 3- or 4- position of the five-membered rings. The ligands are designed to bind a metal
atom at the tris(pyrazolyl) position and be linked into higher order structures(metallosupramolecules or coordination polymers) by coordination of further metal ions at
the peripheral coordination sites .
The structures of a number of metal complexes have been determined. The thallium
and potassium salts form 1D and 20 networks. Discrete ML 2 molecular species are formed
by a number of first row transition metals. A 20 sheet structure is formed by one of theligands with FeS04. The sheets contain uncoordinated pyridyl groups that line the interiorof channels formed by the stacking of the sheets. These pyridyl groups offer the possibilityof further reactivity. A metallosupramolecular 'nanoball' (left) has been synthesised whichcontains eight ligands and fourteen metal atoms. The nanoballs are roughly spherical andhave an internal diameter of ca. 15.8 A, and an external van der Waals diameter of 29 A
(or 2.9 nm) .

P0 55
CRYSTAL STRUCTURE AND MELTING POINT CORRELATIONS OFACETIC ESTERS
Hidehiro Uekusa•, Hirokazu Suzuki•, Yuji Ohashi••Department of Chemistry and Materials Science , Tokyo Institute of Technology, Meguroku , Tokyo 152-8551 , JAPAN . (uekusa@cms.titech .ac.jp)

Low melting point acetic esters are important solvent and also used as industrial
materials. Therefore, understanding their physical and chemical properties is essential for
utilizing these compounds further. As melting point (m.p.) is one of the fundamental
property, explaining m.p. behavior of "m.p. alternation " by structural feature is attracting
the interests of crystallographers[1] .
Different from n-alkane with two functional group (e.g . alkanedicarboxylic acid andalkanediol) , acetic esters (Ac0(CH 2 )n_, CH 3 ) show no m.p. alternation behavior in longer
alkyl chain region , however, smaller acetic esters show prominent m.p. alternation (-96 ,-81 , -91 , -75 , -68 , -60oC for n=1 to 6). In order to investigate this behavior of small acetic
esters , crystal structures of methyl acetate (n=1) to amyl acetate (n=5) were investigatedby single crystal X-ray structure analysis.
As they are liquid in room temperature , single crystals were grown by "in situ
crystallization " method on the R-AXIS RAPID diffractometer. The diffraction data werecollected at 93K within short measurement time just after a single crystal was obtained .
Their crystal structures were determined in good R values (R,=0.039- 0.044 ).
Investigation of the crystal structures revealed that both C-H 0 type hydrogen bonds
between acetic groups and van der Waals interactions between alkyl chains play
important role to stabilize the structure. Two distinctive H-bond motif recognized were"dimer'' (n=2,4 ,5;Fig.1 (a)) and "tetramer" (n=1 ,3;Fig .1(b)) structures around inversion
center. Because of this packing differences, methyl (n=1) and propyl (n=3) acetates havefewer number of H-bond comparing to other acetates. Therefore , lower m.p. of them iscaused by this kind of inefficiency of crystal packing

P0 56
COORDINATION POLYMER WITH ZEOLITE OR ZEOLITE-LIKE
TOPOLOGIES
Yun-Qi Tian ,a.b Lin-Hong Weng ,a Zhen-Xia Chen• , Dong Yuan Zhao• and Xiao-Zeng You c•College of Chemical Science and Engineering, Liaoning University, Shenyang 110036,
China (ytian588@sina.com); bDepartment of Chemistry, Fudan University, Shanghai
200433 , China . estate Key Laboratory of Coordination Chemistry, Institute of Coordination
Chemistry, Nanjing University, Nanjing 210093 , China .

Coordination polymers with stable frameworks of big openings are of current interestand importance for many applications involving catalysis, separation and gas storage. To
create such materials we have developed a strategy for synthesis of coordination
polymers with zeolite or zeolite-like structures , namely, the natural choice of the porous
materials. Cobalt(ll) or Zinc(ll) imidazolates are such coordination polymers synthesizedthat exhibit not only the silicate-like polymorphism , but also the zeolite or zeolite-like
topologies. Up to now, we have explored at least 9 neutral extended three-dimensionalframeworks of [M(im) 2J. (M = Co(ll), Zn(ll) ), which show the characteristics of zeolite
structures and high thermal stability.
We thank the Post-doctor funds of the State and Shanghai-City, the State Key Projectof Fundamental Research and the National Science Fund of China for the financesupport.
References
1 Hee, K. C., Siberia-Perez, D. Y. , et al. (2004) Nature , 427 , 523-527 .
2 Tian , Y. Q., Cai, C. X., Ji , Y. , You , X. Z. , Peng , S. M. and Lee , G. S. (2002) Angew.
Chern. Int. Ed. , 41, 1384.
3 Tian , Y. Q., Cai , C. X. , Ren , X. M., Duan , C. Y., Xu , Y. , Gao , S. and You , X. Z. (2003) ,Chern. Eur. J. 9, 5673 -5685.
4 Tian , Y. 0 ., Chen , Z. X. , Weng , L. H. and Zhao , D. Y. unpublished results

P0 57
CRYSTAL STRUCTURES OF COMPLEXES OF AMINO ACIDS WITH ZINC
AND CADMIUM CHLORIDES: IONIZATION STATES, STOICHIOMETRY,
COORDINATION AND CRYSTAL PACKING
R.V.Krishnakumar•, M.Subha Nandhinib and S.Natarajanb•Department of Physics , Thiagarajar College , Madurai - 625 009 , bDepartment of Physics ,Madurai Kamaraj University, Madurai-625 021 , India (mailtorvkk@yahoo.co.in)

Zinc - amino acid complexes are interesting as zinc is known to compete
successfully with cadmium for protein binding sites. Zinc also plays an important biologicalrole in the formation of a structural motif called zinc fingers which are characteristic ofcertain proteins that bind to DNA. Recently, we have elucidated the crystal structures ofcomplexes of DL-Aianine , Sarcosine , DL-Valine with ZnCI 2 and ~ -Alanine , Sarcosine and
DL-Valine with CdCI 2 . Single crystals of the compounds were obtained from saturated
aqueous solution containing respective amino acids and inorganic salts in a 2:1
stoichiometric ratio. Interestingly, two different crystalline forms were obtained in the caseof sarcosine with ZnCI 2 and in one of the forms the sarcosine molecule adopts an unusual
cationic form which may be justified by a complex series of hydrolytic equilibria involving
the solvent water molecules , the Cl- ions and the sarcosine zwitterion. The coordination
polyhedron around zinc is , in general , a distorted tetrahedron and that around cadmium adistorted octahedron. In halegenozinc - amino acid complexes, the crystal packing ischaracterized by amino acid molecules coordinating to Zn forming a linear chain throughhydrogen bonds. In the case of amino acid - CdCI 2 complexes , the packing of molecules
is characterized by infinite one-dimensional polymeric chains in which the carboxyl groupof the respective amino acid molecules form chelated rings . The results of a detailed
analysis of the ionization states , stoichiometry, coordination geometry and crystal packing
features will be presented .

P0 58CRYSTAL AND MOLECULAR STRUCTUR OF
BIS(HYDRAZINIUM)BIS(OXALATO)NICKEL(II) DIHYDRATE AND
BIS(HYDRAZINIUM)BIS(MALONATO)COBALT(II) DIHYDRATE
V. Manivannan •, K.R. Radhakrishnan b, K. Saravanan c, S. Govindarajan c* and J.J. Vittald•Department of Physics, Presidency College , Chennai , 600 005 , India ; bOepartment of
Physics , Government Arts College, Kumbakonam 612001 , India; cOepartment ofChemistry, Bharathiar University, Coimbatore 641 046, India; d0epartment of Chemistry,
National University of Sigapore , Singapore , 117543.
(manivan_1999@yahoo.com)

New bis(hydrazinium)bis(oxalato)nickel(ll) dihydrate, [(N 2 H5 ) 2 Ni(COO)zl.2Hp (1) andbis(hydrazinium)bis(malonato)cobalt(ll) dihydrate, [(N 2 H5 ) 2Co(CH 2 (C00) 2 )zl.2H 2 0 (2) have been
prepared and their structure determined from single crystal X-ray analysis . The
crystallographic data for the compound 1 are monoclinic, space group P2,fc with a =6.2814 (2) , b = 12.9937 (6) c = 7.1101 (2) A, b = 102.746 (3t , Z = 2 and R = 0.0260. The
compound 2 crystallizes in the triclinic space group P-1 with a= 5.2383 (7), b = 7.5091 (10), c=8.5289 (11) A, Z =1 and final R factor of 0.0376 based on 1672 independent reflections. Boththe crystals contain discrete [(N 2 H5 ) 2 Ni(C00) 2] I [(N 2 H5 ) 2Co(CH 2 (C00) 2 ) 2] and water molecules.
In these complexes the metal ion is coordinated with regular octahedral geometry, the squareplane being occupied by four carboxylate oxygens from the two chelate-bidentate oxalate I
malonate groups and the apical positions by two nitrogen atoms one from each hydrazinium
cation . The structure analysis of the 1 shows that, the oxalate groups are planar and thehydrazinium cations are trans to each other. Both compounds posses a center of inversion , as
the coordinated atoms and the water molecules are trans to each other. In compound 1 theoxalate oxygens are hydrogen bonded to the hydrazinium ions by the N-H .. .0 type of bondpredominantly. Such net works are found to extend throughout the crystal. The 0-H ... 0 type ofhydrogen bond between water and oxalate also exist. Similar type of hydrogen bonding is also
observed in compound 2. As compared to compound 1, the compound 2 undergoes
dehydration at elevated temperature (260"C), indicating that the water molecules are strongly
involved in the hydrogen-bonded network in the latter.

P0 59SYTHESIS AND CRYSTAL STRUCTURES OF POLYNUCLEAR
TITANIUM(IV) AND ZIROCONIUM(IV) COMPOUNDS SUPPORTED BY ANOXYGEN TRIPODAL LIGANDS
Xiao-Yi Yi , Tony C. H. Lam , E. Y. Y. Chan. Qian-Feng Zhang , lan D. Williams , and WaHung Leung*
Department of Chemistry and Open Laboratory of Chirotechnology of the Institute of
Molecular Technology for Drug Discovery and Synthesis, The Hong Kong Un iversity of
Science and Technology, Clear Water Bay, Kowloon , Hong Kong , China (E-mail:chleung@ust.hk)

Metal ions in oxygen-rich coordination environments are of significance because they
are relevant to active sites of oxide based heterogeneous catalysts. In an attempt tomodel metal oxide surfaces , we set out to prepare titanium and zirconium complexes
containing an oxygen tripodal ligand [CpCo{P(O)(OEt) 2M (L 0 E,V Previously, wedemonstrated that the titanyl and zirconyl species can be trapped by NaL0 E1 in water andthe resulting species can react with BF; to give L0 E1MF 3 (M = Ti or Zr). 2 We here present
the characterization and solid-state structures of water-soluble cluster compounds formedby the reactions of NaL0 E, with titanyl sulfate and zirconyl nitrate in water. The core
structures of these clusters are found to be closely related to those of group 4 metaloxides and metal aqua ions . Treatment of L0 E1Ti(IV) complexes with metal ions give
heterobimetallic clusters that have been characterized by X-ray crystallography.

ge
Eta"

p

_.....---co------ _..... OEt
1 OEtp....._

EtO.....- 11 EtO - p 0
II

II
0

OEt

0

e

L oEt

Zr = LoEtZrReferences
1
Klaui , W. Angew. Chem. , Int. , Ed. Engl. 1990, 29, 627.
2
Lam , T. C. H.; Chan , E. Y. Y.; Mak, W. L. ; Williams , I. D.; Wong , W. T. ; Leung , W.-H .
lnorg. Chem. 2003 , 42, 1842.

P060
DIRECT OBSERVATION OF DIFFERENT REACTION ROUTE DUE TO
STERIC HINDRANCE IN CRYSTALLINE-STATE PHOTOISOMERIZATION
Yuji Ohashi . Akira Hirano, Hidehiro Uekusa
Department of Chemistry and Materials Science , Tokyo Institute of Technology,
Ookayama , Meguro-ku, Tokyo 152-8551 , Japan(yohashi@cms .titech.ac.jp)

The li-cyanobutyl group bonded to the cobalt atom in cobaloxime complex crystals isisomerized to y-, P- and a.-cyanobutyl group when the powdered sample is exposed tovisible light as shown in the Scheme .
CH 2CH 2CH 2CH 2CN

I

Co(dmg) 2I

H3 CC*HCH 2CH 2CN HSC2C*H CH2CN H7 C3C*HCNI

Co(dmg) 2

I

B

B

(li)

(y)

I

Co(dmg) 2

I

B
(p)

I

Co(dmg) 2

I

B
(a.)

Scheme: Stepwise photoisomerization of li-cyanobutyl group in cobaloxime
complex crystals
When the single crystal with the li-cyanobutyl group was irradiated with the xenon
lamp , a part of the li-cyanobutyl group was isomerized to y-cyano-butyl group. Further
irradiation caused the decomposition of the crystallinity. The reaction cavity for the
cyanobutyl group is too small to proceed further reactions .
In order to expand the reaction cavity around the li-cyanobutyl group , the bulky
substituent, dibenzylboronyl group , was introduced to the equatorial ligand and the crystal
was irradiated with the xenon lamp in the same conditions.
The crystal structures before and after photoirradiation were analyzed by X-rays.
After 24 hours exposure, the complex with the a.-cyanobutyl group appeared in the crystal
and the ratio of 8- to a.-cyanobutyl groups was 75:25. The intermediate complexes withthe y- and p-cyanobutyl groups were not observed. Since the crystal was graduallydecomposed after 24 hours, the structural change was checked with theIR spectra . The
spectra indicated that not only the original li-cyanobutyl group but also the produced a.cyano-butyl group gradually decreased and the p-cyanobutyl group gradually appeared .
This suggests that the reaction proceeds 8- to j3-cyanobutyl group through a.-cyanobutylgroup , which is completely different from the compound without bulky dibenzylboronylgroup. The y-cyanobutyl group was not observed in the IR spectra . The shape of thecavity for the cyanobutyl group well explains the above reaction.

P061

NOVEL BIS-DIDENTATE NITROGEN LIGAND DERIVED
DIHYDRAZINOPHTHALAZINE

FROM

1,4-

Ling-Kang Liu• and Wen-Fu Changb•institute of Chemistry, Academia Sinica , Nankang, Taipei , Taiwan and bQepartment ofChemistry,
National
Central
University,
Chung-Li ,Tao-Yuan ,Taiwan(liuu@chem .sinica .edu.tw7
Upon reflux with pyridine-2-carbo xaldehyde , 1,4-dihydrazinophthalazine 1 could betransformed into the corresponding Schiff base 2 , whose oxidative cyclization in atreatment with Br2 gave bis-triazole derivative 3 , a novel bis-didentate nitrogen ligand
bridged by a rigid aromatic backbone. The C2-symmetric 3 exhibited very interesting
molecular properties that were pH dependent as spectroscopically characterized . When 3
reacted with Ru(C072 CI 2 , the C 2 -symmetric diruthenium complex 4 resulted .

HNNH,

,
N

~ l
_ o
'_"=••_N~

N
HN,
1

NH ~

The structure of 3 was determined by X-ray diffraction. Unconstrained in the solidstate , the structural parameters of 3 conform to the C 2 molecular symmetry. It is further
noticed th at intramolecularly the distance between two pyridine N atoms is only 3.075 A,
which is shorter than the sum of van der Waals radii , suggesting an attractive interaction .

P062
SOLID CRYSTALLINE FORMS OF DICLOFENAC SODIUM AND
DICLOFENAC ACID
Chuttree Phurat,• Narong Praphairaksit,a Malatee Taiyaqupt,0 Nongnuj Muangsin••Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok, 10330,
Thailand .
0 Department of Geology, Faculty of Science , Chulalongkorn University, Bangkok, 10330,
Thailand .
Different solid forms of a pharmaceutical substance may display different physicaland chemical properties. Pharmaceutical substances may change to different polymorphs,
solvates (pseudo-polymorphism), desolvates , or amorphous materials after standard
pharmaceutical processes such as crystallization , milling , freeze-drying , spray-drying , andsolid-dispersion , which may change their pharmaceutical activities.
Diclofenac ,(2-[2 ,6-dichlorophenyl)amino]-phenyl]acetate)isanexcellent
nonsteroidal anti-inflammatory drug (NSAID} and is mainly used in the treatment ofrheumatoid arthritis and other rheumatoid disorders. Diclofenac has numerous solid forms
including diclofenac acids and diclofenac salts. The exemplary diclofenac acid crystal
forms include its monoclinic forms with the space group P2 ,1c and C2/c (Castellari &Ottani , 1997). Diclofenac acid also exists in an orthorhombic form with the space group
Pcan (Jaiboon eta/. , 2001 ). The examples of diclofenac in its salt forms include potassium
diclofenac dihydrate (Fini eta!. , 2001 ), sodium diclofenac tetrahydrate (Fini eta/. , 2001 ).
In this work, solid crystalline forms of diclofenac sodium and diclofenac acid havebeen identified and characterized using X-ray powder diffraction (XRPD), scanningelectron microscope (SEM}, thermogravimetric analysis (TGA) , solubility and melting
point. In addition , biological activity against COX-1 of all solid crystalline forms andcommercial diclofenac sodium have been tested .
References
1
Castellari , C. & Ottani, S. (1997). Acta. Cryst. , C53 , 794-797 .
2
Jaiboon , N. Yos-in , K., Ruangchaithaweesook, S., Chaichit, N., Thutivoranath , R. ,Siritaedmukul , K. & Hannongbua, S. (2001). Analytical Sciences. 17, 1465-1466.
3
Fini , A. , Garuti , M. , Fazio G., Alvarez-Fuentes , J. & Holgado, M. A. (2001 ). J.
Pharm. Sci , 90(12} , 2049-2057 .

P063
SELF-ASSEMBLY OF FOUR METAL-SQUARATE (Cd(ll) and Zn(ll))
COORDINATION POLYMERS WITH FLEXIBLE 1,2-BIS(4PYRIDYL)ETHANE LIGAND (DPE)Chih-Chieh Wanq ,a Hui-Wun Lin ,a Chin-Hui Liao ,a Cheng-Han Yang ,a and Gene-Hsiang
Leeb•Department of Chemistry, Soochow University, Taipei , Taiwan (ccwang@mail.scu .edu.tw);
blnstrumentation Center, National Taiwan University, Taipei , Taiwan.

Four types of new metal-organic coordination networks, [M(C 4 0 4 MH 2 0) 2][M(Hdpe)(C 4 0 4 ) 0 5 (H 2 0) 3] (M = Zn 1, Cd 2) , [M(C 4 0 4 ) 15 (Hp) 3][H 2 dpe] 05 (2) (M = Zn 3, Cd 4) ,[Zn(dpe)(C 4 0 .)(Hp) 2] (5) and [Cd(dpe)(Hp)4 ](C 4 0 4 ) (6), based on squarate and/or dpe
bridges (dpe = 1 ,2-bis(4-pyridyl)ethylene) have been synthesized and characterized byspectroscopic data and single-crystal X-ray diffraction studies. The structural
determination reveals that compounds 1 and 2 are a 3D network constructed by theinterlock of two charged 2D metal-organic frameworks , the [M(C 4 0 4 ) 2 (Hp)2)2- and[M(Hdpe)(C.0 4 ) 05 (Hp) 3 )2•, that both adopt the square-grid as the basic building unit via
the linkage of metal center with p1.3-squarate and p 1 _2 _3 .4-squarate ligands , respectively, toform the 20 layered frameworks. In the cationic part, two mono-protonated anti-Hdpe+ act
as monodentate ligands coordinated to the metal center at trans-positions andinterpenetrate into the cavities formed by the square grids in [M(C.0 4 ) 2 (Hp) 2)2-. The
molecular structure of compounds 3 and 4 show a 2D network, consisting of the[M(C 4 0 4 ) 15 (Hp)J anion and the free diprononated H2 dpe 2 • cation. The [M(C 4 0 4 ) 15 (H2 0) 3] is a 2D infinite layered framework using a 6,6-membered ring as building unit via thelinkage of six metal centers and two p 13- , four p12-squarate ligands. Compound 5 is a 20
wave-like framework , being constructed from the crosslinkage of the infinite 1D [Zn(~t 1 _ 3 squarate)(Hp)] chains by gauche-dpe ligands. Compound 6 is a 10 linear chain via thelinkage of Cd center and anti-dpe ligand . Hydrogen bond plays an important role on thestabilization of these four metal-organic coordination networks.

P064
HYDROTHERMAL SYNTHESIS, CHARACTERIZATION, AND
SUPRAMOLECULAR STRUCTURE OF [Co(C6H402N)3]·H20
Kittiponq Chainok and Kenneth J. Hailer
School of Chemistry, Institute of Science , Suranaree University of Technology,
Nakhon Ratchasima , 30000 , Thailand (kchainok1 O@yahoo.com)
The hydrothermal synthesis using vanadium pentoxide , cobalt chloride hexahydrate ,1,3-diaminopropane , 2,5-pyridinedicarboxylic acid , and H20 in a molar ratio of 1:1:2:2:593
produced 0.65 g of red crystals of [Co(C6H40 2N)3]·H20 in a yield of 84% based on cobalt.
Single crystal x-ray diffraction, SEMEDX ,FTIR, and TGA were used to characterize thecomplex. Intensity data were collected on a Bruker Nonius KappaCCD autodiffractometerequipped with a molybdenum x-ray source. The structure was solved by direct methods
and refined with the SHELX package . The complex has distorted octahedral coordinationgeometry with three mer pyridine nitrogen atoms and three mer carboxylate oxygen atoms
as shown on the left below. The molecules pack as a series of offset phenyl-phenyl faceto-face (n···n) interactions between ring type 1, propagated by alternate 2-fold sites andinversion sites in the c direction giving an interdigitated double comb motif. The watermolecules bridge the rings of type 1 to rings of type 2 on adjacent n ···TT stacks generatinga two-dimensional network. The third dimension is achieved by phenyl ring 1 to ring 3
edge-to-face interactions between adjacent n···TT stacks.
The EDX spectrum of the red crystals indicates the presence of only cobalt. IR (KBr):
3520(s) 3454(s) 3112(s) 3061 (s) 1681 (s) 1607(s) 1571 (s) 1453(s) 1333(s) 1284(s)1152(s) 1056(s) 859(s) 766(s) 689(s) 492(s) 406(s) cm-1 . Thermal decomposition under0 2 shows loss of water at 156 oC (4.6% loss) followed by a broad step from 308 to 412 oCof 79.8% as the ligands decompose. Reasonably, all of these results correspond to the xray analysis. Crystal data: [Co(C6H40 2N)3)·H20 ; Mr = 425 .24 Daltons ; monoclinic, C2/c
(No . 15); a= 29 .727(4) A, b = 8.5401(6) A, c = 13.8024(11) A, f3 = 95.862(9t, V =3485.71(3) AJ;= 4; Deale = 1.689 glcmJ; J.l = 10.4 cm-1; AMoKa =0.71073 A; T = 298 K.
Data collection: Nonius KappaCCD, 0.5 mm ifg capilliary collimator, R merge = 0.0431 , 6672
unique data, 4349 observed data (/o > 4a(fo)).

z

ORTE P drawing (50% ellipsoids)

Projection down [010]P065
THE ORDER-DISORDER TRANSITION AT 150 K OF POLYMERIC
Ag(bipy)N03
Weenawan Somphon ," Kenneth J . Hallera and A. David Raeb
•school of Chemistry, Institute of Science, Suranaree University of Technology , Nakhon
Ratchasima 30000 , Thailand ; bResearch School of Chemistry, The Australian National
University, ACT 0200 , Australia (weenawanus@yahoo.com).

Ag(bipy)N0 3 , bipy = 4,4'-bipyridine = C10HaN2, has two known crystal forms at room
temperature [1 ,2,3]. The Fddd form contains a disordered nitrate ion and shows previously
unreported planes of diffuse scattering indexable as 3k ± I = 4n for the RT cell a12.952(2), b 9.912(1 ), c 34.428(4) A. Automated data collection used a Non ius
KappaCCD diffractometer equipped with an Oxford Cyrostream 600 . Synthetic precession
photographs showed the symmetry was Fddd at 160 K and above but a loss of systematicabsences indicated F12/d1 (i.e. C2/c) at 150 K and below. The 100 K structure, C2/c, a
12.751(1), b 9.860(1) , c 18.379(2) A, f3 109.98(1) o had twin components related by arotation around c*. The cell for F12/d1 has a'= a, b' = b, c' 34.547(2) A, [3' 89.68(1) 0 . All
intensities were obtained as the sum of two components. Refinement gave a
0.754(1 ):0 .246 twin with no disorder and R(F) = 0.021 for 2293 (out of 2456) reflections
with I > 3o(/). Along a chain , Ag atoms, (3b ± c)/4 apart, move 0.221 (1) A in opposite
directions perpendicular to the chain. Chains are cross linked by Ag-Ag contacts of
2.958(1) A and Ag-O contacts of 2.749(2) and 2.747(2) A. The chains zig-zag so that Ag
atoms avoid closer contact with the nitrates. The 200 K structure, Fddd, a 12.823(1 ), b
9.937(1 ), c 34.450(1) A, was refined as a 1:1 disorder of all atoms initiated by disordering
the 100 K structure . Constrained refinement gave R(F) = 0.028 for 1004 (out of 1270)
reflections with I > 3o(/). The Ag displacement reduced to ±0.123(3) A. The alternativeorientation of the nitrate gave 3 Ag-O contact distances indicating an intermediate step fora change of local ordering . The 16S root mean square angular displacement of thenitrate (up from 10.1 °) showed that the nitrate ions readily rotate by 60 o in their own
plane to initiate the orderdisorder phase change . The diffuse scattering indicates that
mistakes in nitrate positions cause a localised straightening of the adjacent chains thatmoves substantial amounts of these chains along their lengths. In contrast, the actual
position of a nitrate only affects the closest Ag atoms.
References
1
Bi, H., Sun, D. , Cao, R. and Hong, M. (2003) Acta Cryst. E58 , m324-m325 .
2
Robinson, F. and Zaworotko , M. J. (1995) J. Chern. Soc., Chern. Commun.
2413-2414 .
3
Yaghi, 0 . M. and Li, H. (1996) J. Am. Chern. Soc. 118, 295-296.

P066
SUPRAMOLECULAR STRUCTURE OF
AZIDONITROSYLBIS(TRIPHENYLPHOSPHINE)NICKEL
Nongnaphat Khosavithitkul and Kenneth J. Hailer
School of Chemistry, Institute of Science , Suranaree University of Technology, Nakhon
Ratchasima 30000 Thailand .(unchalee@ccs .sut.ac.th)
The sum of the multiple phenyl-phenyl edge-to-face (ef) C- H···rr attractive interactionsof the concerted sextuple phenyl embrace (6PE) gives sufficient interaction energy tomake it a dominant supramolecular motif for triphenylphosphine (TPP) complexes [1] . The
three-dimensional crystal structures of Ni(NCS)(NO)(P(C6Hshh and NiCI(NO)(P(C6Hs)3)z
are dominated by phenyl-phenyl interactions , including the expected strong six-fold phenyl
embraces between adjacent triphenylphosphine ligands . The chloro complex also exhibits
an extensive concerted interaction between a solvent benzene molecule and several
phenyl rings on surrounding molecules . The subject of this report is the reinvestigation of
the crystal structure of the title complex ,Ni(N3)(NO)(P(C6Hs)3)z, [2], in which the sextuple phenyl embrace does not occur.
The title complex was synthesized from NiBr(NO)(P(C6Hs)3)2 by a metathesis reaction
with excess NaN 3 and recrystallized from benzene-hexane as deep blue-black crystals.
The structure of the compound has been redetermined based on an x-ray data set
collected on a KappaCCD diffractometer. The compound crystallizes in the monoclinic
space group P2 ,/c with Z = 4. The discrete pseudo tetrahedral Ni(N3)(NO)(P(C6Hs)3)z
molecules are interconnected into a three-dimensional supramolecular structure by
C- H·· ·n hydrogen bonds to the azido and phenyl rr electron density.
The shortest intermolecular p ... p distances in the azido complex are 7.350 A and7.783 A with colinearities of 86.9° and 117.8°, thus not 6PE. The strongest nonbonded
interaction is the 2.466 A intramolecular C- H··· N interaction to the lone pair on the N
bonded to Ni. While there are several phenyl-phenyl interactions as well , the stronger
interactions to the azido ligand dominate and the highest multiple phenyl embrace only
involves four phenyl rings . However, seven additional C- H···N interactions in the range of
2.6 - 2.8 A surround the azido ligand , making in the major determiner of the extended
crystal structure .
References
1
Dance , 1. , & Scudder, M. (1995). The Sextuple Phenyl Embrace , a UbiquitousConcerted Supramolecular Motif. J. Chem. Soc., Chem. Commun. 1039-1040.
2
Enemark, J. H. (1971 ). Four-Coordinate Metal Nitrosyls 1. the Structure of Azidonitrosylbis(triphenylphosphine)nickel , Ni(N3)(NO)(P(C6Hs)3)2. lnorg. Chern. 10,
1952-1956.

P067
THE CRYSTAL STRUCTURE OF PYRIDINE-3,5-DICARBOXYLIC ACID
Samroeng Krachodnok and Kenneth J. Hailer
School of Chemistry, Institute of Science , Suranaree University of Technology,
Nakhon Ratchasima 30000 , Thailand (Lipopoo@yahoo.com)

Crystals of the title compound were obtained as unreacted starting material from ahydrothermal synthesis reaction. The compound crystallizes in the monoclinic space group
P21 /c with a= 9.6756(4), b = 11.1166(7), c = 6.5808(4) A, 13 = 107.766(4) 0 , and V =674.07(7) A3, T = 298 K. Intensity data were collected on a Bruker Nonius KappaCCD
diffractometer using graphite monochromated Mo Ka x-radiation.
The molecules are interconnected in two-dimensional layers (parallel to the abplane) through O.H·· ·N hydrogen bond interactions between adjacent molecules related bya 21 screw axis , and O.H· ··O hydrogen bond interactions between adjacent molecules
related by the other independent 21 screw axis (left figure below). Thus , the possibility of
the ubiquitous inversion related carboxylic acid dimer structure is precluded.
Layers related by the c glide and inversion centers are held together by face-toface , n.n interactions, supplemented by >C(o+)···0 interactions between carbonyl carbon
and carbonyl oxygen atoms across inversion centers (right figure below).
Crystal data: C7H5N04; Mr = 167.12 Daltons ; transparent pale orange ; thick plate0.06 x 0.10 x 0.26 mm ; monoclinic; P2 1/c (No. 14), a = 9.6756(4 ), b = 11.1166(7), c =6.5808(4) A, 13 = 107 .766(4) and V = 674.07(7) A3, Z = 2, T = 298 K, J.l = 1.4 cm-1; d eale =1.647 Mg/m3; A MoKo = 0.71073 A; Data collection: Non ius KappaCCD; 0.5 mm ifg capillary
collimator; 23425 data collected (triclinic), 8 max = 31.0 o; 2147 unique (2/m), R sym = 0.040 ;
1532 observed Fa > 4a(Fo).
0,>C(o• ) ·· 0 interactions
Layer projected d own (00 1)

P068
INVARIOMS FOR AUTOMATED LOW ORDER DATA CHARGE DENSITYANALYSIS
B. Dittrich•, M. Spackman•, P. Lugerb•School of Biological , Biomedical & Molecular Sciences, University of New England ,Armidale NSW 2351 , Australia , (bdittric@pobox.une .edu .au); blnstitut fOr Chemie I
Kristallographie , Freie Universitat Berlin , Takustr. 6, 14195 Berlin , Germany.
Considerable effort is necessary for an experimental charge density study withrespect to the X-ray diffraction experiment and the modelling of the high resolution data.
By introducion of invarioms[1] , that define an intramolecular transferable atom using thenearest neighbor approximation[2]. invariomic multipole parameters can be predicted . For
this purpose we use theoretical calculations[3] on model compounds that mimic the samechemical environment as an atom in a given crystal structure. For the molecular electron
density theoretical structure factors[4] are calculated and a multipole refinement thenyields the parameters needed. This way approximated aspherical structure factors and an
improved geometry can be derived for a crystal structure of interest. Properties derived
from the density , i.e. Hirshfeld surfaces[5]. the electrostatic potential or topologicalproperties are then accessible. It is emphasized that by using this procedure standard low
resolution data sets can be evaluated . The fact that a defined limited number of invarioms
exists allows additionally the automation of the modelling process . The steps required ,starting from a spherical model , are then :1.) The assignment of an invariom to an atom in a structure2.) Setup of the local coordinate system of that atom
3. ) Transfer of the invariomic multipole parameters
4.) Refinement of geometry and thermal motion
A program for steps one to three has been developed. The usage of theoreticallycompared to the experimentally- derived multipoles[6] has several advantages. Here wewant to present results for a comparison of the invariom density to the theoretical and the
crystal density for a geometry from a high resolution data multipole refinement on the
dipeptide L-Phe-L-Pro . An application of the procedure outlined here to smaller proteins isin progress.
References

1
2
3
4
5
6

Dittrich , B. , Koritsanszky, T., Luger, P., Angew. Chern . 116, in press.
Koritsanszky, T. , Volkov, A., and Coppens , P. , Acta Cryst. A58 , 2002 , 464 .
Gaussian 98 , Revision A.11 .3, M. J . Frisch et al. , Gaussian , Inc. , Pittsburgh PA,
2002.
Chandler, G .S., Spackman , M. A ., Acta Cryst. A34 , 1978, 341 .
McKinnon , J.J ., Mitchell, A. S. , Spackman , M.A. , Chern. Europ ., J. 4 , 1998, 2136 .
Pichon Pesme, V., Lecomte , C. And Lachekar, H. , J . Phys . Chern. 99 , 16, 1995.

P069
NEW FACE-CAPPING BONDING MODE FOR ARENES IN
ORGANOMETALLIC METAL CLUSTERS
Jasmine Po-Kwan Lau , and Wing-Tak Wong*
Department of Chemistry, The University of Hong Kong , Pokfulam Road , Hong Kong , P.
R. China . (h9924717@hkusua .hku .hk)

Heterometallic carbonyl clusters have caught considerable attention because of theirpotential catalytic and stoichiometric reaction. The chemistry of Os-Rh mixed-metal
carbonyl clusters [1 ,2] are particularly interested due to the good combination of highreactivity and sufficient thermodynamic stability of the cluster intermediates occurred in
the reaction. The reaction of benzene (arenes) with Os-Rh mixed-metal clusters afforded
a new capping mode , C3v(sv), for the arene on the cluster surface , which comprises animportant area of research in surface science . The determination of the adsorption
geometry of arenes on metal surfaces can give insight into the elementary steps of the
dissociation and catalytic reactions of these molecules. [3]References
1 J. P. -K. Lau , W. -T. Wong , (2002) J. Organomet. Chern . 659 , 151-158.
2
J. P. -K. Lau , W. -T. Wong , (2003) lnorg. Chern. Comm. 6, 174-177.
3
J. P. -K. Lau , Z. -Y. Lin , W . -T. Wong , (2003) Angew. Chern. Int. Ed. Engl. 42(17) ,1935-1937 .

P070
STRUCTURAL STUDY OF COORDINATION NETWORK BASED ON
METAL ORGANIC LIGANDS
Lap Szeto , Yang-Yi Yang and Wing-Tak Wong*
Department of Chemistry, The University of Hong Kong , Pokfulam Road , Pokfulam , Hong
Kong , P. R. China (lapszeto@hkusua .hku.hk).
Supramolecular crystal engineering has attracted much attention in recent years .
This is because it holds promise to the discovery of new functional solids for applications
in non-linear optics (NL0)[1], porous material sciences[2] . Through the rational design ofselected ligands and metal , the careful study of the resulting crystal packing , the targeted
physical properties can be fine tuned . Studies on some of these supramolecular network
systems based on carboxylates[4,4] (see Figure 1 & 2) will be discussed .
References
1
Evans, 0 . R. and Lin , W.-B. (2002) Ace. Chern. Res. 35 , 511-522.
2
Eddaoudi , M. ; Moler, D.B .; Li , H.; Chen , B. ; Reineke , T.M. ; O'keefe , M.; Yaghi, O.M .
(2001) Ace. Chern. Res. 34 , 419-440 .
4
Yang , Y. Y. , Szeto , L. and Wong , W.-T . (2004) Appl. Organometal. Chern. 17 ,958-959.
4
Yang , Y. Y., Huang, Z.-Q. , Szeto , L. and Wong , W.-T. Appl. Organometal. Chern. In
press.

P071
POWDER NEUTRON DIFFRACTION STUDY OF A CRYSTALLINE-STATE
REACTION OF AN UNSATURATED THIOAMIDE DERIVATIVE
Takashi Ohhara ,a·b Susumu lkeda ,a Kenichi Oikawa ,b Akinori Hoshikawa ,a Takashi
Kamiyama ," Takaaki Hosoya ,c and Yuji Ohashic•Institute of Materials Structure Science , KEK, Tsukuba , lbaraki, Japan; bJapan Atomic
Energy Research Institute (JAERI), Tokai , lbaraki , Japan coepartment of Chemistry andMaterials Science , Tokyo Institute of Technology, Meguro-ku , Tokyo , Japan(ohhara@neutrons. tokai.jaeri. go.jp ).

Crystalline-state reaction , which proceeds with retention of single crystal form , isone of the most interesting topics in crystal chemistry and many reactions have been
analysed mainly by single crystal X-ray diffraction. Recently, author and co-workers
proposed a single crystal neutron diffraction (SND) analysis of a crystalline-state reaction
as follows ; hydrogen atoms in the reactive part of the reactant molecule are replaced with
deuterium atom as markers , then the crystalline-state reaction is proceeded , and finallythe migration of the deuterium atoms according to the reaction is observed by SND . This
analytical method is very powerful to analyse the mechanism of crystalline-state
reaction[1]. However, since SND requires a very large single crystal , it is much moredifficult to keep the single crystal form during the reaction than single crystal X-ray
diffraction study. So , we proposed to apply powder neutron diffraction (PND) instead of
SND .
In this work , we measured the powder neutron diffraction pattern of an unsaturated
thioamide derivative , which is the reactant of the crystalline-state photo-cyclization to forma ~ -thiolactam (Fig.1 )[2], before and after the photo-irradiation , and tried to observe thedeuterium migration according to the photo-cyclization. Hydrogen atoms in the reactive
part of the reactant molecule were replaced with deuterium atoms as markers. Though thetwo phenyl groups are not the reactive part, the hydrogen atoms of those phenyl groups
were also replaced with deuterium atoms to reduce the background of the PND pattern.
The cell parameter before irradiation is a=8.654A, b=1 0.156A, c=1 0.1 02A, ~=98.76 ° . PND
patterns were measured by Vega TOF powder neutron diffractometer at KENS with 15K.
The change of the powder pattern indicates the deuterium migration according to thephoto-cyclization.
References
T. Ohhara , S. Ikeda , H. lmura , H. Uekusa, Y. Ohashi , I. Tanaka, N. Niimura. (2002)
1
J. Am. Chem. Soc. , 124, 14736-14740.
2
T. Hosoya, T. Ohhara, H. Uekusa, Y. Ohashi. (2002) Bull. Chern. Soc. Jpn ., 75,
2147-2151 .

P072
STRUCTURAL CHARACTERIZATION OF THREE CRYSTALLINE
MODIFICATIONS OF CHLOROTHALONIL BY X-RAY POWDERDIFFRACTION
Xiurong Hu . Ziqin Yuan , Jianming Gu , Guanglie Lu and Xiaoyan Tu
Central Laboratory of Zhejiang University, Hangzhou 310028 , P.R.China (gllu@zju .edu.cn)

Monte Carlo/annealing simulation in the direct space was applied to solve the crystal
structures of three crystalline modifications of Chlorothalonils from X-ray powder diffraction
data. Results have shown they have different crystallographic parameters and the way ofstacking. Form A is monoclinic with space group P2,fa including four molecules in the unit
cell , form B and C are monoclinic with space group P 21 and include two molecules in theunit cell. Form A: a=24. 7415(28) A, b=6.2240(11) A, c=6.3364(7) A, ~=95.439(30 t.
V=971.4 A3 ; Form B: a=8 .1615(18) A, b=9.4191 A, c=6.4728(14) A, ~=93 . 7307(64 t.
V=497.8 A3 ; Form C: a=8.6003(10) A, b=9.2382(11) A, c=6.3024(7) A, ~=96.2152(60 t,
V=498.5 A3 .
Three modifications are stacked by two paralleled planar molecular chains along baxis in different stacking ways . Stacking ways for form B and form C are almost same , but
the adjacent two paralleled molecular chains in the form B are in the same plane , while
those in the form C are not. In the form A, there are double planar molecular chains sameas that of form C. These two chains cross each other(crossing angle is equal to ~) andstack alternately along a axis at the interval of 0.5a.

P073
CRYSTAL STRUCTURE AND CONFORMATION OF GEM-CHLORONITROSO- CYCLODODECANE (CH 2 )n_1CNOCI, WITH n=12
C.R. Girija and Noor Shahina Begum*
Department of Studies in Chemistry, Bangalore University, Central College Campus ,Bangalore-560 001 .1ndia.(noorsb@ rediffmail.com)

Gem- chloronitoso compounds find application in organic synthesis and mechanistic
studies , particularly as precursorsof aliphatic nitro derivatives and of vicinal
dinitrocompounds.
The crystal structure analysis of the title compound gem- chloronitrosocyclododecane ,(CH 2 )n_ 1CNOCI , with n=12 , has been determined by the X-ray diffraction
method.
The title compound crystallizes in the orthorhombic space group P2 12 1 21 with a=
8.3801(19)A , b= 9.5432 (21) A , c=16 .3480 (36) A , V=1307.4(5) A3 ,J..l=0.137mm·'
z = 4. The structure was solved by direct methods using SHELXS-97 and refined by byfullmatrix least squares on F2 using SHELXL-97 to a R- value of 0.1111 for 3072
reflections with 1>2o(l) collected using a Seimens Smart-CCD diffractometer with MoKa
radiation .
In the title compound , cyclododecane has the expected "square" [3333]
conformation like all other known saturated twelve membered rings but there is disorder
about the chloronitroso exocyclic group .. The structural and conformational features of thetitle compound will be discussed in detailP074

Chi-Rung Lee•*, Ching-Yi Lee• and Yu Wangb•Department of Chemical Engineering, Minghsin University of Science and Technology,
Hsin-Fong , Hsin-ChU , Taiwan. bQepartment of Chemistry, National Taiwan University,
Taipei , Taiwan . (crlee@must.edu .tw)
A hydrogen bond study was performed on dimethylammonium hydrobis(squarate),(H 2Me 2 )[H(HC.0 4 ) 2 ][1], using a detailed charge density study from accurate X-ray
diffraction and OFT calculation . The molecule has some interesting sets of intra- andintermolecular interactions in the crystalline state - two relatively strong 0 · H ·0 hydrogenbonds and some very weak secondary interactions. The interaction energy between two
H-bonded fragments were also investigated . The anion of this compound contains both asymmetric (0 H · O distance of 2.4321(8)A, bond angle of 179(2)0 ) and an asymmetric(0 H 0 distance of 2.5645(6)A , bond angle of 175(1 )0 ) H-bonds in the crystal. Results on
the electron density distribution will be presented in the form of deformation density and of
Laplacain maps . The ring strain of the four-membered squarate ring is nicely
demonstrated in the deformation density map with the bonding electron density maximum
outward from the C-C interatomic axic, such that two neighboring bonding electron density
maxima give an angle of 110° around C2 , which is much larger than the corresponding
C1-C2-C3 angle of 90.83(4 )0 . The bond characters of the C-0 , C-N and C-C bonds areapparent, and the agreement on the topological properties between experiment andtheory is adequate. All the interactions are verified by the location of the bond critical point
and its associated topological properties. The iso-value surface of Laplacian charge
density and the detailed atomic graph around each atomic site reveal the shape of thevalence shell charge contraction and provide a reasonable interpretation of the bonding ofeach atom.
Reference
1 Lin , K. J., Cheng , M. C. and Wang Y. (1994) J. Phys. Chem., 98 , 11685-11693.

P075
SYNTHESIS AND CHARACTERIZATION OF TWO POLYMORPHS OF
Fe(2,2' -bpy)(HP04)(H2P04)
Wen-Jung Chang ," Yau-Chen Jiang ,b and Kwang-Hwa Liia.c•Department of Chemistry, National Central University, Chungli ; bOepartment of Chemistry ,National Tsing-Hua University, Hsinchu ; clnstitute of Chemistry , Academia Sinica , Taipei,
Taiwan , RO .C. (liikh@cc.ncu .edu.tw)

We have been interested in using the organic ligands 2,2'-bipyridine and 1,10phenanthroline to synthesize new organic-inorganic hybrid compounds, and have recently
reported two compounds in the 2,2'-bpy-phosphate system [1] . As part of continuing workof this system , two polymorphs of organic-inorganic hybrid iron phosphate were isolated .
Both polymorphs were synthesized under hydrothermal conditions and characterized bysingle-crystal X-ray diffraction . Crystal data: Fe(2 ,2'-bpy)(HPO.)(H2PO.) (polymorph 1),
monoclinic space group P2 ,/n, a= 10.904(2) A, b = 6.423(1) A, c = 19.3 14(3) A, i3 =101 .161(3t. V = 1327.0(4) A3 , and Z = 4; Fe(2 ,2'-bpy)(HPO.)(H2PO.) (polymorph 2) ,monoclinic, space group P2,/c, a = 11 .014(2) A, b = 15.827(2) A, c = 8.444(1) A, i3 =109 .085(3t , V = 1395.1(3) N, and Z = 4 . Polymorph 1 adopts a 1D chain structure inwhich each Fe atom is coordinated by two nitrogen atoms from a 2,2'-bpy ligand and four
phosphate oxygen atoms . These infinite chains are extended into a 20 supramoleculararray via n -rr interaction of the lateral 2,2'-bpy ligands. The structure of polymorph 2
consists of the same building units which are linked through their vertices forming an
undulated sheetlike structure with 4.12 net Adjacent 20 layers are extended into a 30
array via rr-11 interaction of the aromatic groups. It is isostructural with Ga(2 ,2'bpy)(HPO. )(H2PO. ) [2] . In this presentation we will report the synthesis , crystal structures,and magnetic properties of these two polymorphs.
References
1
Chang , W-J , Chen , C.-Y. , and Lii , K.-H . (2003) J Solid State Chern. 172, 6-11 .
2
Lin , Z.-E ., Zhang , J., Sun , Y.-0. , and Yang G.-Y. (2004) lnorg. Chern. 43 , 797-801

P076
SYNTHESIS AND CHARACTERIZATION OF THE FIRST METALOXALATOPHOSPHONATE: (C3H12N2)o.s[Ga3(C204)(CH3P03)4]·0.5H20
Chia-Hui Lin• and Kwang-Hwa Liia.b·*•oepartment of Chemistry, National Central University, Chungli ; blnstitute of Chemistry,
Academia Sinica , Taipei , Taiwan , R.O .C. (liikh@cc.ncu.edu.tw)
Many research activities have focused on the synthesis of organic-inorganic hybrid
compounds by incorporating organic ligands in the structures of metal phosphates . The
underlying idea is to combine the robustness of inorganic phosphate frameworks with theversatility and chemical flexibility of organic ligands. A large number of oxalate-phosphates
and bipyridine-phosphates of transition metals and group 13 elements have been reported[1 ,2] . We have recently become interested in the synthesis of metal phosphonates
incorporating multifunctional organic ligands. Here we report the first example of metal
oxalatophosphonate , (C3H,2N2)os[Ga3(C20 4)(CH3P03).)-0 .5H20 , which was synthesizedunder hydrothermal conditions and characterized by single-crystal X-ray diffraction. It
crystallizes in the monoclinic space group P2,/n with a= 8.8514(4) A, b = 16.3030(7) A, c
= 15.0816(7) A, fJ = 97.539(1)0 , V = 2157 .53(17) N, and Z = 4. It adopts a 20 layer
structure with the interlayer space filled with 1 ,3-propylenediammonium cations and watermolecules. Within a layer there are Ga04 tetrahedra and GaOs octahedra connected bymethylphosphonate and oxalate groups. The solid state NMR spectroscopy has also beenstudied .
References
Jiang , Y.-C ., Wang , S.-L ., Lee , S.-F . and Lii , K.-H . (2003) lnorg. Chern. 42 ,16154-6156 and references therein.
Huang, L.-H ., Kao, H.-M. and Lii , K.-H . (2002) lnorg. Chern. 41 , 2936-2940 and
2
references therein.

P077
SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF A NEW
URANIUM SILICATE: Ks(U02)2(Si4013)
Chih-Shan Chen• and Kwang-Hwa Liia.b,*•Department of Chemistry, National Central University, Chungli ; blnstitute of Chemistry,
Academia Sinica , Taipei , Taiwan , R.O.C . (liikh@cc.ncu.edu.tw)

Organically templated metal phosphates have been extensively studied because ofinteresting structural chemistry and potential applications in catalysis. However, in mostcases the organic templates cannot be removed without collapse of the frameworks. This
is in contrast to the high thermal stability and extensive applications of zeolites in refineryand petrochemical processes. Therefore , studies have been directed to the synthesis of
metal silicates to produce more stable frameworks. Recently, Jacobson et al. reported thesynthesis of several uranium silicates under hydrothermal conditions at 180-240 oc byusing alkali metal or organic ammonium cations as templating agents [1-3]. In thispresentation we report high-temperature , high-pressure hydrothermal synthesis , crystal
structure , and solid-state NMR spectroscopy of a new uranium silicate . The title
compound crystallizes in the orthorhombic space group Cmca with a = 22. 178(4) A, b =12.229(2) A, c = 13.093(3) A and V = 3551.1 (1) N. The structure consists of tetrasilicate
units linked together via corner sharing by U06 octahedra to form a 3-D framework which
delimits channels along the a-axis , where the K• cations are located.
References
1
Wang , X., Haung , J. , Liu , L. , Jacobson , A. J. (2002) J. Mater. Chern. 12, 406-410 .
2
Haung , J. , Wang , X. , Jacobson , A. J. (2003) J. Mater. Chern. 13, 191-196.
3
Wang , X. , Haung , J. , Jacobson , A. J. (2002) J. Am. Chern. Soc. 124, 15190-15191.

P078
SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF(H 4 appip)[V 3 (C 2 0 4 ) 2 (HP0 4 UP0 4 )(H 2 0)]·6Hp (appip = 1 ,4-BIS(3AMINOPROPYL)PIPERAZINE), A LAYERED VANADIUMOXALATOPHOSPHATE CONTAINING DOUBLE-SIX-RING UNITS
Ming-Feng Tang• and Kwang-Hwa Lii•-b.*•Department of Chemistry, National Central University, Chungli; blnstitute of Chemistry,
Academia Sinica , Taipei , Taiwan , RO.C. (liikh@cc.ncu.edu .tw)

In recent years, a large number of hybrid compounds have been synthesized byincorporating multidentate organic ligands such as bipyridines and oxalate in the
structures of metal phosphates. The underlying idea is to combine the robustness of
inorganic phosphate frameworks with the versatility and chemical flexibility of organic
ligands. The oxalatophosphates form the largest group among these organically modified
metal phosphates. Most of these oxlatophosphates adopt 3-D framework structures, while
only a few have 2-D layer or 1-D chain structures. As part of continuing work of thissystem , we prepared a new oxalatophosphate that has a new type of layer structure builtof double-six-ring (D6R) units connected by phosphate and oxalate groups. It is one of the
few oxalatophosphates with 2D layer structures and the second example containing D6Runits. It crystallizes in the triclinic space group pl with a= 11.604(2) A, b = 12.391(2) A. c
= 15.220(3) A, a= 71.090(3)", [3 = 82.630(3)" , y = 62.979(3)" , V = 1843.8(5) A3 and Z = 2.
The structure consists of V6 (HP0 4 ) 6 double-six-ring (D6R) units connected by coordinating
CzO/- and P0 43- anions to form anionic sheets in the ab plane with charge-compensating
quadruply protonated 1 ,4-bis(3-aminopropyl)piperazinium cations and water molecules
between the sheets. There are two types of oxalate units in the structure: one type acts asa bridging ligand and chelates two metal atoms while the other oxalate unit chelates only
one metal atom and has two C-0 groups pendant between adjacent layers. Each layer
consists of D6R units as shown below.

P079
ELECTRONIC STRUCTURES OF POL YMORPHS IN
MONOHALOGENATED BENZYL DERIVATIVES OF 2,5-DIAMIN0-3,6DICYANOPYRAZINE DYES
Shinya Matsumoto," Yoko Uchida,8 and Mitsuhiro Yanagitab
80epartment of Environmental Sciences, Faculty of Education and Human Sciences ,Yokohama National University, Yokohama 240-8501 Japan ; bR. & D. Laboratory for HighPerform ance Materials, Nippon Soda Co ., Ltd ., Chiba 290-0045 Japan(smatsu@edhs.ynu.ac.jp).

2,5-Diamino-3,6-dicyanopyrazine dyes have been intensively
NCXNXNR2
studied as a novel fluorophore which can be appl ied to optoelectronical materials such as an emitter for organic electroluminescent R NNCN2
devices , since they exh ibit strong fluorescence in solution and even in
the solid state[1 ,2] . These dyes have also been known to have some 1: R= - CH2 - Q -c l
crysta l polymorphs wi th different colors depending on the substituentson the am ino groups. In this study, th e correlation between electronic 2: R= -CH29
Cl
structures and molecular conform ation in single crystals were
investigated for some polymorphs of the four monohalogenated benzyl 3: R= - CH2- Q -Br
derivatives shown in the diagram: two polymorphs of 1(red and yellow)
4: R= - CH2p
and 4(red and orange), the red phase of 2 and the yellow phase of 3.
Br

The conformation of molecu les in these crystals was found to depend on not thesubstituent but the color of crystals. The amino nitrogens in the red and orange phases
have a trigonal planar geometry ; whereas the tetrahedral conformation of the amino groups
was found in the yellow phase . Semi-empirica l molecular orbital ca lcu lations revea led that
this structural feature can be correlated with the electronic structures of a molecu le incrysta ls. Th e color difference was mainly attributed to the change in the HOMO due to theconformationa l change of the amino groups.
References
1
Matsuoka , M. (2000) in Colorants for Non-textile Applications (H. S. Freeman and A.
T. Peters ed.) , Elsevier Science, 339-381 .
2
Sh irai , K. , Matsuoka, M., Matsumoto, S. and Shiro, M. (2003) Dyes Pigm. 56 , 83-87.

POBO

HYDROGEN BONDING PATTERN AND n-rc-INTERACTIONS IN
1, 7 -bis-(4-HYDROXY -3-METHOXYPHENYL)-HEPTA-3,5-DIONE(TETRA HYDRO CURCUMIN)
Noor Shahina Begum * , C.R. Girija , and Syed . A .A"
Department of Studies in Chemistry, Bangalore University, Central College Campus ,Bangalore-560 001 .India.
•Department of Studies in Chemistry, , Manasagangotri , University Of Mysore ,Mysore-570 006 , India

Tetrahydrocurcumin is the reduced form of curcumin which is known to posses
important cosmoceutical properties.
_
The title molecule , C, H220 6 crystallizes in the triclinic space group P1 with the unit cellparameters a= 7 .9813(30) A , b= 11 .3881 (30) A , c=12.4966 (30) A , a =117.065(3r ,~ =100 .394(10) · , y = 94 .856(3) ·, V = 97666(35) N , I.J = 0.092mm·' and z = 2. The
structure was solved by direct methods using SHELXS-97 and refined by fullmatrix leastsquares on F2 using SHELXL-97 to a R- value of 0.061 for 3244 reflections with 1>2a(l)collected using a Seimens Smart-CCD diffractometer with MoKa radiation . The structure
exhibits interesting bifurcated hydrogen bonds formed between the oxygen atoms of thehydroxyl ,methoxy and diane groups. The dihedral angle 84 .55. between the phenyl ringsin the molecule indicate that they are orthogonally placed .
The packing of the molecule is stabilized by rr- rr interactions and hydrogenbonding.
The molecular packing down the b-axis shows layered structure .Detailed structuralfeatures ,intermolecular interactions and packing modes will be presented .

P081
LANTHANIDE CONTRACT AND PH VALUE CONTROLLED STRUCTURESCHANGE IN A SERIES OF RARE EARTH COMPLEXES WITH PAMINOBENZOIC ACID, CRYSTAL STRUCTURE AND LUMINESCENCEPROPERTY
Jun-Ran Li , Hao-Ling Sun , Chao-Hong Ye , Xin-Yi Wang , Song Gao
State Key Laboratory of Rare Earth Materials Chemistry and Applications , PKU-HKU Joint
Laboratory on Rare Earth Materials and Bioinorganic Chemistry, College of Chemistry andMolecular Engineering , Peking University, Beijing 100871 , China (lijunran@pku.edu.cn)

p-Aminobenzoic acid (HL), a very important biological ligand , can form complexes withmany metal ions . However, the structure of rare earth complexes with HL has seldom
been investigated [1-2]. The relationship between luminescence performance andcoordination mode of a ligand is not as well explored for a complex. A series of rare earth
complexes with p-aminobenzoic acid (HL) were synthesized as [RE 2 L6 (Hp) 2ln [RE=La(1),Ce (2), Pr(3) , Sm(4) , Eu(5) , Tb(6), Dy(7), Er(9)] and [RE 2L6(Hp)4 ]·2Hp [RE=Tb (6"),Ho(8), Yb(10) , Lu(11) , Y(12)] . The crystal structures of 1, 2, 6, 6', 7, 9 and 12 were
determined and isomorphous relationships of the others identified. Their structureschange from a two-dimensional (20) array (the metal ions are nine-coordinated for 1 oreight -coordinated for 2-7 and 9) to a two-nuclear structure (the metal ions are eightcoordinated) for 6', 8 and 10-12, as controlled by lanthanide contraction . The effect of thepH value of the reaction mixtures on the crystal structure was found. The unusual
luminescence characteristic of complexes 6 and 6' revealed the relationship between the
fluorescence property and the number of coordination water molecule and thecoordination mode of a ligand in the complex.

N1

Two-dimensional structure of 6

Two-nuclear structure of 6'

References
1 Rzaczyriska , Z. , belsky, V. K. (1994) Polish J. Chern. 68 , 309-319.
2 Khiyalov, M. S. , Amiraslanov, I. R. , Mamedov, Kh. S., Movsumov, E. M. (1981) Zh .
Strukt. Khim. , 22(3) , 113-119; (1981) Koord. Khim. , 7(3) , 445-449.

P082
BIS(ALKYNYL) MERCURY(II) COMPLEXES OF OLIGOTHIOPHENES AND
BITHIAZOLESWai-Yeung Wong , Ka-Ho Choi and Guo-Liang Lu
Department of Chemistry, Hong Kong Baptist University, Waterloo Road , Kowloon Tong ,Hong Kong , P. R. China. (rwywong@hkbu.edu.hk)
A new class of binuclear mercury(ll) bis(alkynyl) complexes containing
oligothiophenes and bithiazoles as the central organic linkers are prepared . The solidstate molecular structures of [MeHgC=CRC=CHgMe) (R = thiophene-2 ,5-diyl, [2 ,2']bithiophene-5 ,5'-diyl) established by X-ray crystallography reveal that a loose polymeric
structure is formed in each case through weak intermolecular non-covalent Hg··· Hg
mercuriophilic interactions. All the complexes were shown to exhibit rich absorption andluminescence behavior as a function of the number of thiophene rings as well as theelectronic nature of the five-membered rings within the bridging ligand. With increasing
thiophene content, the absorption and emission features are both red-shifted and theemission quantum yields are increased. In the presence of electron-withdrawing imine
nitrogen atoms, the optical spectra for the bithiazole derivatives also show a significant
bathochromic shift as compared to their bithienyl counterparts.
Reference
Wong , W.-Y. , Choi , K.-H ., Lu, G.-L. and Lin , Z. (2002) Organometallics 21 ,14475- 4481 .

P083
COMPARISON OF MOLECULAR PACKING MODES OF CHOLESTEROLDERIVATIVES
Young Ja Park
Department of Chemistry, Sook Myung Women 's University, Seoul , KOREA 140-742.
(yjpark@sookmyung.ac.kr)

We have undertaken a series of crystal structures of the esters and carbonates ofcholesterol. These are cholesteryl formate , methyl carbonate , ethyl carbonate , propyl
carbonate , pentyl carbonate , pentanoate , hexanoate , heptanoate, hexyl carbonate, crotyl
carbonate , crotonate,isobutyrate,
isobutylcarbonate , isopropyl
carbonate ,hemisuccinate , aniline and 2,4-dichlorobenzoate. Among these structures, (1) cholesteryl
ethyl carbonate , propyl carbonate, crotyl carbona te , crotonate are isostructural eachother, (2) cholesteryl pentyl carbonate , hexyl carbonate , hexanoate , heptanoate are also
isostructural. (3) cholesteryl isobutyrate and isobutyl carbonate are also isostructural.
These structures are remarkable in forming layer structures in which the central regionof the layers , composed largely of semi-rigid cholesteryl groups is closely packed and thepacking of the flexible fatty acid or carbonate chains and the isoprenoid tail of thecholesterol form the interface region between layers. Within the so called monolayers
type packing, there is little change from one crystal structure to another. Typical packing
modes will be discussed.

P084

STUDIES ON THE WEAK HYDROGEN BONDS IN CRYSTAL
Zhang-Yuan Zhou, Wing-Kong Kwan , Chi-Hung Yeung, AlbertS . C. Chan
Open Laboratory of Chirotechnology of the Institute of Molecuiar Technology for Drug
Discovery and Synthesis and Department of Applied Biology and Chemical Technology,
The Hong Kong Polytechnic University, Hung Hom , Kowloon, Hong Kong(bczyzhou@inet.polyu .edu .hk)

Hydrogen bonding, defined by L. Pauling in 1939, refers to X-H ... Y interaction
where X and Y are higher electronegative elements such as N, 0 , F and CJ. Weakhydrogen bonding , proposed by Jeffrey and Saenger in 1991 , refers to hydrogen bond ing
between carbon hydrogen and carbonyl oxygen , that is , the weak hydrogen bonding of CH .. . O=C . Such weak hydrogen bonding may be defined as D-H ... A wherein a hydrogen
atom forms a weak bond between two structural moieties D (donor) and A (acceptor) of
which one or even both are only of moderate to low electronegativity. The stability
depends mainly on the electrostatic characteristics of both donor and acceptor.
Recently, the concept of the weak hydrogen bonds (D-H .. .A) has been wellrecognized by the study of structure of a large amount of crystals and is further proventhrough extensive JR and NMR studies.
Herein , we report the weak hydrogen bonding of some organic compounds andtransition metal complexes. Crystal structure analysis shows the presence of weakhydrogen bonding of C-H ... 0 , C-H ... N, C-H ... p. Results of such weak hydrogen bonds
and interaction of pi. .. pi for molecula C,sH, 5 N02 and C37H320 sP2 are shown in Tables 1.

nfor weak hydrogen bonds
Table 1 Bond lengths (A) and bond angles
D ...A (A) D-H ...A
~ H ... A (A)D-H ... An

C(2)-H(2) .. . 0(1)2 .57

3.312 (4)137

C(5)-H(5) ... 0(1')

2.51 ~3 70 (4)154

3.578 (3)125

IC(2)-H(2B) ... Cg (A)*

2.96

r

4~
15_
_
]_ 3.999 (3)3.15
C(4)-H(4) .. .Cg(B)*14
3.05
C( )131
3. 728 (4)' )_* - + - - - (A_c
H( 14C )... Cg._,_~-3. 568 (4)~ CgC ...CgD
ng~.ri~*. Cg refers to the gravity center of aromati c ~References
1 Jia , X. Li , X.S. ; Zhou Z.Y. (2002). Acta Crystallographica Section E2002, E58 , 1
2 Qiu , L.Q.; Qi , J.Y. ; Ji , J.X. ; Zhou , Z.Y. ; Yeung , C.H. ; Choi , M.C.K. ; Chan , A.S.C .
(2003) Acta Crystallographica Section C59, o33-o35

P085
FIRST OBSERVATION OF HELICAL BUNDLES IN CRYSTALSTRUCTURE OF HELICAL PEPTIDE SCAFFOLDS CONTAINING A, BDEHYDROPHENYLALANINE RESIDUE
M. Gupta , Rudresh , S. Ramakumar, V. S. Chauhan.
International Center for Genetic Engineering and Biotechnology, New Delhi- 110067. India;g_ madhvi@hotmail.com)

De novo designed peptide based super secondary structures can provide
scaffolds for the incorporation of functional sites as in proteins . Weak interactions leading
to the self-association of helices ;containing DPhe residue) of similar screw sense havebeen probed by the structure determination in crystals of two peptides : Ac-Giy 1-Aia' -DF 3 Leu4-Vai5-DF6-Leu7-Val: -OF: -Aia 10-Giy 11 -NH , I; Ac-Giy 1-Aia: -DF 3-Leu 4-Aias-oFs-Leu 7-Aia:OF: -Aia 10-Giy 11 -NH ,, II . X-ray diffraction studies reveal that both the peptides adopt 3 10 helical conformation in the solid state . The crystal structures of the two peptides havebeendetermined to atomic resolution and refined to R-factor of ;.15%and 4.01 %respectively. An interesting finding is that a packing motif could be identified in both thestructures , in which a given 310 -helix is surrounded by six other helices reminiscent oftransmembrane seven helical bundles. This arrangement resulted in two kind s ofinterfaces , Leu-Leu and Val-Val in peptide I and Leu-Leu and Ala-Ala in peptide II . The
angle between anti parallel helices are 161 o and 164° in pep tides I and II , respectively. The
outer helices are orientated either parallel or antiparallel to central helix. The parallel
helices interact through C-H .. .0 and C-H ...rr hydrogen bonds while the anti parallel helices
are interacting via C-H ... p hydrogen bonds. Common to both the structures is thehydrophobic interaction between the pairs of leucine residues. The results of the packingof the helices in the solid state may help in achieving the ambitious design strategy fordesigning super secondary structural motifs such as helical hairpin and three or four helix
bundles by connecting them through suitable linkers such as tetraglycine segments.

P086
NEW STRATEGY TO SYNTHESIZE OSMABENZYNES
Ting Bin Wen , Wai Yiu Hung, Herman Ho Yung Sung , ian D. William s and Guochen Jia
Department of Chemistry, The Hong Kong University of Science and Technology,
Clear Water Bay, Kowloon , Hong Kong (chterry@ust. hk)

We re cently reported an unexpected production of the first osmabenzyne[Os(=CC(SiMe 3 )=C(C H3 )C(S iMe3 )=C H)C I2 (PPh3 ) 2] - a six-membered metallacycle withdelocalized structure wh ich is similar to th at of aromatic ring systems such as benzene
and metallabenzenes. We have now developed a genera l strategy to synthesize thi s classof interesti ng com pounds and investigated their chemical properties . Treatment ofcomplex 1 with gold acetylides , in the presence of HEt3 NCI led to the formation ofcomplexes 2.

PPh3

_ _

Cl """-ClI 4'-c- c""-, R/ ol

s~c=c"C-CH 2 Ph
I

Ph

'

H

PPh3

2a . R = tolyl; 2b . R = "Bu ; 2c. R = H

Th e osmabenzyne [O s(°CC(SiMe 3 )=C(C H3 )C(SiMe 3 )=C H)CI2(PPh 3 ) 2] was found toundergo typica l aromatic electrophi lic substitution reactions.

Fig 1. Crystal structure of 2b.

P087
SYNTHESIS AND NLO PROPERTIES OF NEW OCTUPOLAR
MOLECULES
Quanyuan Hu , George K. L. Wong , Herman Ho Yung Sung , lan D. Williams and Guochen
Jia
Departments of Chemistry and Physics , Hong Kong University of Science and Technology,
Clear Water Bay, Kowloon , Hong Kong (chqyhu@ust.hk)
Octupolar molecules are potentially useful as second order non-linear opticalmaterials. In order to reveal the structure-property relationship of these compounds , aseries of octupolar molecules with similar skeleton based on 2,4 ,6-triphenyltriazine(examples shown below) have been synthesized and their optical properties have beenstudied by HRS experiments. In addition to their second order non-linear opticalproperties , the compounds also show strong multi-photon absorption induced
fluorescence effects.

R = OCH 3, N0 2
M = Ru (dppe)zP088
HEXAMERIZATION OF ALKYNES MEDIATED BY OsCI(PCP)(PPh 3)(PCP = 2,6-(Ph 2 PCH 2 ) 2 C 6 H3 )Tinq Bin Wen ,• Zhong Yuan Zhou ,b and Guochen Jia•
•Department of Chemistry, The Hong Kong University of Science and Technology, Clear
Water Bay, Kowloon , Hong Kong and bDepartment of Applied Biology and Chemical
Technology, Hong Kong Polytechnic University, Hung Hom , Kowloon , Hong Kong
(chwtb@ust.hk)

The [2+2+2) cyclotrimerization of alkynes to give six-membered aromatic rings is oneof the most common reactions promoted by transition metal complexes . In contrast,
examples of metal-mediated [2+2+1) cyclotrimerization of alkynes to give
thermodynamically less stable isomeric fulvene derivatives are still rather limited.
Vinylidene complexes may serve as the intermediates in the formation of fulvene products
from the [2+2+1) cyclotrimerizations of alkynes. Our previous studies have shown thatreactions of OsCI(PCP)(PPh 3) with terminal acetylenes rapidly produce vinylidene
complexes OsCI(=C=CHR)(PCP)(PPh 3). During the process of further exploring thereactivity of OsCI(=C=CHR)(PCP)(PPh 3 ) with terminal acetylenes , we found that
OsCI(=C=CHPh)(PCP)(PPh 3 ) could further react with HC=CPh to give the unprecedented~-1,2-bis-(TJ 5 -cyclopentadienyl)-1 , 2-diphenyl-ethane bridged dimeric osmium complexes ,which presumably involves dimerization of the fulvene intermediate generated from[2+2+1) cyclotrimerization of HC=CPh (Scheme 1).
Scheme 1

P089

OSMABENZENES FROM THE REACTIONS OF HC=CCH(OH)C=CH With
OsX 2 (PPh 3 ) 3 (X= Cl, Br)
Haiping Xia ,a.b Guomei He ,b Hong Zhang ,b Ting Bin Wen ,a Herman Ho Yung Sung ,a ian D.
Williams ,a and Guochen Jia•
•Department of Chemistry, The Hong Kong University of Science and Technology, Clear
Water Bay, Kowloon , Hong Kong and bThe College of Chemistry and Chemical
Engineering , Xiamen University, Xiamen , P. R. China (Email : chwtb@ust.hk)
The chemistry of transition metal containing metallabenzenes is attracting
increasing attention both experimentally and theoretically because they can display
aromatic properties and they can mediate organometallic reactions. The synthesis ,isolation and characterization of stable metallabenzenes represent one of the major issuesof metallabenzene chemists . During our investigation on the reactivity of OsCI 2(PPh 3 ) 3
toward terminal alkynes , we have found a new convenient route to prepare
osmabenzenes starting from readily accessible HC=CCH(OH)C=CH . In this presentation ,we will describe the reactions of HC=CCH(OH)C=CH with OsX 2(PPh 3 ) 3 (X = Cl , Br), whichlead to the isolation of the first phosphonium salts of metallabenzenes (Scheme 1). The
reactions involve nucleophilic attack of coordinated alkynes by the nucleophile PPh 3 . Oneof the key intermediate has been isolated , which could react with other nucleophiles suchas 1· to give iodo-osmabenzene .

Scheme 1
H=---'---==-.--=OH(X = Cl , Br)

I ~

+

OH

X J~ h3
/Os
X

9

!p~

~h

~PF 3

PPh3
H

4 OH

( X = Cl , Br )

P090
RUTHENIUM-CATALYZED DIMERIZATION OF TERMINAL ALKYNES
Penq Xue , Hoi Yan Leung , Ka Yin Cheng , Wai Bong Wong , Herman Ho Yung Sung , ian D.
Williams and Guochen Jia
Department of Chemistry, The Hong Kong University of Science and Technology, Clear
Water Bay, Kowloon , Hong Kong (chxuep@ust.hk)

There have been considerable interests in catalytic dimerization of alkynes . The
reactions can be initiated by a variety of metal complexes . In most cases , the reactions
produce a mixture of five isomers A-E . In order to understand the reaction mechanisms
and to develop catalysts for selective production of the dimerization products , we haveinvestigated the catalytic activities of a series of ruthenium compl exes for alkyne
dimerization . Complexes 1-6 are examples of such complexes.
/H~'~ + R~ + ~R + R;c= C= C= c:H +R,/C= C= C= C,R

M

R --- R

2 -

ARB

~

R

C ~

R

H

0

E

RH

PCy3

PPh3

I
/Ru-PPh

Cl

I

I

Aco,

Cl --.._

3

H

c==<"

o-Ru =

Ph

H3CAc/ l
PCy3
4

PPh3

cH

R- c =

R¥Ru]

R

q' J},
R

6

I ,3 .4-trime r

I ,3,5-trime r

It was found that the selectivity depends on the structures of metal complexes aswell as the substrates. For example , aromatic alkynes dimerize to give Z-isomers as the
major products with complexes 1-4 as the catalysts ; when 5 was used as the catalyst,
PhC=CH dimerized to give Z-isomer along with the cyclotrimers. Interestingly, PhC=CH
dimerized to give E-isomer as the major product with 6 as the catalyst. In the presentation ,the preparation of the new catalysts as well as the details of the catalytic results will bepresented .

P091
DILEAD J.l9 ·L-TARTRATE: A CHIRAL METAL-ORGANIC FRAMEWORKWITH NONA-COORDINATION OF A SINGLE LIGAND
Andy L-F. Leung , Ricky W. Li , Herman H-Y. Sung and lanD. Williams
Department of Chemistry, Hong Kong University of Science and Technology, Clear Water
Bay, Kowloon , Hong Kong. (ch_llf@stu.ust.hk)

We have embarked on a program of synthesis of chiral metal-organic solids usingorganic carboxylate ligands. L-tartaric acid can be used in hydrothermal synthesis up to
200°C and still yield enantiopure chiral coordination polymers , as shown by careful
comparison of results from meso-tartrate and OIL-tartrate mixtures. Lead is a highcoordinate metal capable of forming 3D frameworks.
Depending on conditions and pH two anhydrous polymers are formed a 'normal' 1:1 phase[Pb(J..ls-C. H. Os)] (pH4) and a fully deprotonated 2:1 compound [Pb2(J..lg-C. H20 s)] (pH>?).
The structure of the dilead tartrate is noteworthy in having a J..1 9-tartrate tetra-anion which
we believe is the highest connectivity found for a tartrate ligand . A thallium p8 -hydrogentartrate was reported previously [TI(J..l s·C. HsOs)]. [1] Further studies of chiral network
polymers from metals such as lead are now in progress.

Coordination environment for the L-tartrate ion in [Pb2(p 9 -L-TAR)'-]The RGC is gratefully acknowledged for financial support of this work.
6128/01P)
Reference
1
Bott, R.C. , Smith ,G. , Sagatys , D.S., Lynch , D.E. Redd y, A.N.
Z. Kristall. 1994, 209 , 803 .

(HKUSTP092
ORGANO-CERAMIC SYNTHESIS: STRUCTURE OF A HYBRID SOLID
WITH [Ln4(J..L3 -0H)4] LANTHANUM-HYDROXIDE TETRAHEDRA
Candy Z-J. Lin , Herman H-Y. Sung and ian D. Williams
Department of Chemistry, HKUST, Clear Water Bay, Kowloon , Hong Kong(chcandy@ust.hk)

There has been much recent interest in metallo-organic polymers as potential
zeolite analogues [1] and as materials in which the interactions between metal centers canbe well regulated . One problem has been framework stability of the metal-organic
component. This can have both physical (thermal) and chemical aspects. [2] The idea of
forming organic-ceramic hybrids which have some of the stability advantages of zeolites ,yet the chemical tunability of metal-organics is appealing . A number of oxo- or hydroxyorgano-hybrid solids have been prepared for transition metals especially for Cu , Zn , Co ,but few lanthanide analogues have been prepared. Reaction of Ln 3• ions with 2,2bypyridine-4,4'-dicarboxylic acid (BDA-H2) under basic conditions results in the formationof a novel organa-ceramic hybrid [Ln(OH)(BDA)] which has an open 20 grid polymer
structure with [Ln. ().l 3 -0H).] units that are connected via the BOA bridges . (Figure below)
An exclusive binding of the carboxylates is found so that the pyridine functionalities are
pendant. We are now looking at the thermal stability of the framework and seeking tobuild on these findings to form related 3D structures. The RGC is gratefully acknowledged
for financial support of this work. (HKUST 6128/01 P).

References
1
Chui , S. S-Y. , Lo , S.M-F. , Charmant, J.P.H. , Orpen , A.G. Williams , I.D. Science(1999)283, 1149.
2
Lin , C.Z-J. , Suwinska , K., Lipkowski , J., Williams, I.D. ,Chern. Commun (2002) 1187.

P093
A NOVEL POLYMORPHIC PHASE TRANSITION IN A CADMIUMPOLYMER [CD(H20)(2,6-NAP)] INVOLVING A 7 -> 5 COORDINATIONNUMBER SWITCH
Carly H-W. Tse, Samuel M-F. Lo and ian D. Williams ,Department of Chemistry, HKUST, Clear Water Bay, Kowloon , Hong Kong(chcarly@ust.hk)
The extended aromatic dicarboxylic ligand 2,6-naphthalenedicarboxylic acid has
been used to form a series of metal coordination polymers. For M = Cd crystallization at
RT results in a 3-D open framework polymer [Cd(H 20)(2 ,6-NAP)] in which the Cd 2• ionsare ?-coordinate with bi-dentate coordination of the coo· groups. A parallel crystallization
using hydrothermal growth conditions at 180°C gave crystals with slightly different unit cellparameters and powder X-ray diffraction pattern. X-ray analysis revealed a related
structure of same composition and with identical topological connectivity to the RT phase.
However the Cd centre was now 5-coordinate with mono-dentate coordination of the
carboxylates . The change also involves major reorientation of the naphthyl planes in the
structure. Heating the first phase converts it to 100% of the HT form and an irreversible
phase transition occurs between the two. Powder XRD studies indicate that the HT
structure is stable to above 200°C. We are now investigating other Cd-carboxylate andhybrid solids for evidence of similar coordination mode and number switches . We are
grateful to RGC for financial support of this work . (HKUST 6128/01 P).

Polymorphic forms of [Cd(H 20)(2 ,6-NAP)]7-coord left and 5-coord right.

P094
SELECTIVE SYNTHESIS OF POLYOXOMETALLATE CLUSTERS USINGSTRUCTURE-DIRECTING ORGANIC AND INORGANIC CATIONSIcy C-P . Lau . Yi Yu , Herman H-Y. Sung and lanD. Williams
Department of Chemistry, Hong Kong University of Science and Technology, Clear Water
Bay, Kowloon , Hong Kong . (ch_lcpaa@stu.ust.hk)

Mixed molybdenum-vanadium polyoxometallate cluster anions of Keggin andrelated types are known , such as [Mo,2-N ,PO.o]"-.[1 ,2] However a rational means ofsynthesis is sought. Recently we have found that hydrothermal synthesis in these systems
using organic bases as both reducing agents and potential counter-cations can lead to theisolation in pure form of a wide range of such cluster species , in which the Mo-V
stoichiometry and cluster charge is a variable. It is believed the supramolecular effects ofparticular counter-cations including shape, charge , and hydrogen bonding capabilities leadto selective precipitation from a solution containing an equilibrium mixture of numerous
such anions. Our results from crystallizations from organic diamines such as piperazine,
homopiperazine , 1,4-diaminocyclohexane indicate a tendency to crystallize the highly
reduced V-capped Keggin ions such as [MoaVsP0.2]6 - and the dimer [Mo ,sV,2P20 a•l ' 4_
(below) By contrast imidazolium ions crystallize mildly reduced Keggins with different MoV ratio and lower negative cluster charge. These results are contrasted with those frominorganic systems Na+ or K+ as well as the tungsten analogues. The crystallographic
difficulties in assignment of speciation will also be discussed.

References
1
Pettersson , L. , Andersson , 1. , Selling , A. , Grate , J.H . (1994)
lnorg. Chem. 33, 982.
2
Cindric, M. , Kamenar, B. and Strukan , N. (1995) Polyhedron 14, 1045.
The RGC is gratefully acknowledged for financial support of this work.
6128/01 P)(HKUST

P095
CHIRAL COORDINATION POLYMERS BY HYDROTHERMALSYNTHESIS: CRYSTALLIZATIONS OF ALKALINE EARTH TARTRATESYu-Fong Yen , Andy L-F. Leung , early H-W. Tse , Ricky W . Li andlan D. Williams
Department of Chemistry, HKUST, Clear Water Bay, Kowloon , Hong Kong(chyen@ust.hk)

Enantiomerically pure chiral network polymers have been synthesized byhydrothermal reaction of L-tartaric and L-malic acids with alkaline earth metal ions M2• M =Mg, Ca , Sr and Ba. The crystal structures of the products have been determined. In eachcase refinement of the absolute structure parameters are consistent with retention ofchirality. Powder XRD can confirm that the structure type found by single crystal
determination is phase pure , but cannot itself serve as a check of enantio-purity, sincemirror image crystals will generate the same powder pattern .
Proof of the chiral retention comes from two sources: firstly parallel reactions of the
M2+ ions with D/L- or meso-tartrate mixtures gives different products than the purely Lenantiomer alone , suggesting that chiral scrambling does not proceed under the reaction
conditions. Secondly Circular Dichroism measurements on the solids gives characteristic
spectra indicative of non-racemic solids.

Figure: coordination environment and polymer structure for calcium L-tartrate
Crystal data: C. H. CaOs, Fw 188.1 , T = 1OOK orthorhombic, C222 1 , a = 7 .6160(8) , b
9.9220(1 0), c = 7.1881 (?)A , V = 543.2A 3 , Z = 4, De= 2.30Mgm·3 , 11 = 1.13mm·', R,(obs) =1.86% , wR2(all) = 4.38% for 602 data (20max = 56 .5°) and 51 parameters , L'.e =+0.33/-0.22eA- 3 , q = 0.04(4 ).
The RGC is gratefully acknowledged for financial support of this work.
6128/01P) .

(HKUST

P096
HYDROTHERMAL CRYSTALLIZATION AND STRUCTURE OF
LUMINESCENT 1-D LANTHANIDE POLYMERS [Ln2(biphenateh(H20)2]
Samadara Thushari , Herman H-Y. Sung , Kam-Sing Wong and lan D. Williams
Departments of Chemistry and Physics , Hong Kong University of Science andTechnology, Clear Water Bay, Kowloon , Hong Kong . (samadara@ust.hk)
Construction of systems with fast energy transfer between Ln ions is offundamental importance and may have applications in the development of efficientluminescent materials. We have used aromatic carboxylates with 1,2 or chelating
functionalities in order to construct 1D lanthanide chain polymers with variable Ln--Ln
distances and interactions, which might be used to probe structure-property relationships .
Hydrothermal reaction of biphenic acid (BPA-H 2) with Ln 3 • ions gives the coordination
polymer [Ln 2(22-BPA)3(H20)2]. This structure has a simple 1D chain with single Ln---Ln
separations of 5.52A and a bridging 0 atom . The photo-luminescent properties of thesesystems with different Ln compositions have been studied and enhanced emission is seen
for mixed-metal polymers such as Sm-Gd over the Sm or Gd homopolymers.
Other systems are now being studied , such as the more complex 1D chain polymer[Nd2(12)(22-BPA)2(H20),s] which is formed with the addition of phthalic acid. In thisconnected Lns rings are found with three Ln---Ln separations of 5.13-5 .71A and one or
two bridging 0 atoms.

View down 1D chain polymers from biphenic acid (left) or biphenic and phthalic acids(right) with variable Ln---Ln interactions.
We thank the RGC (HKUST 6128/01 P) for financial support of this work .

P097
STRUCTURES OF IMIDAZOLE MANGANESE VANADATES:
CRYSTALLIZATION OF TEMPLATED VERSUS HYBRID SOLIDS
Yi Yu , Teresa S-C. Law, Herman H-Y. Sung and Jan D. Williams
Department of Chemistry, Hong Kong University of Science and Technology, Clear Water
Bay, Kowloon , Hong Kong. (chwill@ust.hk)

Organic groups can modify the structure of inorganic oxides in two different ways,
the first being as templating or structure directing agents , in which they can act as countercations for porous anionic frameworks or oxide cluster anions. The second in which they
are themselves incorporated as part of the framework forming new hybridorganic:inorganic solids. Our recent work on organically modified manganese vanadates[1-3] has shown that both types of compound may be formed through hydrothermal
recations , but relatively little work has been devoted to differentiating the necessary
conditions for one or the other. Investigations in the imidazole-MnVOx system indicatesthat concentration and temperature are critical parameters. Two polymorphic forms of atemplated solid [lmH][Mn3(0H),(V. 0 ,3)] (left) can be formed rather than hybrids such as[Mn2(1m)a(V.0 ,2)] (right) by either use of higher T or by increased volume of water. The
suppression of the crystallization of the hybrid solid through dilution effects is consistent
with its formation as a kinetic product, which is relatively soluble in water compared to theanionic framework . The RGC is gratefully acknowledged for financial support of this work.

(HKUST 6128/01 P)
References1
Law, T. S-C ., Sung , H. H-Y, Williams , J.D. lnorg. Chern. Commun. (2000) , 3,
420-423 .
2
Williams , J.D ., Law, T. S-C. , Sung , H.H-Y. and Zhang , X.X.
Solid State Sciences, (2000) 2, 47-54.
3
Law, T. S-C. and Williams, J.D. Chern. Mater. (2000) 12 , 2070-2072.

P098
METAL FORMATE NETWORK SOLIDS: SOLVOTHERMAL SYNTHESIS,STRUCTURES AND MAGNETIC PROPERTIES OF a-[Co(02CH)2], ~­[Ni(02CH)2] And [M(OH)(02CH)] M =Co, Ni
Alvin W-H . Siu , lanD. Williams , Herman H-Y. Sung , John A. Cha ,Candy Z-J. Lin , and Xi Xiang Zhang.
Departments of Chemistry and Physics , Hong Kong University of Science andTechnology, Clear Water Bay, Kowloon , Hong Kong , China. (chalvin@ust.hk)

Metal coordination polymers have been of growing interest for their magnetic
properties , both as model systems and for potential applications . Investigations on cobalt
and nickel formates show that new ferromagnetic 3D network solids can be formed .
Solvothermal reaction of cobalt and nickel formate dihydrates in aqueous , alcoholic or
acetic acid can result in recrystallization of new anhydrous phases. The anhydrous cobalt
and nickel phases isolated have distinct crystal structures which are designated here as a[Co(02CH )2] and J3-[Ni(02CH)2]. Both phases have 3D coordination polymer networks inwhich octahedral metal centers are connected together in chains through two different
bridging oxygen modes as shown .

M

M

~

M

M

0

Bridgi ng Modes for Cobalt and Nickel Formate

These two modes affect the J-interactions between the metal centers and hence
the macroscopic magnetic properties. The structure-property relationships of these will be
discussed as well as their relationship to the mixed formate-hydroxides [M(OH)(0 2CH)](Figure) which can be formed under more forcing hydrothermal conditions.
The RGC (6128/01 P) and ITF (AF/155/99) are thanked for financial support.

P099

1:1 AND 1:2 ADDUCTS OF BIPYRIDINES WITH BIPHENIC ACID
Fanny L-Y. Shek , Wan-Yee Wong , Samuel M-F . Lo , Herman H-Y. Sung and ian D.
Williams
Department of Chemistry, Hong Kong University of Science and Technology, Clear Water
Bay, Kowloon , Hong Kong. (fanny@ust.hk)
Hydrothermal reactions of 4,4-bipyridine and related compounds with 2,2'-biphenyl
dicarboxylic acid (biphenic acid) at 11 0°C over several days gives different molecularadduct crystals depending on the conditions and stoichiometry of the hydrothermal
reaction and the nature of the bipyridine itself. For 2,2'-bipyridine a 1:1 adduct [2 ,2bipy][2 ,2-BPA-H2] (shown on left) is formed whilst 4,4-bipyridine gives a 1:2 adduct [4,4bipy][2 ,2-BPA-H2]2 (shown on right). The 1:1 adduct has simple 1 D zigzag H-bond chainsin which each bipy has H-bonds to biphenic acid neighbors and vice versa. In the 1 :2
adduct the bipyridines form H-bond chains with diphenic acid dimers which are formed bycommon 0-H---0 hydrogen bond bridge pairs . These results are compared andcontrasted to results for other similar bipyridines such as 1,2(4-pyridyl) ethylene which canform both 1:1 and 1:2 adducts , and the supramolecular aspects of these systems are
discussed.

1:1 and 1:2 phases of bipyridines and 2,2-diphenic acid

The RGC is gratefully acknowledged for financial support of this work . (HKUST 6084/02P)

P0100EFFECT OF SOLVOTHERMAL CONDITIONS ON CRYSTALLIZATION OF
METAL COORDINATION POLYMERS: EXAMPLES OF THE ZINC AND
COBALT PYROMELLITATE- BIPYRIDINE SYSTEMSSamuel M-F. Lo , Stephen , S-Y Chui , and lan D. Williams
Department of Chemistry, Hong Kong University of Science and Technology, Clear Water
Bay, Kowloon , Hong Kong (chwill@ust.hk).
A wide range of phases can be crystallized in metal-organic coordination polymer
systems through systematic variation of solvothermal conditions. These include reagent
stoichiometry, pH , temperature , time , solvent and concentration . The effect of these
conditions can be deduced through powder XRD analysis of the resulting product solids
combined with individual single crystal structure determinations. Metal pyromellitate (1245)- 4,4-bipyridine systems are excellent examples to explore this theme . For Zn 2+ threedifferent compounds have been isolated : a 2-D framework [Zn z(1245)(4,4'bipy)(Hz0 )2]n .2n(Hz0) can be found at room temperature , [1] whilst [Znz(1245)(1245Hz)(4,4 '-bipy-H )2]n and 3-D [Znz(1245)(4,4'-bipy)]n. n(HzO) are formed at 200°C withdifferent time of heating . For Co2+ the situation is even more complex , so far six
coordination polymers could be identified and isolated by use of different reaction
conditions , five of which are shown below. (Figure 1).
4 5 00

4 000
35 0 0
3 00 0

2

2 500

'-'

2 00 0

~

"1500
1000

Co rn pounCis B+ C

110" C
500]

Room Tc~p .

0

0

5

10

-¢ 15

1'"\Ac-, ry"

20

25

30

35

Two-th e t a I degr-ees

Figure 1: Powder XRD patterns of some of the hydrothermal products of cobaiUpyromellitic
acid/4,4'-bipyridine
A= [Coz(4,4 '-bipy)2(H zO)s]n(1245).2n(HzO) [2];B = [Co(H 2 0 ). (4,4' -bipy)]n[Coz(H 2 0 ). ( 1245-H )z( 4,4'-bipy)z]n.2n HzO;
C = [Co(1245-Hz)(4,4 '-bipy)(H zO)z]n;
D = [4,4'-bipy-H][Co(1245-H)(4,4'-bipy)(H 20 )2]n and E =[Coz(1245)]
References
1
Wu , C-D ., Lu C.Z, Wu , D.M ., Zhuang , H-H . and Huang , J-S. Inorganic Chemistry
Communications (2001) 4 , 561.

P0101A CHIRAL ORGANIC SALT FROM HYDROTHERMAL REACTION OF
4,4-BIPYRIDINE AND L-TARTARIC ACID WITH 50% PROTON TRANSFER
Wan-Yee Wong , Fanny L-Y. Shek, Samuel M-F. Lo , Herman H-Y. Sung and lanD.
Williams
Department of Chemistry, Hong Kong University of Science and Technology, Clear Water
Bay, Kowloon , Hong Kong. 5ch_wwy@stu .ust.hk)

Hydrothermal reaction of 4,4-bipyridine and L-tartaric acid at 11 0°C for 3 days leads
to crystallization of the 1:1 salt [4,4-bipy-H][L-C4Hs0 6][H20] as light yellow rods . This result
is interesting from two aspects , first the chirality of the L-tartrate is retained and the
crystals are enantiopure orthorhombic P2 ,2,2,. Secondly although the product is a 1:1
salt only a single proton is transferred from the diacid to the dibasic entity. This contrasts
the typical behavior for such systems in which either neutral molecular adducts are formed
with 0-H---N hydrogen bonds , or in which full proton transfer occurs and N-H---0hydrogen bonds are seen. The supramolecular arrangement plays an important role inthis and the [tartrate-H)'" anions and water molecules form a 3-D H-bonded network withporous 1-D channels into which the monoprotonated bipyridines fit as structure-directing
guests.

Chiral network structure of [44-bipyH][L-TAR-H] monohydrate
The RGC is gratefully acknowledged for financial support of this work.
6084/02P)

5HKUSTP0102
S-ALKYLATION OBSERVED ON TRI(2-THIOPHENYL)PHOSPHINO TIN
COMPLEXES
Michael Y. Chiang•, Chi-Hui Chang• and Jing-Wei Lin•
Department of Chemistry, National Sun-Yat Sen University
Kaohsiung , 804 Taiwan (Michael@mail.nsysu.edu.tw)

Tri(2-thiophenyl)phosphine (L) is an useful ligand in metalloenzyme modeling studies
for mimicking cystein-rich bindings with its multi-thiolate sites . (;] We have combined itwith the organa-tin reagents to study the alkylation on sulfur atoms that may shed somelights on the biological alkylation reactions in general.[2] Reactions of tri(2thiophenyl)phosphine with SnCI 3 Me and SnCI 3 Bu yielded the corresponding Sn(R)(L)
complexes (R=Me and Bu). Subsequent sublimation for both complexes produced crystals
in space groups P2 ;/n. The crystal structural analyses show ed that the alkyl groups weretransferred from the tin center to one of the sulfur atom of the ligand L in both cases .
These two resulting crystal structures are the direct evidences of the reductive elimination
demonstrated on thiolato-tin complexes for the first time. Their structures are similar inmorphology but different in skeletal arrangement. Both structures are dimeric with bothbridging and terminal thiolates. The thioethers resulted from the alkylation were notcoordinated to any of the tin centers.
References

2

Nguyen , D. H. ; Hsu , H. -F. ; Millar, M.; Koch , S. A. (;996) J. Am. Chern. Soc., 118,
8963 .
Peariso , K.; Goulding , C. W.; Huang, S.; Matthews, R. G. ; Penner-Hahn , J. E. (;998)
J. Am. Chern. Soc., 120, 84 ;0-84 ;6.

P0103
ELECTRON DENSITY DISTRIBUTIONS ON WEAK INTERMOLECULAR
INTERACTIONS: CH· 0 INTERACTIONS IN TEMPO RADICALS
Masanori Yasui ,a Kansui Takino ,a Fujiko Iwasaki," and Daisuke Hash izumeb•Department of Applied Physics and Chemistry, The University of ElectroCommunications, Chofu , Tokyo 182-8585, Japan ; b The Institute of Ph ysical andChemical Research (RIKEN) , Wako , Saitama 351-0198 , Japan (yasui@pc.uec.ac.jp).
Some of TEMPO radical derivatives (TEMP0=2 ,2,6,6-tetramethyl-pyperidyl-1-oxyl)show ferromagnetic interactions at extremely low temperatures [1] . Almost derivatives,that we have determined their crystal structures , have intermolecular CH· 0 interactions
between the radical 0 atom and CH 3 or CH 2 groups. We concluded that theseinteractions play an important role in the intermolecular magnetic interactions [2] . We
carried out the topological analyses of experimental electron density distributions toestablish the nature of these CH · ·0 interactions in conjunction with their role in magnetic
properties.
We used crystals of 4-(4-X-benzylideneamino)-TEMPO derivatives , (1 ):X=Me ,(2):X=H , (3):X=CI , (4):X=Br for the electron density studies . The topological properties ona covalent bond of N- 0 radical moiety show significant features against the normal single
or double bonds . The V' p at BCP of N-0 bond have about a half value of those at single
bonds while p at BCP are greater than those of double bonds. We conclude that thesefeatures can be ascribed to the anti-bonding properties of unpaired electron of radical
moiety. We found that some electron concentrations locate around the N and 0 atoms
above and below the >N- 0 plane , which are assigned to rr* molecular orbital. Eachderivative has 2 to 5 CH 0 interactions of which distances ranged from 2.33 to 3.21 A. Allof these interactions can be approved from their topological properties. We found that atleast one H atom has a significant interaction with the TI* orbital of the radical 0 atomwhich can explain the intermolecular magnetic interaction.

References
1
Togashi , K. , lmachi, R. , Tomioka , K. , Tsuboi , H., Ishida , T ., Nogami , T. , Takeda , N. ,and Ishikawa , M. (1996) Bull. Chem. Soc. Jpn ., 69 , 2821-2830
2
Iwasaki , F., Yoshikawa , J. H., Yamamoto , H., Kan-nar,i E., Takada , K. , Yasui , M .,Ishida, T. , and Nogami , T. (1999) Acta Cryst. 855, 231-245.

P0104
RAPID DISMUTATION OF H2 0 2 BY COFACIAL BIS-CORROLE CATALASE
MODELSFei Yam , Nga-Chun Ng, Hai-Yang Liu , Lam-Lung Yeung and C. K. Chang
Department of Chemistry, The Hong Kong University of Science and Technology, Clear
Water Bay, Hong Kong , PRC (yamfei@ust.hk)
In living cells , catalases protect organisms from oxidative damage by mediating rapid
dismutation of H2 0 2 . While many of these enzymes are hemoproteins , those of bacterial
origin contain manganese as a cofactor. We here report a new cofacial bis-corrole withxanthene as the spacer group synthesized by a simple modified Rothemund condensation
reaction. The metal complexes of this meso-substituted bis-corrole have remarkablestability towards oxidative degradation. The catalytic results indicate that cofacial biscorrole is a superior model for the biomimetic multi-electron transfer process[1-3]. The dimanganese(lll) bis-corrole exhibits significantly enhanced catalytic activity in decomposing
Hp2 to 0 2 as compared to those of the monomeric Mn(lll) correlate and dimeric Mn(lll)porphyrin[4].

I~0\Figure. Chemical and crystal structures of the free base corrole dimer
Acknowledgement. This work was supported by the Research Grant Council of Hong
Kong.
References
1
Guilard , R., Jerome, F. , Barbe , J-M. , Gros, C. P. , Qu , Z. P. , Shao , J. G. , Fisher, J.,
Weiss, R. , Kadish , K. M. lnorg. Chem. (2001), 40 , 4856-4865.
2
Kadish , K. M. , Qu , Z. P., Shao , J. G. , Gros , C. P. , Barbe , J-M ., Jerome, F. , Bolze ,F., Burdet, F., Guilard , R. lnorg. Chem. (2002) , 41 , 3990-4005.
3
Kadish , K. M. , Shao , J. G., Qu , Z. P., Gros , C. P. , Bolze , F. , Barbe , J-M ., Guilard ,R. lnorg. Chem. (2003), 42 , 4062-4070.
4
Chng , L. L. , Chang , C. J. , Nocera, D. G. J. Org. Chem. (2003) , 68 , 4075-4078 .

P0105
TWO NEW DITERPENOIDS FROM EUPHORBIA EBRACTEOLATA:STRUCTURAL STUDIES OF A DIASTEREOMERIC PAIR
Herman H-Y. Sung•, lan D. Williams•, Hai-Ming Shib, Hua-Xu Zhub, Nancy Y. lpc and ZhiDa Minb.
•Department of Chemistry, The Hong Kong University of Science and Technology, Clear
Water Bay, Kowloon , Hong Kong , PRC . (hermans@ust.hk)
bDepartment of Natural Medicinal Chemistry, China Pharmaceutical University,
Nanjing 210038, PRC .
csiotechnology Research Institute, The Hong Kong University of Science andTechnology, Clear Water Bay, Kowloon , Hong Kong, PRC.

The root of Euphorbia ebracteolata Hayata (Euphorbiaceae) has been used for thetreatment of pulmonary tuberculosis and chronic tracheitis. The extract has also beenreported to have antitumor activity as well. Two new diterpenoids , Yuexiandajisu D and E,
were isolated from the roots of E. ebracteolata and colorless crystals for both compounds
were successfully obtained from a mixture of chloroform and methanol for X-ray analysis.
Yuexiandajisu D and E shown that they both belong to chiral space groups oforthorhombic P2,2,2, and monoclinic P2 1 respectively, indicated both have pureenantiomeric compositions . Yuexiandajisu D and E are diastereomers, with same formulaof C2oH3oOs. The difference being the stereochemistry at specific chiral centers, whichsignificantly affected the conformation of the rings and their planarity, resulted in different
overall molecular configurations and matrices of intra- and inter-molecular hydrogenbonds.

Perspective view of Yuexiandajisu D (left) and Yuexiandajisu E (right)
The Innovation and Technology Commission , HKSAR, is grateful acknowledged forfinancial support of this work. (ITS/119/00)
References
1
Shizuri , Y. , Kosemura , S. , Yamamura , S. , Ohba , S., Ito, M. , Saito, Y. Chem Lett.
(1983), 65.
2
Mdee , L. K. , Waibel , R. , Nkunya , M. H. H. , Jonker, S. A. , Achenbach , H.
Phytochemistry (1998) , 49 , 1107-1113.
3
Che , C.T. , Zhou , T. X. , Ma , Q. G. , Qin , G. W. , Williams , I. D. , Wu , H. M., Shi , Z. S.
Phytochemistry(1999) , 52 , 117-121 .

P0106
X-RAY ABSORPTION FINE STRUCTURE INVESTIGATION OF VANADIUMON TIO/SI0 2 AND Sl0 2 SUPPORTS
Hsiu-Mei Lin•, Sheng-Tsang Kaobb, Jen-Ray Chang c, Shin-Guang Shyu•·",•Institute of Chemistry, Academia Sinica , Nankang, Taipei , Taiwan ;bQepartment of Chemistry, National Central University, Chungli , Taiwan ;cOepart of Chemistry Engineering , National Chung Cheng University, Chia-Yi , Taiwan(sgshyu@chemSsincaSeduStw)

Vanadia on TiO sfSi0 5 has higher catalytic oxidation reactivity than vanadia on
Si0 5 supportS Vanadium oxytripropoxide was used as vanadia pre(tJrsor in the deposition
of V 5 0 5 on both Ti0 5/Si0 5 and Si0 5 supportsS Both catalysts have similar ~ 0 5 content as
indicated by ICPMass analysesS Oxidation of ethanol by air vas used as a probe reaction
to evaluate the catalytic reactivity of the catalystsS The ~ 0 5/Ti0 5/ Si0 5 catalysis has ahigher conversion rate than the V 5 0 5 /Si0 5 S An X-ray absorption study at vanadium Kedge
has been performed on the Vp sfTi0 5/Si0 5 and the Vp 5 /Si0 5 catalysesS The Fouriertransform of EXAFS of V 50 sfTiOsfSi0 5 indicates that the vanada is present as anindividual site since no V-V interaction was observedS Howeter, in the V 5 0 5 /Si0 5 , a V-Vinteraction was observed indicating polymeric structure of the vanadia on Si0 5 S The
difference in their catalytic reactivities is proposed being due to the difference of thevanadia structure of the catalystSP0107
THE RESEARCH OF CRYSTAL STRUCTURES BY ELECTRONCRYSTALLOGRAPHY TECHNIQUE
Liping You . a: Junliang Sun ,b Zhaofei Li ,b Guobao Lib and Jianhua Linb
•Electron Microscopy Laboratory, Peking University, Beijing , 100871 , China ; bCollege ofChemistry and Molecular Engineering , Peking University, Beijing , 100871 , China ;'(youlp@ pku.edu .cn)

Electron microscopy is a powerful tool to the microstructure of the materials ,particularly when dislocation and other mismatch imperfections are present in thematerials. Recently significant progress has been achieved in using the electron
microscopic technique to the crystallographic problems. Herein this presentation we reportour recent efforts of using this technique to the crystal structures of a series of newmaterials , including , for example , some microporous materials [1] and some compoundswith incommensurate structures [2] . By using selected area electron diffraction (SAED) ,we were able to determine the right unit cell and the space group. The structure model
can be determined by combining high-resolution transmission electron microscopes(HRTEM) , image simulation and crystallographic image processing. This technique isparticularly useful to learn the structure details of the incommensurate compounds. As an
example , Figure a shows the electron diffraction pattern viewed down the [001] direction ,from which one can see clearly the incommensurate is only along the c-axis ..
Furthermore , the corresponding HRTEM image provides a clear view of the structure
modulation . Combined with other crystallographic technique , for instance the Rietveld
refinement of the powder X-ray data , one could figure out the structure details of these
difficult crystallographic problems.
Reference
1
Jing Ju , Jianhua Lin , Guobao Li , Tao Yang , Hongmei Li , Fuhui Liao , Chun-K
Loong, Liping You , ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 42 (45) :5607-561 0 (2003)
2
Guoxin Lu , Stephen Lee , Jianhua Lin , Liping You , Junliang Sun and Joshua Teal
Schmidt, Journal of Solid State Chemistry 164, 210-219 (2002)

P0108SYNTHETIC ROUTES TO A NEW CLASS OF BLUE-EMITTINGOLIGOACETYLENIC SILANES
Suk-Yue Poon and Wai-Yeung Wong *Department of Chemistry, Hong Kong Baptist University, Waterloo Road , Kowloon Tong ,Hong Kong , P.R. China (02411016@hkbu .edu.hk)

A new series of blue-emitting oligoacetylenic silanes and germanes containing 9,9dihexylfluorene and 9-butylcarbazole as the organic linking groups are prepared. All these
new compounds have been fully characterized by spectroscopic and mass spectrometricmethods and some of their X-ray crystal structures have also been determined. Most ofthese new molecules were found to show interesting photophysical properties.
Acknowledgement:This work was supported by Hong Kong Research Grants Council (HKBU 2054/02P)
References
1 Wong , W.-Y. , Wong , C.-K. , Lu , G.-L. , Cheah , K.-W. , Shi , J.-X . and Lin , Z. (2002) J.
Chem. Soc., Dalton Trans. 4587- 4594.
2
Wong , W.-Y., Wong , C.-K., Lu , G.-L. , Lee , A .W.-M ., Cheah , K.-W. and Shi , J.-X.
(2003) Macromolecules 36 , 983- 990.

P0109TRIPLET EMISSION IN SOLUBLE MERCURY(II) POLYYNE POLYMERSLi Liu and Wai-Yeung Wong*
Department of Chemistry and Centre for Advanced Luminescence Materials, Hong Kong
Baptist University, Waterloo Road , Kowloon Tong , Hong Kong , P. R. China(01400878@hkbu.edu .hk)

The first examples of soluble high-molecular-weight d 10 mercury(ll) polyyne
copolymers incorporating a 9,9-dialkylfluorene moiety have been prepared andphotophysically characterized . These copolymers have been shown to utilize a heavyatom effect in exhibiting strong phosphorescence .
Acknowledgement
This work was supported by Hong Kong Research Grants Council (HKBU 2048/01 P)
References
1 Wong, W.-Y. , Choi , K.-H ., Lu , G.-L. and Lin , Z. (2002) Organometallics 21 ,4475- 4481.
2 Wong , W.-Y. , Choi , K.-H ., Lu , G.-L ., Shi , J.-X ., Lai , P.-Y. , Chan , S.-M . and Lin , Z.
(2001) Organometallics 20 , 5446- 5454 .
3Wong , W.-Y. , Liu , L, Shi , J.X. (2003) Angew. Chern. Int. Ed. 42 , 4064- 4068 .

P0110
GRAFTING Ti0 2 ON MCM-41 AS A Ti0 2 SUPPORT FOR VANADIA FOR
CATALYTIC OXIDATION OF ETHANOL-EXAFS AND XANES ANALYSES
OF VANADIUM
Hsiu-Mei Lin ,a Sheng-Tsang Kao ,b Jen-Ray Chang,c Shin-Guang Shyu ,a.b
alnstitute of Chemistry, Academia Sinica , Nankang, Taipei , Taiwan ;bOepartment of Chemistry, National Central University, Chungli , Taiwan ;cOepart of Chemistry Engineering , National Chung Cheng University, Chia-Yi , Taiwan(sgshyu@chem .sinca .edu .tw)

Titanium oxide was grafted on the surface of MCM-41 to produce a mesoporous
TiOz!MCM-41 composite to serve as a catalyst support. Vanadia was grafted on this titania
support to produce V 2 0 sfTiOz!MCM-41 and catalytic oxidation of ethanol by air was used
as a probe reaction to study the influence of the support on the catalytic behavior of thiscatalyst. Catalyst Vp 5!Ti0z!MCM-41 has reactivity five times higher than the reactivity of
vanadia on MCM-41 . EXAFS analysis of vanadium indicates that vanadia on bothsupports have similar structures and polymeric morphologies. The enhancement ofreactivity was due to the direct dispersion of vanadia on Ti0 2 in Vp 5!Ti0z!MCM-41 as
indicated by the EXAFS and XANES studies . This Ti0 2 grafted MCM-41 mesoporous
framework thus has high potential for use as a mesoporous Ti0 2 support. Such support issuperior to traditional anatase Ti0 2 , pure mesoporous Ti0 2 or Ti0z!Si0 2 supports owing to
its much larger surface area and better thermal stability at elevated temperature.

P0111
DIRECT OBSERVATION OF THE HYDROGEN TRANSFER IN THE SOLIDSTATE ORGANIC PHOTOREACTION WITH NEUTRON DIFFRACTIONMETHOD
Hosoya Takaaki,a Uekusa Hidehiro ,a Ozeki Tomoji ," Ohashi Yuji ," Ohhara Taka shi ,bTanaka lchiro ,b and Niimura Nobuoc•Department of Chemistry and Materials Science, Tokyo Institute of Technology, 0okayama , Meguro , Tokyo 152-8550, Japan ; bNeutron Structural Biology, Neutron
Research Center, Japan Atomi c Energy Research Institute, Tokai-mura , Naka, lbaraki
319-1195, Japan ; coepartment of System Engineering , lbaraki University, Naka-naru sawacho , Hitachi , lbaraki 316-8511 (thosoya@chem .titech.ac.jp)

1) It has been found that N,N-dibenzyl-1-cyclohe xenecarbothioamid e 1 is photoisomerized to optically active ~ -thiolactam 2 in high optical yield (-97%ee) in the solidstate .[1] Although X-Ray diffraction stud y of crystalline-state photoreaction from 1 to 2
revealed the mechanism of chiral ~ -thiolactam formation ,[2] the hydrogen transfer process
remained unsolved. In order to make clear the mechanism , the neutron diffraction
technique was applied to a new compound 2 with all benzyl hydrogen atoms of 1 were
repla ced with deuterium atoms. The photo-product 2 from 1 has a methylene carbon atomwith a hydrogen and a deuterium atoms , -C *HD-, "chiral methylene". The absoluteconfiguration of this "chiral methylene" indicates the direction of deuterium migration , i.e.,
via intramolecular or intermolecular. We used neutron-IP diffractometer BIX-111 todetermine the absolute configuration of this chiral methylene . The difference Fourier map
clearly showed negative and positive peak around the chiral methylene , corresponding toa hydrogen and a deuterium , respectively. This result revealed that a deuterium atom
bonded to the benzyl carbon atom was migrated to the intramolecular cyclohexene carbon
to occupy the equatorial position of the produced cycloh exyl ring. Because the deuterium
should occupy the axial position if it was migrated from the neighboring benzyl carbon .
2) Light-induced reversible color change of substances is known as photochromism
and has attracted attention due to their potential applications such as optical data storage
etc. Salicylideneaniline derivatives have the property of photochromism or
thermochromism , which is reversible color change with vari ation of temperature . The color
change from stable yellow to unstable red is brought about by the change of molecularconformation . This reaction involves a proton transfer in the keto-enol tautomerization .
Previously, photo-irradiated trans-keto form of N-3,5-di-tert-butylsalicylidene-3-nitroaniline
3 were observed by X-rays. [3] However, the transferred proton was not observed because
the population of trans-keto form was about 10%. We try to observe the transferred
proton of trans- or cis-keto form with neutron diffraction method . Crystals of 3 and N-3 ,5di-tert-butylsalicylidene-3-carboxyaniline 4 were prepared , photo-irradiated and performed
the neutron diffraction analysis. Now, we are on structure analysis.
References
1
Sakamoto , M. , Takahashi , M., Kamiya , K., Yamagu chi , K., Fujita , T., and
Watanabe , S., J. Am. Ch em. Soc., 118, 10664 (1996).
2
Hosoya , T ., Ohhara , T., Uekusa, H., Ohashi , and Y., Bull. Chem. Soc. Jpn ., 75 ,2147(2002).
3
Harada , J ., Uekusa, H., and Ohashi , Y., J. Am. Chem. Soc., 121 , 5809 (1999).

P0112SYNCHROTRON STRUCTURE DETERMINATIONS OF INORGANIC
GIANT MOLECULES
Tomoji Ozeki ,a Shin-ichi Adachi ,b and Toshihiro Yamasec
aoepartment of Chemistry and Materials Science , Tokyo Institute of Technology andCREST, JST, 2-12-1-H-63 0-okayama , Meguro-ku , Tokyo 152-8551 , Japan ; bPhoton
Factory, Institute of Materials Structure Science , High Energy Accelerator Research
Organization and ERATO JST, 1-1 Oho , Tsukuba , lbaraki , 305-0801 , Japan ; cchemical
Resources Laboratory, Tokyo Institute of Technology and CREST, JST, 4259 Nagatsuta,
Midori-ku , Yokohama 226-8503 , Japan (tozeki@cms .titech .ac.jp).

Albeit the preconception that inorganic materials generally assume either very small
molecules or extended structures consisting of small building units seems to be widely
accepted , recent advances in synthetic inorganic chemistry (exploiting the recent
advances in crystallography both in instrumentation and in data processing) havedemonstrated that many inorganic (both purely inorganic and inorganic-organic hybrid)compounds assume molecules with the dimensions of several nanometers or even larger.
The demand for analysing the structures of such inorganic giant molecules using single
crystal X-ray diffraction is rapidly growing. When investigating the structures of thesecompounds , it is desirable to collect atomic resolution data with high redundancy. Atomic
resolution data is critically important in order to obtain unambiguous structural information
since these molecules tend to exhibit unprecedented geometry and thus rigid body
approximations based on the known geometries of commonly appearing fragments are
not applicable . Highly redundant data is also necessary in order to analyse the structure
at high precision to certify such unprecedented geometries.
To collect diffraction data of inorganic giant molecules with the quality satisfying
abovementioned demands , X-ray diffraction studies have been carried out using a tailored
CCD diffractometer system on the NW2 beamline of the Advanced Ring (AR) , Photon
Factory (PF) , High Energy Accelerator Research Organization (KEK) [1] where X-rays withthe photon energy as high as 23 keV are available for the diffraction study. The
diffractometer is equipped with a three circle goniometer with a quarter x cradle to allow
highly redundant data collection and a 20 arm carrying a CCD detector that can travel up
to 110 degree , ensuring the ability to observe high resolution data that can also be utilized
for the charge density analyses .
Successful results have already been obtained for both polyoxometalates (purely
inorganic compounds) and coordination compounds (inorganic-organic hybrid system)with the dimensions of several nanometers. Unit cells of some of the sample crystals
measure ca 130 A, which rival to smaller to medium sized biological macromolecule
crystals . Even for these large unit cell crystals , diffraction data up to 0.7 A data weresuccessfully obtained at high redundancy, which assures high quality structure analyses.
Details of the diffractometer system and the results of the structure analyses will bepresented .
References
1
Mori , T., Nomura, M., Satoh , M., Adachi , H., Uchida , Y. , Toyoshima , A ., Yamamoto ,S., Tsuchiya , K. , Shioya , T . and Kawata , H. (2003) SRI2003 Abstract No 2.58 .

P0113
CRYSTAL STRUCTURES OF TWO ALDOL CONDENSATION PRODUCTS
Yin-Su Wu and Jiwen Cai
School of Chemistry and Chemical Engineering , Sun Yat-Sen University, Guangzhou
510275 , P. R. China )pu scjw@zsu.edu.cn)

In order to explore and identify stereoselective and environmental benign organic
reactions , direct aldol reactions of 4-nitrobenzaldehyde with 3 different ketones catalyzed
by NaHC0 3 , Zn-proline , NaHCO/ Zn-proline and L-proline/Zn-proline were carried out inaqueous media. Reverse additive preference was observed in c-pentanone and chexa none , with the syn or anti isomer as the major product, respectively. The structuresof the corresponding products were characterized by single-crystal structural analyses.
Both of the isomers form racemic dimmer via a pair of strong inter-molecular hydrogenbonds formed between the carbonyl and hydroxyl groups. A chelate or non-chelatetransition state is proposed to account for the different diastereoselectivity.

Fig. 1

Fig . 2We thank the financial support from the National Natural Science Foundation of China)Grand Nos. 20271 053).
References
1 Dickerson, T . J.; Janda , K. D. J. Am. Chem. Soc. 2002 , 124, 3220-3221.
2 Darbre , T.; Machuqueiro , M. Chem. Comm. 2003 , 1090-1091
3 Cordova , A. ; Notz, W. ; BarbasW , C. F. Chem. Comm. 2002 , 3024-3025
4 Peng , Y.-Y. ; Ding , Q.-P.; Li , Z.; Wang , P. G. ; Cheng , J.-P. Tetrahedron Lett. 2003 , 44 ,387 1-3875.
5 Lindstrom , U. M. Chem. Rev. 2002 , 102, 2751-2772.

P0114
SEPARATION AND CHARACTERIZATION OF CRYSTALLINECEFUROXIME AXETIL DIASTEREOMERS
Chuan-Qi Zheng ,a and Jiwen Caib
8
School of Life Sciences , SunYat-Sen University, Guangzhou 510275 , P. R.ChinabSchool of Chemistry & Chemical Engineering , SunYat-Sen University, Guangzhou
510275 , P. R.China (puscjw@zsu .edu.cn)

Cefuroxime axetil (CFA) , an ester prodrug of cefuroxime , is a cephalosporin antibiotic
having a broad spectrum of activity against both gram-positive and gram-negative
microorganisms . The ester portion of CFA, namely the 1-acetoxyethyl group , contains anasymmetric carbon atom , and accordingly CFA exists in the form of a mixture of the SSRand SSS- diastereoisomers. Oral administration of the R,S-mixture of CFA results in only
about fifty percent bioavailability. The R-isomer of CFA is more stable and results ingreater bioavailability than the S-isomer.
We will report an efficient crystallization method to separate the isomers. The crystal
structure of the SSR-isomer will also be reported for the first time. This study is supported
by Science and Technology Programs of Guangdong Province , Grand No. 2003C1 04030).

Fig .1 Structure of cefuroxime axetil

Fig .2 Packing arrangement of cefuroxime axetil

P0115
THE CRYSTAL STRUCTURES OF A SREIES OF DINICKELCOMPLEXES BRIDGED BY UNUSUAL (N,O,O')- COORDINATED AMINO
ACIDS
Li Wang , Jiwen Cai , Jin-Wang Huang
School of Chemistry & Chemical Engineering , SunYat-Sen University, Guangzhou
510275 , P. R.China (puscjw@zsu.edu .cn)

a-Amino acids are interesting biological ligands with multiple functional groups,
which display variant coordination modes under different chemical environment . A
systematic investigation of the coordination behavior of amino acids under different
chemical environment is necessary in order to reveal the roles played by amino acids inimportant chemical processes involving metal ions.
Three novel dinickel complexes , coordinated by mixed ligands of tren and racemic
aminoacids ,
namely[Ni 2(tren) 2(dl-alaninato )(Hp)]I 3·2Hp( 1),[Ni 2(tren) 2(dlleucinato)(Hp)]I 3·2.5Hp(2),[Ni2(trenMdl-phenylalaninato)(Hp)]I 3· Hp(3) have beensynthesized and structurally characterized by x-ray crystallography.They represent thefirst series of dinickel(ll) complexes bridged solely by the unusual (N ,O,O')-coordinateda-amino acids. In complexes (1-3) , one of the nickel(ll) center is coordinated by four Natoms of the tren ligand , one 0-atom of the carboxylate group of the amino acidato
ligand and one water molecule . The other nickel(ll) center is also coordinated by thefour N-atoms of the tren ligand , one carboxylic 0-atom and the amino N-atom of theamino acidato ligand , resulting in an asymmetric dinuclear core with chromophores of
NiN.0 2 and NiNp[1]. This project is supported by the National Natural Science

References
1 Li Wang , Jiwen Cai , Zong-Wan Mao and Jin-Wang Huang,(2003) Transit Metal
Chern. , in press .

P0116
VARIATION IN THE COORDINATION MODES OF DIFFERENTARENEDISULFONATES TO TRANSITION METAL IONS
Dong-Sheng Deng and Jiwen Cai
School of Chemistry and Chemical Engineering , Sun Yat-Sen University, Guangzhou
510275 , P. R. China (puscjw@zsu .edu .cn)

Metal sulfonates have been of great interest because of their catalytic functions[1]and absorbing capacities[2] . However, owing to their weak coordination strength of
sulfonate toward transition metal ions , the coordination chemistry of metal sulfonates is
not well explored and rationalized[3]. Herein , we report the structural characterization of aseries of divalent transition metal arenedisulfonates , in the present of imidazole ligand . In
the same reaction condition , Cd 2• shows the strongest coordination strength toward thesulfonate groups , and different arenedisulfonates have different coordination modes . The
S0 3· oxygen of the 2,6-naphthalenedisulfonate and 1,5-naphthalenedisulfonate cancompete with water molecules and coordinate to Cd 2• . While there is no direct interaction
between Cd 2 • and S0 3· in 4.4'-biphenyldisulfonate . The overall structures are held
together by strong intermolecular hydrogen bonds .
This project is supported by the National Natural Science Foundation of China(Grand No. 20271 053).
References
1
S. Kobayashi and T. Wakabayashi. Tetra . Lett., 1998, 5389 .
2
J.-S. Zhou , J. Cai , L. Wang and S.-W. Ng. Dalton Trans. , 2004 , 1493.
3
J. Cai , C.-H . Chen , C.-Z. Liao , J.-H . Yao , X. -P. Hu and X.-M . Chen . J. Chem. Soc.
Dalton . Trans., 2001 , 1137.

P0117
A CONTEMPORARY APPROACH TO MORPHOLOGICAL CONTROL OF
NANOCRYSTALS
Mingmei Wu , Xianfeng Yang , Gan Lin , Caihong Wang , Wenjiao Lin , Lifang Liang , Xijiang
Chen , Ningsheng Xu, Qiang Su
State Key Laboratory of Optoelectronic Materials and Technology, School of Chemistry
and Chemical Engineering , Sun Yat-Sen (Zhongshan) University, Guangzhou 510275, P.
R. China (ceswmm@zsu.edu.cn)

The properties of inorganic nanocrystals are significantly influenced by theirstructure , size and shape. Much attention has been focused on controling their growthusing organic surfactants as templates or structure-directing agents. However, themorphology traditionally found was dependent on inherent crystal struture. Here we
present a variety of examples of inorganic nanocrystals with different shapes related totheir crystal structures. [1 ,2] Both rutile and anatase display the same tetragonal crystal
system and point group of 4/mmm . However, they belong to different space groups andthus different surface arrangements of atoms. This is a crucial factor affecting thedifferential growth kinetics for each phase and thus the nanocrystal morphology. [1-3]
In the presence of small organic molecules and I or inorganic additives in thegrowth media , both the phase and nanocrystal morphology, such as zero-dimentional
nanocubes (nanograins) and one-dimentioal nanorods (nanowires) ca n be controlled. One
dimentional nanostructures have been of great interest because of their attractive andunique physical properties due to their marked anisotropy. The stacking of cubic moieties
with cubic crystal structures and confined growth along a specific direction yield onedimentional nanorods (nanowires) of BaTiOJ and BaF2 by using organic surfactants as
templates. [2] However, the free kinetic growth of hexagonal ZnO , ZnS and CdS
semiconductors give rise to one-dimentioal nanorods (nanowires) and even tubular
structures with hexagonal symmetry. Even more complex multi-armed , heteronanostructures of these semicondutors composed of both cubic cores with (111) lattices
and hexagonal arms with [001] growth directions can be developed through modulating
the growth conditions with time . With this method, spherical, plate-like , and tubular
crystals of both mono- and multi-component rare earth fluorides can also behydrothermally grown. Modification of their morphology can enhance their physicalproperties such as photoluminescence.
References
1
Lee , S.M ., Cho , S. N. Cheon , J. Adv. Mater., (2003), 15, 441 .
2(a) Cao, M. , Hu , C., Wang , E. J. Am. Chem. Soc. , (2003), 125, 11196. (b) Urban , J.
J., Spanier, J. E., Ouyang , L., Yun , W . S., Park, H. Adv. Mater. (2003), 15, 423 .
3(a) Wu , M.-M ., Lin , G., Chen , D.-H., Wang, G.-G ., He, D., Feng , S.-H. , Xu , R.-R.
Chem. Mater., (2002), 14, 1974. (b) Chen , X.-J. , Xu, H.-F., Xu , N.-S. , Zhao, F.-H .,Lin , W .-J. , Lin , G., Fu , Y.-L. , Huang, Z.-L., Wang , H.-Z. and Wu , M.-M. lnorg.
Chem., (2003), 42 , 3100 . (c) Liang, L.-F., Xu, H.-F. , Su , Q., Konishi , H. , Jiang , Y.8. , Wu , M.-M ., Wang , Y.-F ., Xia , D.-Y. , lnorg. Chem. , (2004), 43 , 1594.
Acknowledgement: This work is supported by NSF of Guangdong and China .

P0118CRYSTAL STRUCTURES AND MAGNETISM OF A SERIES OFTETRANUCLEAR HETEROMETALLIC Co(III)-Ln(lll) COMPLEXES
Feng He , Yang-Yi Yang , Xiao-Minq Chen*
School of Chemistry and Chemical Engineering , Sun Yat-Sen University, Guangzhou
510275 , China (exstxr@zsu.edu .cn)

There has been growing interest in the design and synthesis of heterometallic 3d-4f
complexes motivated by their interesting structures , as well as their special properties incatalysis , precursors of magnetism [1] . In the past years , we described the syntheticroutes offered by betaine and its derivatives to produce 3d-4f complexes [2-4] , As an
extension of our work, we herein report an new approach to multinuclear Co-Ln species.
Treatment of CoCI 2 , Ln(N0 3 ) 3 (Ln = La , Ce , Nd , Sm , Gd , or Dy) and 2hydroxymethylpyridine (Hhmp) in a ratio of 1:2:2 resulted in dark red crystals[Co 2 Ln 2 (hmpMN0 3 ) 3 (Hp)], which are isostructural , and the structure of Nd compound isshown below. The Co(lll) ion exhibits a distorted octahedral environment with threeoxygen and three nitrogen atoms from three hmp ligands. The oxygen atoms of hmp act
as bridges between Co(lll) and Nd(lll) ions. The Nd(lll) ion is ten-coordinated by ten
oxygen atoms , nine of which are from three bidentate nitrate group and three hmp while
the last oxygen atom is from a water molecule . This water molecule exhibits anunprecedented linear bridging mode to link the Nd(lll) ions in two dinuclear [CoNd] units.
Except the La complex, all these complexes exhibit moderately strong antiferromagnetic
interactions.

References
1 Winpenny, R. E. P. (1998) .Chem. Soc. Rev. 27 , 447.
2 Chen , X.-M ., Aubin , S.M. J. , Wu , Y.-L. , Yang, Y.-S ., Mak, T . C.W. , Hendrickson, D.
N.
(1995) J. Am. Chem. Soc. 117, 9600.
3 Yang, Y.-Y., Wu , Y.-L. , Long , L.-S. , Chen , X.-M . (1999) . J. Chem. Soc. , Dalton
Tran s. 2005.
4 Yang , Y.-Y. , Huang , Z.-0. , He , F., Chen , X.-M. , Ng , S.W. (2004). Z. Anorg. A/lg.
Chem. 630 , 286.

P0119CRYSTAL STRUCTURE OF DINUCLEAR COPPER (II) COMPLEX OF
DIMETHYLGL YOXIME WITH BRIDGING CHLORIDE
J. Kowiththaya•, S. Siripisarnpipat•, V. Ngumviriyakul•, N. Chaichitb, S. Sukvinich••Department of Chemistry , Faculty of Science , Kasetsart University, P.O. Box 1011
Kasetsart, Chatuchak, Bangkok, 10903 , Thailand , bDepartment of Physics , Faculty of
Science and Technology, Thammasart University, Bangkok 12121 , Thailand ;(fascists@ku .a c.th)

A new dinuclear complex with bridging chloride , [Cu 2 (DMG) 2 CI 2 (1J-CI) 2] has beensynthesized by adding an acidic solution of CuCI dropwise into a hot acetone solution ofligand. The reaction mixture was stirred at room temperature , a yellow powder wasobserved in a solution. After two days , a green crystalline product was obtained andrecrystallized from hot acetone.
Originally, the dioxime complex of Cu(l) was planned to synthesize . The data
revealed that the structure of the green crystal is a dinuclear copper(ll) complex ofcomposition {Cu2(DMG)2CI4} . This means the buthyl group , which connects two oxime
moieties , was eliminated during the course of the reaction. The dinuclear complex
crystallizes in triclinic system , space group P1 , with a= 7.7161 (2) , b= 8.1414 (3), c=
8.1983 (2) A, a= 108.143 (1 ), ~= 101 .283 (2) , y= 110.856 (2 t , V= 429 .24 N , De= 1.939
g/cm 3 , Z= 1, A(Mo Ka )= 0. 71073 A, T= 298 (K) , R1 = 0.0432.
The crystal structure consists of two [Cu(DMG )2CI] units linked by two chloride ions .
In each [Cu(DMG )2CI] moiety, the coordination geometry around copper atom is adistorted square pyramid . Each copper atom coordinates with two oxime nitrogens, one
chloride and two bridging chloride ions . The five membered ring formed by DMG group ineach unit is planar to each other but is perpendicular to the plane formed by two coppers
and two bridging chloride. Infrared spectrum of the title compound exhibits v(OH) at 3302
and 3215, v(CN) at 1630(b) and v(NO) at 1089 and 1064 em·' . The electronic absorption
spectrum of the title compound in methanol displays a broad band centered at 842 nm
confirmed the divalent state of copper ion .

References
1
Thohinung , S. 2000. Synthesis and crystal structures of two diimine- dioxime
complexes of cobalt. M.S. thesis , Kasetsart Univ. , Bangkok.
2.
Li , C.H., Wang , R.J. , Kou , H.Z. and Li , Y.D. , lnor. Chern. Commun. , 5, 403 , 2002.
3.
Zhan , S., Hu , C., Chen , X., Meng , Q. , Lu , C., Wang , G. and Zheng , P., Polyhedron ,18, 2035 , 1999.
4
Ruiz, R. , Lloret, F., Julve, M., Faus , J., Munoz, M.C. and Solans, X., lnorg .
Chim.Acta ., 268 , 263 , 1998.

P0120CONFORMATION OF EIGHT MEMBERED RING: 6-[BIS (2-CHLOROETHYL)AMINO ]-12- OXO- DIBENZO [d,g],[1,3,2] DIOXAPHOSPHOCIN
6- OXIDE.
M.Krishnaiah , N.Jagadeesh Kumar
Department of Physics S.V. University, Tirupati-517502 , India. (mkphysvu@yahoo .co .in)
Organophosphorous compounds have wide scope for applications in life destroying
activity as pesticides , insecticides, nerve gases , antioxidants and stabilizer in polymers
and oils. N-mustered phosphorous derivatives are of particular interest because of theirchemotherapeutic properties in cancer. In continuation of conformational studies oneight-membered hetrocyclic compounds , the title compound has been studied to evaluate
the effect of the substituents on geometric changes and conformation of the eightmembered ring . In the title compound , C, 7 H16 C,2 N0 4 P, crystallizes in a monoclinic systemwith space group P2,fc. The crystal data are a = 21 .273(4) , b = 8.5380(11 ), c =19.353(5)A; ~ = 90.864(6 r, V = 3514 .7(12)A 3 , Pc = 1.513Kgm·3 , Z = 8, f.(M 0 k0 ) =0.71073A , F(OOO) = 1648 and final R = 0.039 for 4949 observed reflections. The structure
was solved by direct methods using SHELX-86 and refined by full matrix least squares
method using SHELX-97 . The structure reveals distorted boat (DB) conformation for the
dioxaphosphocin ring with phosphonyl '0' (P=O) in equatorial orientation and 'oxo' groupin a pseudo equatorial arrangement. The planar benzene groups are fused to heterocyclicring at an angle of 53 .7° in molecule-\ and 50 .3°in molecule II with one another. The bondlengths around P-atom and 'oxo' group (C=O) are increased due to N-mustered groupattached to P-atom as an exocyc\ic substitution . The structure is stabilized by van derwalls interaction .

P0121
ELECTRON DENSITY AND ELECTRONIC CONFIGURATION OF
BIOMIMETIC MODEL DINITROSYL IRON COMPLEX [S 5 Fe(N0) 2]1.-Jui Hsu ,a Jey-Jau Lee ,D Chung-Hung Hsieh, c Tze-Yuan Wang ,a Gene-Hsiang Lee,d JinMing Chen ,.DJyh-Fu Lee, b Shyue-Chu Ke ,• Wen-Feng Liaw,c Yu Wang•"National Taiwan University, Taipei , Taiwan
DSynchrotron Radiation Research Center, Hsinchu , Taiwan
cNational Tsing Hua University, Hsinchu , Taiwan
dlnstrumentation Center, National Taiwan University, Taipei , Taiwan"National Dong Hwa University, Hualien, Taiwan

The NO coordinated iron compounds of dinitrosyl iron complexes (DNICs) are theproduct from the degradation of the iron sulfur-rich protein due to its binding of NO group.
The DNICs have been suggested as possible forms for the stabilization and the transportof NO in biological system. Recently, the title model compound was synthesized and wasdemonstrated not only a precursor of Roussin 's black salt [Fe 4 S3 (N0) 7 ) -, but also a NO
donor to react with the NO trapping agents , such as iron dithiocarbmate complexes , togive the mono nitrosyl product (NO)Fe(S 2 CNR 2 ) 2 which was generally considered as thebonding between NO+ and Fe(l) . The bond angles , Fe-N-0 , of the title compound are
172.50(7) and 165.71 (8), and the stretching frequencies of NO are in the range -1695 1741 em-• . Because of the ambiguity of the traditional way to discriminate the oxidation
states of NO•, NO• and NO- group , the X-ray absorption spectroscopy of Fe K- , L-edge and
N/0 K-edge were used to investigate the oxidation state of metal and NO groups.
Meanwhile, the detailed electron density distribution and chemical bonding characters of
the title compound were studied by X-ray diffraction data with multipole model and the
topological analysis . A comparison between the di-nitrosyl and mono-nitrosyl complexes
will be made in terms of the experimental and theoretical results. Moreover, the magnetic
susceptibility and electron paramagnetic resonance results will be included to illustrate theelectronic configuration among Fe and NO groups. Finally, based on the EnemarkFeltham notation , all results toward the conclusion that the best way to describe thepresent dinitrosyl and mononitrosyl cases are {Fe• 1 (•N0) 2} 9 and {Fe• 1 (N0• 1 ) }' .

P0122
MULTIPLE-WAVE X-RAY DIFFRACTION AT RESONANCE: AN ITERATIVEBORN APPROXIMATION
W.-H . Sun•, Y.-R . Lee•, S.-C. Weng•, S.-Y. Cheng•, W.-C. Sun•, S.-L . Chang••Department of Physics, National Tsing-Hua University (sws0928@yahoo .com.tw)
The anomalous dispersion behavior of multiple-wave x-ray diffraction for
noncentrosymmetric crystal of zinc-blend structure at atomic absorption edges(resonance) is investigated and the spectral distribution of three-wave diffraction
intensities are measured. A resonance perturbation Born approximation is used to accountfor the measured intensity distributions and the asymmetric intensity ratio Rv of three-wave
diffraction. In this approach , the third-order Born approximation is adopted for the threewave fundamental equation , thus leading to the asymmetry parameter Rv. The real part!J.f(Q) and imaginary part 4f'(Q) of dispersion corrections on the atomic scattering factors
versus the photon energy are deduced then from Rv. The fine structure function X and the
distances between the nearest and the next nearest atoms are also determined. The
differences between this Born approximation and the exact dynamical calculation will be
discussed .
We believe that the iterative Born approximation make this resonance multiple-wave
diffraction technique applicable to diffraction from thin films.

P0123C-C BOND CLEAVAGE OF ALKYL AND ARYL CYANIDES BY A
DINUCLEAR COPPER(II) CRYPTATE
Tongbu Lu , Xiaomei Zhuang , Danni Que , Yanwu Li , RuoQqiu Wu , and Shi Chen
Instrumentation Analysis & Research Center, and School of Chemistry and Chemical
Engineer, Sun Yat-Sen University, Guangzhou 510275 , China (cesltb@zsu.edu.cn)
The activation of carbon-carbon bonds by transition metal complexes in homogeneous
media remains a challenge in the field of organometallic chemistry[1] . Recently, someorganometallic complexes have shown to activate the carbon-carbon bonds of aryl andalkyl cyanides[1-2] . The above activation of C-C bonds is accomplished by air sensitive
metalloranic compounds through an 11 ' or q2-nitrile intermediate. We have found that an
air stable dinuclear copper(ll) cryptate can also cleave the C-C bonds of aryl and alkyl
cyanides at room temperature , where the activation of the C-C bond is due to thefavorable formation of a stable cyanide bridged dinuclear copper(ll) cryptate.
In this presentation , we will report the synthesis , structure , and cleavage mechanismof the dinuclear copper(ll) cryptate .
References
1 Taw, F. L., Mueller, A. H. , Bergman , R. G., and Brookhart, M. (2003) J. Am. Chern.
Soc. 125, 9808-9813; Taw, F. L. White , P. S., Bergman , R. G. and Brookhart, M.
(2002) J. Am. Chern. Soc. 124, 4192-4193 .
2 Churchill , D. Shin , J. H. Hascall , T. Hahn , J. M. Bridgewater, B. M. and Parkin , G.
(1999) Organometallics , 18, 2403-2406 ; Garcia , J. J. , Brunkan, N. M. and Jones,
W. D. (2002) J. Am. Chem . Soc. 124, 9547-9548 .

P0124
CRYSTAL STRUCTURE AND CHARACTERIZATION OF A NEW
CARBOXYLATO-MPO ORGANIC-INORGANIC HYBRID MATERIAL
Yueh-Chun and Sue-Lein Wang*
Department of Chemistry, National Tsing Hua University, Hsinchu 300, Taiwan(slwang@mx.nthu .edu.tw).

A

newzeolitic

phosphate-basedorgan1c-1norganic

hybridmaterial ,(H 2 tmdp)[(ZnHP0 4 ) 2 (BDC)] (1 ), (BDC = 1,4-benzene dicarboxylate or terephthalic anion;
tmdp = 4,4'-trimethylene dipyridine) has been prepared and structurally characterized. It
exhibits a highly porous framework built up with tetrahedral inorganic sheets pillared by
BDC groups. The conclusive structure was solved and refined using the intensity datacollected from a lamellar twin. The 3D anionic framework is built up with neutral ZnHP0 4
layers and BDC anions acting as pillars. In the inorganic layers, each Zn0 4 tetrahedronshares three oxygen atoms with HP04 tetrahedra , resulting in three-connected twodimensional nets (4 .82]. A similar 2D topology can be observed in zeolite gismondine,
where the porous nets are flat with the Si0 4 tetrahedra around the 8R apertures all
pointing to the same direction . In 1, the inorganic nets are curved with the sequence ofalternating Zn0 4 and HP04 tetrahedra being UUUUDDDD (U up , D down) toward theinterlayer space and linking to the pillaring BDC units. The resulting network has multidimensional intersecting channels running along [011], (111] and all three axial directions
with template cations locating at channel intersections. The channels running along c are
zigzag with spacious interior and oval-shaped openings. The non-framework space wascalculated to take up to 48% of the unit cell volume. Besides the interesting zeolitic
property, the new material is photo-luminescent and can disassemble in the water to givea unique acid-base type of mixed crystals. In this paper, we present the synthesis ,structure, sorption , photoluminescence and dissolution properties and an inverting mixed
molecular crystal of compound 1.

P0125
STRUCTURAL CHARACTERIZATION OF TWO ORGANICALLYTEMPLATED GALLIUM PHOSPHATE
Yu-Lun Lai and Sue-Lein Wang*
Department of Chemistry, National Tsing Hua University, Hsinchu 300, Taiwan(g923467@oz.nthu .edu. tw)

One new gallium phosphates ,(H 4 appip)[Ga 4 0 2 (P0 4 ) 4 ] (1 ; appip = 1,4-Bis(3-aminopropyl)piperazine ) and one vanadium gallophosphate (H 2 dapM(V0) 2 Gaz0 2(P0 4 ) 4 ] HzO (2; dap = 1,3-diaminopropane ) have been synthesized under hydrothermal
conditions and characterized by single-crystal X-ray diffraction and thermogravimetricanalysis. Compound 1 adopts a 2D layer structure where the gallium atoms are all inpenta-coordiantion. Compound 2 adopts a chain structure in which the vanadium sites arein penta-coordination while gallium sites are in tetra-coordination. Despite structuraldimensionality, 1 and 2 possess a common building unit (SBU) which is a uniquetetrameric metal-oxygen cluster. This type of SBU is rarely observed in the structure ofmetal phosphate. Crystal data of 1, a = 12.2562(7)A , b = 9.7196(5)A , c = 9.9095(3)A, fJ =101.66(3t, Z=2 , V=1156.10(26)A 3 , Monoclinic, P2,fc, R=0.0191 ; 2, a= 9.1754(4)A, b =10.7853(5) A, c = 15.6519(7)A,a = 93.25(0t , fJ = 92.53(0t, y= 95.11(0t , Z=1, V=
1538.39(22)A3 , triclinic, P-1 , R=0.027 .

2

P0126
MIMICRY OF DIMETALLIC HYDROLASES: SYNTHESES, STRUCTURES
AND ACTIVITIES OF ASYMMETRIC HOMO- AND HETERO-DINUCLEAR
MODELS
Gen-qiang Xue , ian D. Williams , and Xiao-Yuan Li
Department of Chemistry, The Hong Kong University of Science and Technology Clear
Water Bay, Kowloon , Hong Kong (chxyli@ust.hk)
Dimetallic hydrolases (DMH) catalyze the hydrolysis of a target bond , such as aphosphoester or a peptide bond , on a specific substrate. The active sites of DMH are
either homo- or heterodinuclear metal ions asymmetrically coordinated to the side chainsof enzyme residues. We report here the design , syntheses and characterization of a new
asymmetric ligand and its dinickel complex, as well as the catalytic activity of the complex
in the hydrolysis of a phosphoester bond on a model compound , bis-4nitrophenolphosphate(BNPP). Our studies were designed to address several issues: (i)the differential roles of two metal ions ; (ii) the binding mode of substrate; (iii) the identityand binding mode of nucleophile; (iv) the effect of medium to the catalytic activity. Our
results suggest that it is the terminal water/hydroxide , instead of the bridging
aqua(hydroxide) , that serves as the hydrolytic nucleophile.

Figure 1. Thermal Ellipsoid plot of the cation of the dinickel complex

P0127
STRUCTURAL ANALYSIS OF FIVE-COORDINATE TRANSITION METALBORYL COMPLEXES WITH DIFFERENT D-ELECTRONCONFIGURATIONSKing Chung Lam ," Wai Han Lam ," Zhenyang Lin ," Todd B. Marder,b Nicholas C. Normanc"Department of Chemistry, Hong Kong University of Science and Technology, Clear Water
Bay, Kowloon , Hong Kong; bOepartment of Chemistry, University of Durham , South Road ,Durham DH1 3LE , UK; cschool of Chemistry, University of Bristol , Bristol BS8 1TS, UK(chunglam@ust.hk)

The site preference of boryl ligands in five-coordinate transition metal boryl
complexes having d6 , d 7 and d8 electron configurations '- 3 has been investigated with theaid of density functional theory calculations. The preferred site for a boryl ligand depends
on the electron count of the complex under consideration. Our studies show that the verystrong a-donating boryl ligands choose to occupy coordination sites such that thoseorbitals accommodating metal d electrons have minimal metal-boryl o*-antibonding
character.

Beat'0PR 3I ,,,Cl ~ Rll'-Bcat
R3P

Beat

I

Me3P-Rh·' '"II\PMe3

I ........... PMe 3
PMe 3

References
1
Baker, R. T .; Calabrese, J. C. ; Westcott, S. A. ; Nguyen , P. ; Marder, T. B. J. Am.
Chern. Soc. 1993, 115, 4367.
2
Dai , C. ; Stringer, G. ; Corrigan , J. F. ; Taylor, N.J.; Marder, T. B.; Norman , N.C.
J. Organomet. Chern. 1996, 513, 273 .
3Dai , C. ; Stringer, G.; Marder, T. B. lnorg. Chern. 1997, 36 , 272 .

P0128X-RAY CRYSTAL STRUCTURE OF PLASMODIUM V/VAX
DIHYDROFOLATE REDUCTASE: ANTIFOLATE RESISTANCEMECHANISM
Palanqpon Konqsaeree ,a.b Puttapol Khongsuk,a.b Ubolsree Leartsakulpanich ,<Penchit Chitnumsub ,< and Yongyuth Yuthavongc•Department of Chemistry, Faculty of Science , Mahidol University, Bangkok, Thailand ;bCenter for Protein Structure and Function , Faculty of Science , Mahidol University,
Bangkok, Thailand ; <National Center for Biotechnology and Genetic Engineering(BIOTEC), National Science and Technology Development Agency (NSTDA),
Pathumthani , Thailand . (scpks@mahidol.ac.th).

Malaria is an endemic disease in vast areas of tropical and sub-tropical regions of
the world . It is estimated that 300 million people are affected by this disease with over two
million deaths annually [1]. Treatment and control of malarial relies on the improvement of
antimalarial medicines and the situation has been worsened as most of antimalarial drugs
used in the field , except artemisinin , have become less effective especially the two mostwidely used chloroquine and the antifolate sulphadoxine/pyrimethamine . Pyrimethamine , a2,4-diaminopyrimidine, specifically inhibits dihydrofolate reductase (DHFR) of thebifunctional dihydrofolate reductase-thymidylate synthase (DHFR-TS) enzyme , andprevents the nucleotide biosynthesis and amino-acid metabolism in the parasite.
Plasmodium vivax , the most prevalent malarial parasite with often causing relapses inmalarial patients, was shown to be susceptible to antimalarial antifolates. High-level
pyrimethamine resistance results from the accumulation of mutations in pvDHFR aroundthe active site (Ser117 Asn , and Ser58Arg). After being cloned and expressed , the wildtype Plasmodium. vivax DHFR domain (pvDHFR) has been successfully crystallized in ourlaboratory. The crystals belonged to the monoclinic space group C2 , with unit-cellparameters a= 136.53, b = 55.61 , c = 45.75 A and f3 = 107.46°.
The X-ray crystal structures of wild-type and mutants of PvDHFR in complex withpyrimethamine have been determined and refined to 1.8 A resolution. The nanomolarbinding constant of pyrimethamine in the active site of DHFR is contributed from extensivehydrogen bonds and rr-rr interactions. Significantly, the structural comparison between thewild-type and the mutants enzymes as well as biochemical kinetic results revealed the
drug-resistance mechanism was due to the steric effect at codons Ser117 . Efforts areunderway to analyze the structural information for a development of novel inhibitor design.
In the meeting , the mechanisms of the drug binding and of the antifolate-resistance in
pvDHFR will be discussed.
References
Warhurst, D. C. (2002) Sci. Prog. 85 , 89-111.
2
Yuthavong , Y. (2002) Microbes. Infect., 4 , 175-182.

P0129SELF-ASSEMBLY OF MULTINUCLEAR RUTHENIUM THIOSALICYLATESUPRAMOLECULESStephen Sin-Yin Chui , Sharon Lai-Fung Chan , Chi-Ming Che*
Department of Chemistry, The University of Hong Kong , Pokfulam Road , HKSAR, China(chuisy@hkusua.hku .hk)

Well-characterized Rux(SR )y based coordination compounds is sparse in literature[1]due to the difficulties in growing sing le crystals as well as their intrinsic chemical problems.
In this work , systematic studies on the solvothermal synthesis and the crystal structures ofa new class of multinuclear ruthenium thiosalicylate (TSA) clusters [Ru 3(TSA) 6 (H •.x)(Ax)] (x= 0, 1; A= N(C2Hs)• x = 1, 2; A= C3HsN2 x = 2, 3) and Ru. (TSA)a(H. )] 4 , revealed that they
form various interesting 1-D supramolecules of different topologies, directed by verystrong inter-cluster hydrogen bonds[2]. Replacement of all H ions on 1 and 4 by Na ionsleads a zeolitic supramolecular framework 5 with ca 8 x 7 A ion channels .
SSYC acknowledges financial support from The University of Hong Kong , SAR China , forthe award of the Postdoctoral Fellowship , through the AoE Scheme.
References
1
I. G. Dance , Polyhedron 1986, 5, 1037; E. I. Stiefel , Transition Metal Sulfur
Chemistry: Biological and Industrial Significance ; E. I. Stiefel , K. Matsumoto, Eds .,ACS Symposium Series No. 653 ; American Chemical Society: Washington , DC ,1996, 1 and references cited therein.
2
G. R. Desiraju , T. Steiner, The Weak Hydrogen Bond In Structural Chemistry andBiology, IUCr Monographs on Crystallography, Oxford Science Publications.

P0130THE CRYSTAL STRUCTURE OF SODIUM DIVANADYLDICITRATEDODECAHYDRATE
Pham Thanh Huyen• and Kenneth J. Hallerba Petrochemical and Catalysis Material Laboratory, Faculty of Chemical Technology, Hanoi

University of Technology, Hanoi , Vietnam ;School of Chemistry, Institute of Science , Suranaree University of Technology, Nakhon
Ratchasima 30000 , Thailand ;(pthuyen@mail.hut.edu .vn).

bNa.{(V0)2[(0)(CH 2COO)C(COO)(CH2COO)h}-12H20 was synthesized by reactionof vanadium pentoxide with citric acid in the presence of sodium hydroxide. The
compound crystallizes in the monoclinic space group P2,/c with a = 11.2799(8), b =15.7282(1 0), c = 8.6547(8) A, ~ = 104.74(1) o , and V=1484.94(16) N , T = 298 K. Intensity
data were collected on a Bruker Nonius KappaCCD diffractometer using Mo Ka xradiation.
The complex consists of two inversion related square pyramidal vanadium(IV) atoms
bridged through their basal oxygen atoms by two citrate ligands. Each citrate ligand forms
a six-member chelate with one vanadium atom and a seven-member chelate with theother. The apical positions are occupied by vanadyl oxygen atoms .
Both crystallographically unique sodium cations are coordinated by six oxygen
atoms. One sodium interacts with the three crystallographically unique carbonyl oxygen
atoms , each on a different complex (d[Na-0) - 2.35 A), the vanadyl oxygen atom(d[Na-0) = 2.53 A) , and two water molecules (d[Na-0] - 2.40 A). The carbonyl andvanadyl interactions link the complex anions into a sheet structure , while the watermolecules bridge to the second sodium cation , which interacts with six waters of hydration(d[Na-0) - 2.4-2.5 A), leading to a second sheet structure which alternates with thelayers of vanadyl citrate complex , approximately perpendicular to!!_.
Crystal data: C,2H8 Na. O,sV2·12H20 ; M, = 822 .27 Daltons; transparent blue; irregularfragment 0.20 x 0.32 x 0.45 mm ; monoclinic; P2,/c (No . 14), T = 298 K, a= 11.2799(8) A, b
= 15.7282(10) A, c = 8.6547(8) A , ~= 104.74(1) 0 , v = 1484.94(16) N , = 2, 11 = 8.06
em·'; d eale = 1.821 Mg/m 3 ; AMoKa = 0.71073 A; Data collection: Nonius KappaCCD; 0.5 mm ifg
capillary collimator; 57636 data collected (triclinic); 7011 unique (2/m), R sym = 0.044 ; 4525
observed Fo > 4a(Fo), R , = 0.047 , P max = 1.07(12) e!N.

z

P0131
TROILITE WITH SPACE GROUP P31c FOUND IN METEORITE
Takeshi Nakagawa ,a Michael E. Zolensky, b Katsuhiro Kusaka , a Yoshikazu Miyatac andKazumasa Ohsumia•Institute of Materials Structure Science , High Energy Accelerator Research Organization,
Oho 1-1 , Tsukuba , 305-0805 , Japan ; ' NASA,2101NASA Parkway Houston , TX 77058
U.S.A. ; cThe Graduate University for Advanced Studies , Oho 1-1 , Tsukuba , 305-0805 ,Japan (Kazumasa.ohsumi@kek.jp ).

Kivesvaara meteorites are known as the least altered CM2 chondrite , and conta in
microscopic iron sulfides, probably stoichiometric pentlandite and pyrrhotite[1]. The
specimen in a thin section has a dimension of about 20 pm in diameter. The chemicalcomposition of an iron sulfide (K2) was determined to be Fe 0943 Ni 0 _006 S using EPMA
(M.E.Z.).
The Laue pattern of K2 was taken at BL-4B1 of KEK, using polychromaticsynchrotron radiation beam with the size of 1.6 ~~m in diameter. All reflections in thepattern were indexed with hexagonal cell of troilite having a=A and c=2C referred to a
NiAs-type subcell (A=3.45A, C=5.7A). The axial ratio was consistent with that averaging
among those of King & Prewitt(1982), Yund & Hall(1968) and Taylor(1970)(c/a =(1 .968(1 )).
The a-axis and c-axis dimensions are 5.963A and 11 .70(2)A respectively, calculated using
the a-axis cited from King & Prewitt(1982).
_
Next, the structure of K2 was refined as troilite with space group P 6 2c using 43
reflections. The initial parameters were adopted from King & Prewitt(1982). The residual R
factor converged to 0.0192 , though temperature factors are much different from the initial
parameters. Furthermore , the observed intensities of some strong reflections were not inagreement with the _s:alculated values. Conse~ently, the space group of K2 wasassumed not to be P 6 2c but the sub-groups of P 6 2c which are P321 , P31 c and C2cm .
Both in the case of P321 and C2cm , the refined positional and temperature parameters
diverged in the process of the refinement. The refinement with P31c successfully
converged to the residual R factor of 0.00580 with the 20 refined parameters, including ascale factor and those of optimizing incident X-ray spectra. The temperature factors of K2
are suitable for all the known pyrrhotites . The bond lengths of (Fe ,Ni)-S range from 2.05
to 2.87 A with the average of 2.5(4)A, and are_compatible for common iron sulfides. It is
concluded that the space group of K2 is not P 6 2c but P31 c. In addition , the vacancy and
Ni are not distributed randomly over two Fe sites but in crystallographic independent sites ,respectively.
Troilite with P31c was first found in the meteorite.
References
1 Zolensky, M. E. & Le , L. (2003). Lunar and Planetary Science XXXIV.1235.
2
King , H. E. Jr& Prewitt, C. T. (1982). Acta Cryst. 838 , 1877-1887.
3 Yund , R. A. & Hall, H. T. (1968). Mater. Res. Bull. 3, 779-784 .
4 Taylor, L. A. (1970). Carnegie lnst. Washington Yearb. 68 , 259-270.

P0132
A RE-INVESTIGATION OF THE CRYSTAL STRUCTURE OF NATURALCHEVKINITE
Guowu Li•, Zhengsheng Ma•, Nicheng Shi•, Ming Xiong• and Haifu Fanb
•China University of Geosciences , Beijing 100083, China ; blnstitute of Physics, Chinese
Academy of Sciences, Beijing 100080, China (liguowu@tom .com)
The crystal structure of natural chevkinite has been redetermined with single-crystal
samples found in Beiyunebo Interior Mongolia , China . The chemical formula of the sample
is Ce 4 Fe 2Ti 3Sip 22 . Crystals are monoclinic with unit cell parameters a= 13.4656(15) A, b
= 5.7356(6) A, c = 11 .0977(12) A, ~ = 100 .636(2), V = 842.39 (16) A3 and Z=2 . According
to the present work the space group is P2 ,fa in contrast to C2/m from the previous
studies . Least-squares refinement based on P2,fa converged to an R-factor of 0.027 . In
order to illustrate the relationship between the two space groups P2 ,fa and C2/m, thedistribution of diffraction intensities were inspected . Pseudo extension was found thatreflections with h+k=2n are systematically strong , while that with h+k=2n+1 are weak . By
neglecting systematically weak (h+k=2n+1) reflections the space group becomes C2/m.
No significant difference in atomic parameters , except the x-coordinates of 0 atoms, canbe observed between the two refined models according to the space group P2 ,fa andC2/m respectively, see Fig.1.

P2da

C21m

Fig .1 The difference of oxygen atomic arrangement in space group P2 ,fa and C2/m
There is a mirror plane in C2/m perpendicular to the b axis , however, in P2 ,1a oxygen
atoms are related by a corresponding pseudo mirror plane.
It is concluded that the crystal structure of natural chevkinite is a superstructure withspace group P2,Ja . It possesses pseudo symmetry corresponding to the space group
C2/m.

P0133
STRUCTURE CHANGE OF Mn 2 0 3 UNDER HIGH PRESSURE CAUSED BY
CHARGE DISPROPORTIONATION
TakamitsuYamanaka ," Takaya Nagai," Tomoo Fukuda• and Koichi Kittaka••Department of Earth and Space Science , Graduate School of Science Osaka University
1-1 Machikaneyama Toyonaka , Osaka 560-0043 Japan(yamanaka@hpc.cmc.osaka-u .ac.jp)

It has been known that many of M2 0 3 compounds have a corundum structure (M=AI , V,
Ti , Cr, Fe) with space group of R3c. When an ion radius ratio has a relation ofr(M)/r(0)>0 .87 , the structure is characterized by A-type rare earth structure (M=Iantanides)with P3m. In the case of 0.60< r(M)/r(0)<0.87 , the structure is named by C-type rare earth
with space group of Ia 3 whose structure is represented by Eup 3 (M= Eu , Er, Gd , In, Lu ,Nd. Pr, Sc, Sm , Th, Tl , ZY, Yb). In the C-type rare earth structure the cation sizes permit
oxygens to approach cubic close-packing. Since many possible positions for cations arevacant, a large unit cell is required and contains 16 molecule.
Prewitt et at. , (1969) 11 proposed Mnp 3 changed from Rare Earth C-type to corundum
structure under compression . Syono et al. , (1997) 21 reported a high-pressure phase over
20GPa . Mnp 3 has a different structure from corundum structureHigh-pressure single crystal structure analysis up to 11 GPa
Single-crystal structure analyses at 0.0001 , 5.47 , 8.8 and 9.64GPa were carried out
using synchrotron radiation at BL-10A, Photon Factory (PF) at Tsukuba by single crystal
diffraction study using diamond anvil cell (DAC). Structure analyses at 0.0001 GPa , 4.7
GPa and 7.0 GPa were using laboratory X-ray source. The intensity measurements werealso made with a four-circle diffractometer (RIGAKU AFC-5) using MoKa radiation oflaboratory X-ray generator with 50kV and 180mA. The reliable parameters R ( = wiiFobsl IFcalllfiFobsl) of the refinements were converged to within R = 0.05.
M1 site is an almost ideal octahedron of Mn06 but the M2 site has a largely distorted
octahedron. Average distance of Mn2-0 more compressed than that of Mn1-0 . Bothoctahedra do not show a remarkable change of Jahn-Teller effect induced from Mn 3• .
Phase transition confirmed by SR powder diffraction study up to 40GPa
Powder X-ray diffraction study was executed at BL-18C at KEK with increasingpressure up to 40GPa. New high-pressure phase was observed above 20GPa . No abruptchange was found in the lattice constant . The high-pressure phase was not quenchable ,inferring a reversible transformation . A high-pressure phase has distorted orthorhombic
symmetry rather than rhombohedral such as corundum , ilmenite or LiNb03 type structure.
Charge disproportionation such as 2Mn 3•= Mn 2•+ Mn•• .is possible under high pressure .
The isothermal equation of state (EOS) is Ko=176.5(4 .8)GPa and Ko '=7 .56(0.67),
which indicatea little smaller than the reported data of Alp 3 , Vp 3 , Crp 3 and Fep 3 .
References
1 C.T.Prewitt , Inorganic Chemistry, Vol.8 , No.9, 1985-1993, 1969
2 Y. Syono (1997) Abstract of Japan High Pressure Science and Technology

P0134
THE STRUCTURAL BASIS OF STABILITY AND SUBSTRATE
SPECIFICITY OF A PLANT CYSTEINE PROTEASE FROM AN
INDIGENOUS FLOWERING PLANT, Ervatamia Coronaria
Chandana Chakrabarti , Piyali Guha Thakurta , Sampa Biswas , and J.K. Dattagupta
Crystallography & Molecular Biology Division , Saha Institute of Nuclear Physics ,Bidhannagar, Kolkata 700 064 , India (chandana@cmb2 .saha .ernet.in)

The ervatarnins , highly stable cysteine proteases , purified from the latex of the
medicinal plant Ervatamia coronaria , belong to the papain family of cysteine proteases ,members of which share similar amino acid sequences and also a similar overall foldcomprising two domains. The crystal structure of Ervatamin C of this family has been
determined at 1.9 A. The unknown primary structure of the enzyme could be traced fromthe good quality electron density map .
This protease is reported to have an unusual stability and a difference in its substratespecificity from the others in the family , which has been explained from the crystal
structure .
A comparison of amino acid sequences of the papain family cysteine proteases
shows some natural substitutions of conserved amino acid residues in both the domains
and at the interdomain cleft of Ervatamin C. These substitutions result in an increase in
the number of intra- and interdomain hydrogen bonding interactions. In addition , in
Ervatamin C, four disulfide bridges are found , only three being present in the othermembers of the family. All these factors contribute to an increase in the stability of the
enzyme .
Biochemical studies indicate that Ervatamin C is only partially inhibited by leupeptin ,a potent inhibitor of the papain family of cysteine proteases . However, it hydrolyses
natural protein substrates with high specific activity. These observations can be explainedon the basis of the substitution of an important amino acid residue at the active site cleft ofthe enzyme.

P0135
STRUCTURAL BASIS FOR CATALYTIC RACEMIZATION AND
SUBSTRATE SPECIFICITY OF N-ACYLAMINO ACID RACEMASE FROM
DEINOCOCCUS RADIODURANS
Wen-Ching Wang•· , Wei-Chun Chiu•. Chun-Li Wu•, Cheng-Yu Chen•, Jai-Shin Liu•, and
Wen-Hwei Hsub
•Institute of Molecular and Cellular Biology and Department of Life Science , National
Tsing Hua University, Hsinchu , Taiwan"Institute of Molecular Biology, National Chung Hsing University, Taichung , Taiwan(wcwang@life .nthu.edu.tw4

N-Acylamino acid racemase (NAAAR4 that catalyzes racemizatbn of N-acylaminoacid is valuable to produce enantiopure a -amino acids in couple with an aminoacylase .
In this investigation, NAAAR from a radiation-resistant ancient bacterium . Deinococcus
radiodurans, was cloned and overexpressed . Enzymatic ana lysis showed that theexpressed protein had NAAAR activity toward various substrates and an optimal
temperature of 60 oc. Km values were 24 .8 and 12.3 mM for N-acetyi-D-methionine andN-acetyi-L-methionine, respectively. The crystal structure of NAAAR was solved using
MAD method and refined to 1.3 A (R = 13.8%4. It reveals a tightly packed octamer and aclassical architecture of the enolase superfamily comprising a capping domain and a(pI a 4 P barrel domain. The NAAAR-Mg 2• and NAAAR NAAAR-N-acetyi-L-glutamine·Mg 2•
structures were also determined respectively. A solvent-accessible binding pocket
containing Lys170-Asp195-Giu220-Asp245-Lys269 catalytic site is thu s identified , giving
insight into the catalytic mechanism and substrate specificity.

P0136
COMPARISON OF THE STRUCTURE AND FUNCTION OF INFLUENZA
VIRUS NEURAMINIDASE AND PARAINFLUENZA VIRUS
HAEMAGGLUTININ-NEURAMINIDASE (HN)
P.M. Colman
Structural Biology Division , The Walter and Eliza Hall Institute of Medical Research , 1G
Royal Parade , Parkville , Victoria 3050 , Australia (pcolman@wehi.edu .au)

The membrane glycoproteins of parainfluenza viruses , like influenza viruses , havethree important functions in the viral life cycle ; receptor-binding (Haemagglutinin) ,membrane fusion (F) and neuraminidase (N) activity. These three functions are distributed
differently between the two membrane glycoproteins of each type of virus. Recently
described structures of the HN protein of Newcastle Disease Virus [1) and Parainfluenza
Virus type 3 [2) provide insights into the molecular basis for the dual function of themolecule (receptor binding and neuraminidase activity) and the way its activity relates to
the F protein [3,4].
ReferencesI
Crennell , S ., Takimoto , T., Portner, A. and taylor, G. (2000) Crystal structure of themultifunctional paramyxovirus hemagglutinin-neuraminidase. Nature Struct. Bioi. 7,1068-1074.
2
Lawrence , M.C., Borg , N.A. , Streltsov, V.A. , Pilling , P.A. , Epa , V.C. , Varghese , J.N.,
McKimm-Breschkin , J.L. and Colman , P.M. (2004) Structure of thehaemagglutinin-neuraminidase from human parainfluenza virus Type Ill. J. Mol.
Bioi. 335 , 1343-1357.
Chen , L. Gorman , J.J ., McKimm-Breschkin , J. , Lawrence , L.J. , Tulloch , P.A. , Smith ,3
B.J. , Colman , P.M. and Lawrence , M.C. (2001) The structure of the fusion
glycoprotein of Newcastle disease virus suggests a novel paradigm for themolecular mechanism of membrane fusion. Structure 9, 255-266.
Colman , P.M. and Lawrence , M.C. (2003) The structural biology of Type I viral4
membrane fusion . Nature Reviews Molecular Cell Biology, 4, 309-319.

P0137
STRUCTURAL INVESTIGATION OF MYCOBACTERIUM SMEGMA TIS
DPSSiddhartha Roy,a Satyabrata Das,a Surbhi Gupta , a K . Sekar,b Dipankar Chatterji• and
M. Vijayan••Molecular Biophysics Unit ; bBioinformatics Centre , Indian Institute of Science , Bangalore
560012 , India (sroy@mbu .iisc.ernet.in)
Dps (QNA binding Qrotein from §tarved cells) constitute a family of proteins that
protect DNA from oxidative damage during nutritional deprivation. Here we report thestructure of this protein from Mycobacterium smegmatis in three crystal forms [1]. The
dodecameric molecule can be described as a distorted icosahedron. The moleculeappears to have been made up of stable trimers [2] , as in the proteins from Escherichia
coli and Agrobacterium tumefaciens unlike those from other sources , which appear to froma dimer first. Trimerisation is aided in the three proteins by the additional N-terminal
stretches they possess. The M. smegmatis protein has an additional C-terminal stretch
containing basic residues . The stretch , known to be involved in DNA binding, is situatedon the surface of the molecule . Availability of the structures homologous of Dps molecules
permits a delineation of the rigid and flexible regions in the molecule. The subunit
interfaces around the molecular dyads, where the ferroxidation centres are located , arerelatively rigid. Regions in the vicinity of the acidic holes centered around molecular
threefold axes, are relatively flexible . So are the DNA binding regions . DNA molecules canoccupy spaces within the crystal without disturbing the arrangement of the protein
molecules. The DNA molecules can also be located in grooves which criss-cross the
crystal.
References1
Siddhartha Roy, Surbhi Gupta , Satyabrata Das , K. Sekar, Dipankar Chatterji and
M. Vijayan . " Crystallization and preliminary X-ray diffraction analysis of
Mycoba cterium smegmatis Dps". Acta Cryst (2003) 059 , 2254-2256.
2
Gupta , S & Chatterji , D. "Bimodal protection of DNA by Mycobacterium
smegmatis DNA-binding protein from stationary phase cells". J.Bioi.Chem . (2003)
278 , 5235-5341 .

P0138AWAY FROM THE EDGE: SAD PHASING FROM THE SULFURANOMALOUS SIGNAL MEASURED IN-HOUSE WITH CHROMIUM
RADIATION
C. Yang•, J. W. Pflugrath•, D. A. Courville•, C. N. Stence•, S. P. Williamsb, K. P. Madaussb
and J. D. Ferrara••Rigaku/MSC , Inc. , 9009 New Trails Drive , The Woodlands , TX 77381 ; bGiaxoSmithKiine ,5 Moore Drive , RTP , NC Z7709(cyang@rigakumsc.com)
Anomalous scattering with soft X-ray radiation opens new possibilities in phasing
for macromolecular crystallography. Anomalous scattering from sulfur atoms collected on
an in-house chromium radiation source (.II = Z.Z9 A) was used to phase the X-ray
diffraction data from thaumatin (ZZ kDa), trypsin (Z4 kDa) and glucose isomerase (44 kDa)
crystals. The contribution to the anomalous term , lJ.f"=1 .14 e·, from sulfur for CrK 0
radiation is doubled compared to that for CuKa radiation , lJ.f"=0.56 e·. For thaumatin andtrypsin , the direct methods programs RANTAN or SHELXD successfully found sulfur
positions using data sets with resolution limited to 3.5 A. The statistical phasing program
SHARP was able to produce interpretable electron density maps using the sulfur
anomalous signal alone at a low resolution (-3.0 - 3.5 A). Much less data , that is lower
redundancy, is required for this sulfur SAD phasing procedure compared to the highly
redundant data reported in the sulfur SAD phasing procedure with CuK 0 radiation [1 , Z] .
Glucose isomerase has a lower sulfur-amino acid ratio than that of most of proteins
resulting in a Bijvoet ratio (<lJ.F>/<F>) of only 0.6% when using CuK0 radiation . S-SAD
phasing of Gl is very difficult and has only been done using 1.54 A radiation from asynchrotron collected with high redundancy [3].
However, using CrKa radiation , theBijvoet ratio is doubled to -1 .Z% and an automatically interpretable electron density map
can be obtained at low resolution (3 .0 A) with 180° data using SOLVE/RESOLVE.
The structure of a novel protein containing 7 monomers of Z4Z amino acids eachwith 16 sulfurs per monomer has been solved using the phased molecular repla cement
method . The sulfur signal was enhanced using CrKa radiation using data collected with
only Z-fold redundancy. The methods used in solving this structure will be described.
Furthermore , CrKa radiation can also improve the strength of the anomalous signalof many other elements in macromolecules , like selenium , calcium , zinc, and phosphorus ,because of increased lJ.f" . This experimental study shows using CrK0 radiation from an
in-house rotating anode X-ray generator can provide sufficient phasing power from sulfur
anomalous signals for routinely phasing protein diffraction data. In addition , the longer
wavelength of CrKa radiation can greatly increase the in-house ability to resolve large unit
cells and enhance the diffraction power for small crystals . These indicate CrK 0 radiation
may be a good alternative to CuK 0 radiation for an in-house source and well suitable forhigh throughtput crystallography.

References
1
Yang , C & Pflugrath , J.W . (Z001)Acta Cryst. 057 , 1480-1490.
Z
Debreczeni , J. E., Bunk6czi , G., Ma , Q. , Blaser, H. & Sheldrick, G. M. (Z003)
Acta Cryst. 059 , 688-696 .
3
Ramagopal , U.A. , Dauter, M., Dauter, Z. (Z003)Acta Cryst. 059 , 10Z0-10Z7.

P0139CRYSTAL STRUCTURE OF DISINTEGRIN A DOMAIN SWAPPEDHOMODIMER FROM SAW-SCALED VIPER (ECHIS CARINATUS) AT 2.5 A
RESOLUTION
Pun it Kaur, Sameeta Bilgrami , Shailly Tomar, Savita Yadav, Janesh Kumar, Talat Jabeen ,Sujata Sharma and T. P. Singh.
Department of Biophysics, All India Institute of Medical Sciences , New Delhi 110 029 ,India (punit@aiims.aiims.ac.in)

Disintegrins are a class of small (4 - 14 kDa) proteins that bind to integrins
specifically. The binding site in disintegrins is generally characterized by the presence of
Arg-Giy-Asp motif. The present molecule has been isolated from the venom of Echis
carinatus. It exists as a homodimer interlinked by two disulfide bonds using its first two Nterminal Cys residues. The monomeric cha in contains 64 amino acid residues. The threedimensional structure of disintegrin has been determined by multiple isomorphous
replacement method. It has been refined to an R-factor of 0.191 for all the data to 2.5A
resolution. This is the first structure of a biological homodimer of disintegrin. The two
subunits of the homodimer are related by a two-fold crystallographic symmetry. Thus the
crystallographic asymmetric unit contains a monomer of disintegrin. The monomer folds
into an up-down topology with three sets of anti-parallel j3-strands . The N-terminal
anchored two chains of the dimer diverge away at their C-termini exposing the Arg-GiyAsp motif into opposite directions thus enhancing their binding efficiency. This is one of
the unique features of the disintegrin homodimer and results in clustering of the integrin
molecules. The homodimer binds to integrins and also plays a role in signaling pathway.

P0140INTRODUCTION OF THE PROTEIN DATA BANK JAPAN (PDBj)
T. Kosada ,a R. lgarashi ,"·b Y. Kengaku ,S·b S. Saeki ,"·b Y. Morita ,"·b M. Kusunoki ,"K. Kobayashi ,b A. Paehler,b N. lto ,b and H. Nakamura••Institute for Protein Research , Osaka University, 3-2 Yamadaoka, Suita-shi , Osaka 565-0871 ,Japan (kosada.117@protein.osaka-u .ac.jp); bJapan Science and Technology Agency.

The Protein Data Bank (PDB) is the sole international public repository for three
dimensional structure data of biological macromolecules and serves for supporting essential
biological sciences . Macromolecular structures in the PDB help to solve crystallographic structure
determination. Also understanding macromolecular structures will aid researchers inunderstanding how proteins work. This information could give benefits to pharmaceutical andbiotechnological industries in understanding various diseases and in developing drugs thatenables to target diseases more effectively. The PDB was established at Brookhaven National
Laboratory in 1971 . The full responsibility for the operation and enhancement of the PDB wastransferred to the RCSB (Research Col laboratory for Structural Bioinformatics. USA) in July 1999.
In 1999, the Protein Data Bank Japan (PDBj) was founded at the Institute for Protein
Research , Osaka University, to mirror a PDB site and to accept and process PDB entries in Asiaand Oceania with collaboration of RCSB. The PDBj enhances the PDB capabi lities and has
performed the following activities:
1 PDB search web site [1]. http://pdb.protein.osaka-u.ac.jp
2 FTP download site [1] . ftp://ftp.protein.osaka-u.ac.jp
3 PDB deposition site [1] . http://pdbdep. protein.osaka-u .ac.jp
4 Questions about PDB search and deposition [1]. pdbhelp@protein .osaka-u.ac.jp
5 Process and Release of Deposited entries.
6 Exploiting an XML format database[2], a 3D viewer, and secondary databases[3].
7 BioMagResBank (BMRB) Mirror site[1].
The PDBj, RCSB and MSD-EBI (Macromolecular Structure Database at the European
Bioinformatics Institute) process deposited PDB entries since 1999 in collaboration.
The PDBj, RCSB and MSD-EBI have formed the world wide Protein Data Bank (wwPDB)
on 2003[4]. The mission of the wwPDB is to maintain a single archive of macromolecular structural
data that is freely and publicly available to the global community. The legacy of the PDB format will
not be modified unless there is a compiling reason for a change.
The PDB has 23813 structures as of 07-Jan-2004 . Convenient methods of finding someentries from such many entries and the deposition method including the above list 1. to 6. will bepresented here .
Also the contribution of PDBj deposition and processing PDB entries will be shown. PDBj
processed 142, 364, 652 , and 1021 entries in 2000 through 2003 , respectively. These entries
include deposition from RCSB. 98, 139, 289, 673 entries in 2000 through 2003, respectively we redeposited at the PDBj deposition site. The number of depositions and processing through the
PDBj are increasing .
The PDBj provides timely service for users and depositors of Asian and Oceanian region
almost without considering world time difference. The PDBj would like to solicit you to deposit yourentries through the PDBj deposition site.
References
1
All PDBj sites can access through http://www.pdbj.org
Xml-based Protein Structure Search Service (xpss:http://www.pdbj.org/xpsss/).
2
3
Kinoshita , K. , Nakamura , H. (2004) Bioinformatics , in press.
4
Berman , H., Henrick , Kim. , and Nakamura , H. (2002) Nat. struct. bioi. 12, 979-1024.

P0141REFOLDING, PURIFICATION AND CRYSTALLIZATION OF APICALMEMBRANE ANTIGEN 1 FROM PLASMODIUM FALCIPARUM
Tao Bai , Aditi Gupta and Adrian H. Batchelor
University of Maryland , School of Pharmacy, Baltimore , MD , 21201 , USA(tbai001 @umaryland.edu)

Malaria is one of the leading causes of both morbidity and mortality in the tropicaland subtropical world . AMA 1 (apical membrane antigen 1) is considered to be one of thebest anti-malaria vaccine candidates. The ama1 gene is well conserved in the plasmodium
genus and partly conserved in Toxoplasma gondii and other apicomplexa. The bulk of theprotein is extracellular and separated into 3 domains on the basis of intra-domain
disulphide bonds. Limited proteolysis experiments are used to elucidate a relatively nonflexible core region of AMA 1, and refolding/purification is used to generate two fragmentsof AMA 1. Interestingly, several chromatographically distinct AMA 1 variants are identified
that are presumably differentially refolded proteins. One of these AMA 1 preparations
proves to be highly crystallizable and an unusual and yet simple crystal dehydration
method is identified that results in the generation of high resolution low ·mosaicity crystals.

P0142CRYSTAL STRUCTURE OF A NOVEL SIGNALLING GLYCOPROTEINFROM BOVINE REVEALS A NEW RECOGNITION SITE
Janesh Kumar, Jayshankar Jasti, Sujata Sharma , Bhaskar Singh , Asha Bhushan and Tej
P. Singh
Department of Biophysics , All India Institute of Medical Sciences , New Delhi-110029
Uaneshdubey@yahoo.com).

A recently discovered new fam ily of 40 kDa glycoproteins present in the dry
secretions of animals , culture supernatants of the MG-63 human osteosarcoma cell line ,cultures of human synovial cells and human cartilage cells. These proteins are implicatedas protective signalling factors that determine which cells are to survive during theprocesses of drastic tissue remodeling. The first member of this family was discovered asa prominent protein in the whey secretions of non-lactating cows. In order to develop anunderstanding of the precise roles of these proteins, a detailed three-dimensional
structure of signalling protein from cow (SPC-40) has been determined. The protein was
purified from the dry secretions of non-lactating cow. It was also cloned and sequenced .
The crystal structure was determined and refined to an R factor of 0.19 to 2.0 A resolution.
The structure shows a classical ([3a) 8 barrel fold resembling TIM arrangement. It also hasa small a+[3 domain similar to that of chitinases. However, it has no chitinase activity due
to mutations in the residues involved in chitinase activity. The structure also reveals that
SPC-40 cannot bind to saccharides I polysaccharides. The protein seems to be involvedin the recognition through protein-interactions. Overall , this protein shows a 40-50%
sequence identity with chitinases and chitinase-like proteins but lacks chitin hydrolyzing
property and carbohydrate binding capability. Thus , it might have evolved from chitinases
but has acquired new functions through specific point mutations and by altering its
mechanism of recognition.

P0143
CRYSTAL STRUCTURE OF THE SMALL FORM OF GLUCOSE-INHIBITEDDIVISION PROTEIN A FROM THERMUS THERMOPHILUS HB8
W. Iwasaki•, H. Miyatake• and K. Miki•·b•RIKEN Harima lnstitute/Spring-8, Koto 1-1-1 , Mikazuki-cho, Sayo-gun , Hyogo 679-5148,
Japan. bDepartment of Chemistry, Graduate School of Science , Kyoto University, Sakyoku , Kyoto 606-8502, Japan (wiwasaki@spring8.or.jp)

Glucose-inhibited division protein A (GidA} plays a role in !RNA modification. It isinvolved in the biosynthesis of hypermodified nucleotide 5-methylaminomethyl-2thiouridine in the wobble position of bacterial tRNAs, which stabilize codon-anticodon
interactions. The inactivation of gidA in E. coli caused a two-base translational frameshift.
The gidA gene is widely distributed and highly conserved in both prokaryotes andeukaryotes. A subset of organisms has a second gidA gene , which encodes a smaller
GidA protein (GidAsmaul· The crystal structure of GidAsmau from Thermus thermophilus HB8
has been determined at 1 .65 A resolution by the MAD method of the Hg derivative. The
crystal annealing technique was crucial for the data collection. The structure of GidAsmau
consists of two segments: domain 1 with a Rossmann fold , which is characteristic of adinucleotide binding fold , and domain 2. Although FAD was not added to the crystallization
media , it was bound to GidAsmau at full occupancy. The topology of GidAsmau satisfies thefeatures of flavoproteins , revealing FAD as a genuine cofactor of GidA. It remains
unknown whether GidA catalyzes oxidation-reduction reactions, but the structural featuresof GidAsmau strongly suggest that FAD is required for the protein to function. There are twolong inserts in GidA of conventional size, compared to GidAsmau· The structure of GidA waspredicted using the structure of GidAsmau· The two inserts are thought to create two
additional domains in GidA, which would form a catalytic site and recognize substrate!RNA.

P0144
CRYSTAL STRUCTURE OF SPHERICAL PARTICLE OF TOBACCO
NECROSIS VIRUS COAT PROTEIN LACKNG N-TERMINAL ARM AT 2.6 A
RESOLUTION
Keiichi Fukuyama ,a Shu lshitobi ,a and Kazuhiko Saeki••Department of Biology, Graduate School of Science, Osaka University, Toyonaka , Osaka
560-004 3, Japan (fukuyama@bio.sci.osaka-u .ac.jp).

Tobacco necrosis virus (TNV) is a spherical plant virus that consists of a single
stranded RNA genome (3.8kb) and 180 identical protein subunits (30 kDa). The crystal
structure of TNV determined at 2.25A resolution revealed that the subunits are arranged ina T=3 icosahedral manner [1 ,2] . At the quasi six-fold axis of the TNV particle , the Nterminal segments (arms) of the C subunits gather together to form [3 -annulus producing
hexameric association of the subunits , whereas at the five-fold axis , the arm is disordered
to give pentameric association . The arm may produce multiple ways of subunit
associations that are essential for the formation of T=3 icosahedral particles.
We expressed the truncated coat protein of TNV, which lacks the N-terminal arm(23K). The 23K protein was highly expressed in Escherichia coli, but formed inclusion
body. The protein , solubilized with urea and then refolded by dialysis, was assembled tospherical particles in the presence of calcium ion . This particle is smaller than the native
TNV particle , indicative of T=1 particle . The particles crystallized in the space group of
P4,2 12 (a=b=311 .1A, c=176 .9A) , with half of the particle in the asymmetric unit.
Its X-ray diffraction data to 2.9A resolution were collected at 1OOK with beam line
BL41 XU , SPring-S . The structure of T=1 particle was determined by the molecularrepla cement method using A subunit in the T=3 particle and refined to R factor of 19.4%.
The present analysis has revealed in detail how the subunit proteins are arranged in the
T=1 particle . Characteristics of the tertiary and quaternary structures will be presented.
References
Oda , Y. , Saeki , K., Takahashi , Y., Maeda , T. , Naitow, H., Tsukihara , T. , and1
Fukuyama , K. (2002) J. Mol. Bioi. 300 , 153-169.
Saeki , K., Takahashi , Y., Oh-oka , H. , Umeoka, T. , Oda , Y., and Fukuyama , K.
2
(2001 ) Biosci. Biotechnol. Biochem. 65 , 719-724 .

P0145X-RAY CRYSTAL STRUCTURE ANALYSIS OF A COMPLEX BETWEENCARBOXYPEPTIDASE YANDA PROTEIN INHIBITOR
Yasuo Hata ,a Minoru Hayashida," Tomomi Fujii ,a Joji Mima ,b Rikimaru Hayashi,c Yoshimi
Uedab•institute for Chemical Research , Kyoto University, Uji, Kyoto 611-0011 , Japan ; bQivision ofApplied Life Sciences , Graduate School of Agriculture , Kyoto University, Sakyo-ku , Kyoto
606-8502 , Japan ; coepartment of Food Science and Technology, College of Bioresource
Sciences, Nihon University, Kameino , Fujisawa , Kanagawa 252-8510 , Japan(hata@scl. kyoto-u .ac.jp)

The serine carboxypeptidase inhibitor in the cytoplasm of Saccharomyces
cerevisiae , IC, specifically inhibits vacuolar carboxypeptidase Y (CPY) and belongs to afunctionally unknown family of phosphatidylethanolamine-binding proteins (PEBPs) [1] .
The N-terminal amino acid residue of IC is acetylated . The N-terminal acetyl group isessential for achieving a tight interaction with CPY and for its complete inactivation of CPY[2]. It is revealed from a biochemical analysis that IC binds to CPY through multiple
interaction sites [1] . In order to elucidate the molecular mechanisms of the complex
formation between IC and CPY and the expression of the multiple functions by the PEBP
family, we have carried out X-ray crystallographic analysis of the CPY-IC complex.
IC was purified by means of a high-level expression system [3] . The purified IC exists
as a monomeric beta-protein in solution with a molecular weight of 24,400 and consists of
219 amino acid residues. CPY was treated with endoglycosidase H before preparation of
the complex with !C . CPY consists of 421 amino acid residues and the molecular weight ofthe deglycosilated CPY was 53,000. The CPY-IC complex was prepared by mixing theequal moles of CPY and !C. Crystals of the complex were obtained at 25' C by a hangingdrop vapor-diffusion method using ammonium sulfate as a precipita nt. They belonged tospace group P2 1212 1 with the unit cell dimensions of a=81.0 A, b=186.1 A, and c=64 .9 A.
The asymmetric unit of the crystal contains one CPY molecule complexed with one IC
molecule. Diffraction data were collected up to 2.9 A resolution with a Rigaku imaging
plate system R-AXIS IV using CuKa radiation from a rotating anode X-ray generator
RU-300H operated at 40kV-1 OOmA. The structure analysis of the complex is under way bya molecular replacement method using atomic coordinates of CPY (PDB code: 1YSC) as
an initial model structure.
References1
Mirna , J. , Narita, Y. , Chiba , H. and Hayashi, R. (2003) J. Bioi. Chem. 278,
29792-29798 .
2
Mirna , J., Kondo , T. and Hayashi, R. (2002) FEBS Lett. 532 , 207-210 .
3
Mirna , J. , Suzuki , H., Takahashi , M. and Hayashi, R. (2002) J. Biochem. (Tokyo) 132 ,967-973.

P0146
CRYSTALLIZATION AND PRELIMINARY X-RAY STUDY OFCARNOSINASE FROM MICE
Tetsuo Yamashita, Hirota Otani , Genji Kurisu , Masami Kusunoki , Nobuaki Okumura ,Katsuya Nagai
Institute for Protein Research , Osaka University, 3-2 Yamada-oka , Suita, Osaka
565-0871 , Japan (t.yama@protein.osaka-u .ac.jp)
Mammlian tissues contain several histidine-containing dipeptides and related peptides
such as carnosine , homocarnosine and anserine (1 ). Carnosine(l1-alanyi-L-hisitidine) is
most well characterized among these dipeptides and is present in various tissues
including the brain and the skeletal muscles(2). In the brain , a high concentration ofcarnosine is found in the olfactory epithelium and its neuronal projection to the olfactoryblub(3). Carnosine-like immunoreactivity was also found in several nuclei of the
hypothalamus including the superchiasmatic nuclei and anterior hypothalamus , indicatingthat carnosine have specific function in the olfactory and the hypothalamus.
Although carnosine is a classical dipeptide, the molecular mechanism of synthesis anddegradation remains unknown. Carnosine is hydrolyzed into r.. -alanine and L-hisitidine bya peptidase carnosinase.
We started crystallographic study of carnosinase from mice to understand its enzyme
mechanism from a structural viewpoint. The enzyme is expressed in Escherichi coli
BL21 (DE3)plysS cells as a fusion protein with glutathione-S -transferase(GST) using a
pGEX4T-3 plasmid. The GST fusion protein was purified by affinity chromatography using
a glutathione Sepharose 48 column and cleaved by thrombin. The purified enzyme wascrystallized by the hanging drop vapour diffusion method at 4 oc and crystals appeared in
2-3 days. X-diffraction diffraction data from a crystal were collected to 3.3 A resolution ona Rigaku R-AXIS IV imaging plate diffractometer with Cu Ka radiation on a Rigaku Ultra-X
18 rotating anode generator operated at 40kV, 1OOmA at 1OOK. Structure analysis isunderway.
References
Sakai M, Kani K, Karasawa N, Yoshida M, Nagatsu I. an electron
1
microscopic study. Brain Res. 1988 Jan 12; 438(1-2): 335-8 .
DeMarchis S , Modena C, Peretto P, Giffard C, Fasolo A. J Comp Neural. 20002
Oct 23 ; 426(3): 378-90 .
Yamane T, Niijima A, limori S, Tsuruoka N, Kiso Y, Nagai K. Neurosci Lett. 2001
3
Nov 2; 313(1-2): 78-82.

P0147
FACTORS THAT INFLUENCE SUCCESS IN PROTEIN CRYSTALLIZATION
Heather M. Baker,• Ivan lvanovic,• and Edward N. Baker••School of Biological Sciences , University of Auckland , Private Bag 92019 , Auckland , New
Zealand (h .baker@auckland .ac.nz).

With rapid advances in the speed and power of methods of protein structure
determination by X-ray crystallography , attention must increasingly turn to protein
expression , purification and crystallization as the main bottlenecks. Here we discuss someof the factors that influence th e success of protein crystallization efforts , from ourexperience over the past few years, including our involvement in a lab-scale structural
genomics effort. Illustrative examples are given.
Protein quality. In structural genomics projects there is a tendency to use only one
or two chromatographic steps in protein purification . However, success in crystallization isstrongly correlated with protein quality. A single band on an SOS gel may not show
microheterogeneity or aggregation . We use dynamic light scattering as a sensitive monitor
of quality , usually testing fractions across a peak . The freshness of a protein sample canalso be critical.
Crystallization screens. Many different crystallization screens have now beendeveloped. Some conditions rarely or never give crystals. We have combined current
screens with our own in-house screens to give 96-well screens suitable for robotic
crystallization.
Additives. Additives such as metal ions and detergents can alter crystallization
behaviour. In the case of the TB protein MshB good crystals were only obtained in thepresence of j3-octylglucoside , which bound both in the active site and in an intermolecularsite.
Seeding . Seeding can be performed in various ways. For the TB protein LeuA, thefirst crystallization could never be reproduced and all subsequent crystals (including the
SeMel protein) were seeded from these. For mutants of transferrin , crystals were grown
reproducibly by seeding with wild type protein .
Crystal size. Small crystals are frequently found to be more perfect. In the case of
the superantigen SpeJ , the largest crystals that could be grown had a maximum
dimension of SOp. No diffraction could be seen on a home source , but data to 1.7 A
resolution were obtained at SSRL.
Use of robotics. The use of robotic systems, and very small volumes, cansignificantly improve success [1 ,2] due to reproducibility, speed of equilibration and theability to be much more rigorous with protein quality, since smaller amounts are needed .
Our experience with nanolitre crystallization will be discussed .
References
1
Sulzenbacher, G. et at., (2002) Acta Cryst. 058 , 2109-2115.
2Page , G . et at., (2003) Acta Cryst. 059 , 1028-1037.

P0148CONCENTRATION AND CALCIUM DEPENDENT MONOMER-DIMER AND
ACTIVITY-INACTIVITY TRANSITIONS IN PHOSPHOLIPASE A.: CRYSTALSTRUCTURE OF A CALCIUM INDUCED DIMER AT 1.6 A RESOLUTION
Tala! Jabeen , Sujata Sharma , Nagendra Singh , Rajendra K. Singh , Punit Kaur and Tej P.
SinghDepartment of Biophysics , All India Institute of Medical Sciences , New Delhi -110029

Phospholipase A2 (PLA 2 ) catalyzes the hydrolysis of the 2-acyl ester bond ofphospholipids and produces lysophospholipds and fatty acids. The formation of current
heterodimer between two PLA2 isoforms from cobra venom was induced by calcium atconcentrations higher than 5 mg/ml. The dimer was crystallized in space group P4 1 with
a= b= 64 .5 A, c= 57.1 A. The structure was determined by molecular replacement method
and refined to an R factor of 0.21 for data rendering to 1.6 A resolution. Two calcium ionsare found, one intramolecularly in the calcium binding loop of molecule B and another at
the intermolecular site coordinating two molecules. The intramolecular calcium binding site
in molecule A is empty. Both calcium ions are seven-fold coordinated. The two molecules
are held with several direct intermolecular contacts at the two ends of their elongatedsurfaces. The central region between the two molecules is filled with water molecules. The
calcium binding loop of molecule A has shrunk and forms a 270 - 33 N hydrogen bond tostabilize its structure. This loop is further stabilized by interactions involving Arg 31 ofmolecule B with loop carbonyl oxygens. The two isoforms stay away at low concentrationsin the absence of calcium ions and show no activity. In the presence of calcium ions , bothisoforms are active but do not form dimers at low concentrations. At higher concentrations(>5mg/ml) and in the presence of excess calcium , they form a heterodimer and lose theiractivity. This suggests that they are stored in the inactive form in the venom and get
activated at low concentrations in the presence of calcium , a condition present in the prey.

P0149NATIVE PEPTIDES AS POTENT INHIBITORS OF SERINE PROTEASES:
CRYSTAL STRUCTURE OF A COMPLEX FORMED BETWEEN aCHYMOTRYPSIN AND ITS AUTOCATALYTICALLY PRODUCEDOCTAPEPTIDE AT 2.2 A RESOLUTION
Nagendra Singh•, Talat Jabeen•, Sujata Sharma•, lpshita Royb, M. N. Guptab, Sameeta
Bilgrami•, A. P. Baxla•, Sharmistha Dey•, Marcus Perbandtc, Ch . Betzelc and Tej P. Singh••Department of Biophysics, All India Institute of Medical Sciences , New Delhi 110 029 ,India , Department of Chemistry, Indian Institute of Technology Delhi , New Delhi 110 016 ,India, clnstitute of Medical Biochemistry and Molecular Biology, University of Hamburg, c/o
DESY , 22603, Hamburg , Germany (nagendratomar@hotmail.com)

Enzymes are involved in a wide range of biological processes providing essential
physiological inputs . At the same time their destructive roles are also well known.
Therefore , these enzymes are often secreted as inactive precursors together with thesynthesis of their proteinaceous inhibitors to prevent their activation at the unwanted site
and time. Despite these precautions they have been found associated with a number of
disease states. In order to control such undesirable roles of proteases, there is animmense to develop strong synthetic inhibitors. We have induced chymotrypsin into autohydrolyzing itself and allowed it to go on until the enzyme was completely inhibited. The
inhibited enzyme wa s crystallized and the structure of the complex has been determinedat 2.2 A resolution . The extra electron density at the binding site of chymotrypsin was
clearly interpreted into an octapeptide . The carbonyl carbon of inhibitor was covalently
linked to Ser Or in a manner exactly similar to acyl-enzyme adduct. In addition to it,
peptide formed a series of hydrogen bonds with the enzyme. It is an unprocedently strong
complex. The binding studies confirmed these observations with a binding constant of 1.2
x 10·' 2 M. The overall structure of enzyme is similar to its native structu re indicating that noconformational change occurred upon complex formation.

P0150ANAEROBIC AND AEROBIC STRUCTURES OF FERREDOXIN II FROMDESULFOV/BR/0 GIGAS REVEAL ELECTRON TRANSFER MECHANISM
Chun-Jung Chen ,ac Yin-Cheng Hsieh ,b Ming-Yih Liu ,d and Jean LeGalld•Biology Group , National Synchrotron Radiation Research Center, Hsinchu 30077 ,Taiwan ; "Institute of Bioinformatics and Structural Biology; coepartment of Physics,
National Tsing-Hua University, Hsinchu 30077 ; dQepartment of Biochemistry andMolecular Biology, University of Georgia , Athens , GA 30602, U. S. A.
(cjchen@nsrrc. rog .tw)Ferredoxin II (Fd II) is a small electron transfer protein , isolated from the strict
anaerobic sulfate-reducing bacterium , Desulfovibrio gigas. The protein contains 58 aminoacids and an iron-sulfur cluster.
The cluster [3Fe-4S] spontaneously undergoes
conversion to [4Fe-4S] when it is used as an electron mediator in the phosphoroclastic
reaction. This two-form interconversion appears to have physiological significance. We
have recently obtained both aerobic and anaerobic Fd II crystals in the high-resolution
quality. Both structures are independently determined by the iron single-wavelength
anomalous dispersion (Fe-SAD) method using synchrotron radiation X-ray.
The structure of aerobic Fd II has been refined to 0.9 A ultra-high resolution in thespace group P2 1 2 1 2. Its [3Fe-4S] cluster is bound with Cys8 , Cys14 , and Cys50 , whereas
Cys 11 extends away from cluster. Cys 18 and Cys42 form a disulfide bridge to maintainthe protein folding. Five isolated Zn 2 • ions around the protein are located and bound with
Glu , Asn and Asp , respectively, which indicates the transition metals , other than iron ,could be incorporated into [3Fe-4S] center. On the other hand , the anaerobic Fd II
structure from the crystals grown under anaerobic condition has also been refined to 1.4 A
resolution in the different space group C222 . The anaerobic structure shows the different
iron-sulfur cluster and disulfide bridge conformations as well as crystal packing. Here we
present the structure comparison between aerobic and anaerobic Fd II at ultra-highresolution which reveals the unique iron-storage function and electron transfer mechanismof ferredoxin II from Desulfovibrio gigas.

P0151CRYSTAL STRUCTURE OF CHORISMATE SYNTHASE: A NOVEL FMNBINDING FOLD AND FUNCTIONAL INSIGHTS
Se Won Suh and Hyung Jun Ahn
Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul
151-742, Korea (sewonsuh@snu.ac.kr)

Chorismate synthase catalyzes the conversion of 5-enolpyruvylshikimate 3phosphate to chorismate in the last step of the shikimate pathway. Chorismate serves as acommon precursor for the synthesis of aromatic amino acids and many aromaticcompounds in microorganisms and plants. This makes chorismate synthase an attractive
target for discovering antimicrobial agents and herbicides. Chorismate synthase requires
reduced FMN as a cofactor but the catalyzed rea ction involves no net redox change.
Chorismate synthase from He/icobacter pylori is a homotetramer of 365-residue
subunit. We have determined its crystal structure in both FMN-bound and FMN-free forms[1 ,2]. Each monomer possesses a novel FMN-binding protein fold , " ~-a-~ sandwich fold. "Highly conserved regions, including several flexible loops, cluster together around thebound FMN to form the active site. The unique FMN-binding site is formed largely by asingle subunit, with a small contribution from a neighboring subunit. Most part of thecofactor is bound deeply within the protein. We have modeled the su bstrate binding to there-face of the isoalloxazine reing of FMN.
References
1
Ahn , Yoon , Lee , and Suh (2004) J. Mol. Bioi. 336 , 903-915.
2Ahn, Yang , Lee , Yoon , Kim, and Suh (2003) Acta Cryst. 059 , 569-571.

P0152PROBING THE DNA KINK STRUCTURE INDUCED BY THE
HYPERTHERMOPHILIC CHROMOSOMAL PROTEIN SAC7D USING SITEDIRECTED MUTAGENESIS AND X-RAY CRYSTALLOGRAPHY
Chin-Yu Chen•. c. Ting-Wan Lin•, Chia-Cheng Chou•.b, Tzu-Ping Ko•, and And rew H.-J .
Wanga.d•Institute of Biological Chemistry and bCore Facility X-ray Crystallography, Academia
Sinica , Taipei 115, Taiwan ; cDepartment of Chemistry and dlnstitute of Biochemical
Sciences , National Taiwan University, Taipei 106, Taiwan .(cutecoca@gate.sinica.edu.tw)

Sac7d is a small , abundant, non-specific DNA-binding protein of thehyperthermophilic archaean Sulfolobus acidocaldarius. Sac7d causes a single-step sharp
kink in DNA (-60°) via the intercalation of both Val26 and Met29. In this paper, Val26 andMet29 were systematically changed to either smaller or larger sizes to probe their effects
on the kink site in DNA. The crystal structures of five Sac7d mutants (V26A, M29A,
V26A/M29A, M29F and V26F/M29F) in complex with GCGATCGC (or GTAATTAC) havebeen analyzed at high resolution (1.45 A- 2.25A). The DNA binding pattern of the V26A
and M29A single mutants is similar to that of the wild type, whereas the V26AIM29A
protein binds DNA without side chain intercalation resulting in a smaller overall bending of
helix (-50°). The M29F mutant uses the Phe29 side chain to the C2pG3 step orthogonallywithout stacking with base pairs , yet inducing a sharp kink (-80 °). In the V26F/M29FGCGATCGC complex, Phe26 intercalates deeply into DNA bases by stacking with G3base, whereas the side chain of Phe29 is stacked on the G15 deoxyribose.
Thermodynamic studies show that all mutants still bind to DNA, but with weaker affinity.
The DNA kink patterns caused by different binding combinations of hydrophobic side
chains may be relevant in understanding the manner with which other minor groove
binding proteins interact with DNA.

P0153
SECONDARY BINDING SITE OF TRYPSIN REVEALED BY CRYSTALSTRUCTURE OF TRYPSIN-OVOMUCOID INHIBITOR COMPLEX
B. Syed Ibrahim and Vasantha Pattabhi
Department of Crystallography and Biophysics , University of Madras, Guindy Campus ,Chennai 600 025 , India (b_syed_ibrahim@yahoo.com).
Crystal structure of trypsin-kazal type ovomucoid turkey egg white inhibitor(OMTKY2) complex has been determined at 1.9A resolution. Though the entire inhibitor
was used for complexation and crystallization , only second domain is bound to trypsin ,inhibiting its activity, suggesting that other domains have been hydrolyzed by trypsin.
OMTKY2 exhibits the canonical Kazal-type fold and the reactive site residue Lys 25
interactions are similar to other trypsin -inhibitor complexes. The crystal structures of thesecond and third domain of the inhibitor are similar with a central a-helix and a short twostranded anti parallel ~sheet.
A heptapeptide fragment from the first domain is bound at the interstitial region of
the crystal and interacts with both trypsin and the inhibitor. This binding site which is asecondary binding site of trypsin is similar to ecotin binding site in trypsin-ecotin complex.
Crystal structures of peptide complexes with porcine ~ -trypsin solved by us suggested that
peptides bind the active site of trypsin if a Lys/Arg is present in the sequence or else theybind at the interstitial region . Peptide interactions with trypsin will be discussed in details.

P0154
CRYSTAL STRUCTURE OF THERMOSTABLE LIPASE FROMSPECIES OF GEOBACILLUS STRAIN T1

NEW

Raja Noor Zaliha Raja Abd . Rahman :· Takahiko Yamamotob ,b Leow Thean Char, Abu
Bakar Salleh ! Mahiran Basri ,a Kazufumi Takano ,c Shigenori Kanaya ,c Hiroyoshi
Matsumura ,b Tsuyoshi lnoue ,b and Yasushi Kai"
aEnzyme and Microbial Technology Research , Faculty of Science & Environmental
Studies , University Putra Malaysia , 43400 UPM, Serdang , Selangor, Malaysia ,bDepartment of Materials Chemistry, Graduate School of Engineering , Osaka University,
2-1 , Yamada-oka, Suita, Osaka, Japan , 565-0871 , coepartment of Material and Life
Science, Graduate School of Engineering , Osaka University, 2-1 , Yamada-oka , Suita ,Osaka , Japan , 565-0871 (rnzaliha@fsas.upm.edu .my)A new species of Geobacillus strain T1 was shown to produce a thermostable
lipase (1]. The gene encoding T1 lipase was cloned , sequenced and expressed. Purified
enzyme displayed a temperature optimum and pH of 70°C and pH 9, respectively. The
mature enzyme was successfully crystallized within 24 h by hanging-drop vapor-diffusion
method at 20°C. Crystals of T1 lipase were flash-frozen in N2 stream at -180°C and X-ray
diffraction data were collected at SPring-S BL44XU , Japan . They diffracted to 1.8 A
resolution and belonged to C2 space group with cell parameters of a = 117.31 A, b =81.04 A, c =99.22 A, and (J = 96.91 °. Structure determination was preceded by molecularreplacement using Bacillus stearothermophi/us P1 lipase structure as a search model.
Structure of T1 lipase as in P1 lipase structure , in a closed conformation , has its active
site buried under a long lid helix .
Reference
1
Leow, T. C. , Rahman , R. N. Z. A. , Basri , M. and Salleh , A . B. (2004) High level
expression of thermostable lipase from Geobacillus sp. Strain T1 . Biosci ,Biotechnol ,. 68: 96-103

P0155STUDIES ON THE CRYSTAL STRUCTURE AND FUNCTION OF
CUCURMOSIN, A RIBOSOME-INACTIVATING PROTEIN FROMSARCOCARP OF CUCURBITA MOSCHA TA
Minq-Huang Chen ,a Shan Liu ,a· b Zhi-Ren Wang ,a Liqing Chen•· c•State Key Laboratory of Structural Chemistry, Fjian Institute of Research on the
Structure of Matter, The Chinese Academy of sciences, Fuzhou , Fujian , 350002 , P.R.
China ; bLanzhou University, Lanzhou , Gansu , 730000 , P.R. China ; cLaboratory for
Structural Biology, Department of Chemistry, Graduate Programs of Biotechnology,~hemistry and Materials Science , University of Alabama in Huntsville, Huntsville,
AL35899 , USA (cmh@ms.fjirsm .ac.cn).

The flesh of the fruit of Cucurbita moschata contains a type-1 ribosome-inactivating
proteins (RIPs) [1 ,2], which we named cucurmosin. Cucurmosin was purified to apparent
homogeneity by acid fractionation , and ion-exchange chromatography. The protein was
found to have a molecular mass of 27kDa and contains glycosidic linkages. The
cytotoxicities of cucurmosin on human leukemia K562 and rat melanoma B16 cells were
determined , which suggests potential promising roles of cucurmosin in treating somecancers or using as an efficient moiety of immunotoxins. The N-terminal amino acidsequence of cucurmosin determined up to residue 26 was compared to the sequences ofseveral other RIPs . The percentages of identical residues in comparisons with pepocin (aRIP from Cucurbita pepo) , trichosanthin (a RIP from Trichosanthes kirilowii) , ricin A chain(a type-2 RIP from Ricinus communis) , were 95%, 69.2% , and 40%, respectively.
Cucurmosin has been crystallized using polyethylene glycol as a precipitant. The
crystals belong to space group P212 121 with cell parameters a=41.5A, b=58.4A, andc=99.3A [3). A data set to 1.0A resolution was collected with synchrotron source. The
molecular replacement calculations using trichosanthin as the search model yielded astrong , unambiguous solution [4) . The preliminary refinement of this solution against
1.65A cucurmosin data drove the R factor down to 0.312 , confirming the high degrees ofsequence and structural homology between the cucurmosin and trichosanthin . Initialinspection of the composite omit map calculated by omitting no more than 5% of the total
structure each time showed that the high resolution map is so good that it will allow direct
amino acid sequence determination of cucurmosin. We are currently using the map to
guide side chain identification. Further model fitting/refinement is in progress.
We are grateful for financial support from the National Natural Science Foundation ofChina , Natural Science Foundation of Fujian Province, and International Cooperation
program of Fujian Province , China.
References
1 Van Damme EJ .M ., Hao Q., Chen Y. , Barr A. , Vandenbussche F., Desmyter S. , Rauge
P. , Peumans WJ . (2001) Critical Reviews in Plant Sciences. 20 , 395-465
2 Chen MH. , Shi XL. , Ye XM ., Xie JM. , Zhao R. , Rao PF ., Wang ZR. (2004) Chinese J.
Struct. Chem . 23 , 232-235
3 Chen MH. , Ye XM ., Cai JH , Lin YJ. (2000) Acta Cryst. 056,665-666
4 Shi XL ., Zhan EX. , Ye XM. , Meehan EJ. , Chen MH. , Chen LQ . (2003) Chinese J. Struct.
Chem. 22, 165-168

P0156
CRYSTAL STRUCTURE OF INORGANIC PYROPHOSPHATASE FROMHEL/COBACTER PYLORI
Y.-J. Sun , T.-C. Chao , C.-Y. Huang, and H.-M. Huang
Institute of Bioinformatics and Structural Biology, National Tsing Hua University, Hsinchu
300 , Taiwan , ROC (yjsun@life .nthu .edu.tw)

Inorganic pyrophosphatases (PPase) catalyze the hydrolysis of pyrophosphate(PPi) to orthophosphate (Pi) and controls the level of PPi in the cell. PPases play anessential role in the energy conservation and provide the energy for many biosynthetic
pathways. PPases have been found in many organisms from bacteria to human . H. pylori
PPase was isolated from Helicobacter pylori with molecular weight of 20 kD. The crystal
structure of H. pylori PPase has been solved and refined to an R-factor of 21 % at 1.9 A.
The three-dimensional structure of H. pylori PPase is composed of two extended a-helices
and eight (3-strands and form a barrel structure . The oligomeric structure of H. pylori
PPase is a hexamer in crystal and solution states.

P0157AVAILABILITY OF THE X-RAY DATA COLLECTED WITH A CRROTATING-ANODE FOR PHASING PROTEIN CRYSTALS
Takashi Yamane ,• Atsuo Suzuki ,a Seiji Okazaki ,a Hideki Tanizawa ,a Tatsuo Hikage ,bVenkatachalam Rajakannan ,c Devadasan Velmurugan ,c and Kanagaraj Sekard•Department of Biotechnology, School of Engineering , Nagoya University, Nagoya
464-8603 , Japan ; bHigh Intensity X-ray Laboratory, Nagoya University, Nagoya 464-8603 ,Japan; cOepartment of Crystallography and Biophysics , University of Madras, Chennai
600025 , India; dBioinformatics Centre , Indian Institute of Science , Bangalore 560012 ,India. (yamane@hix.nagoya-u .ac.jp).

In the recent years , the use of longer X-ray wavelength (A.= 1.5 - 2 .6 A) has become
popular in macromolecular crystallography[1 , 2]. The main reason for this is that theanomalous signal of sulfer (S) can be significantly obserVed . The enhanced anomalous S
signal in single-wavelength anomalous dispersion experiments (S-SAD) relies on the S
atoms naturally occurring in proteins. Therefore the use of S-SAD may decrease the load
to search heavy atom derivatives to all protein crystals. In order to demonstrate theavailability of S-SAD , the data collection using a Cr rotating-anode system was carried out.
The highly redundant data of the proteinase K and phospholipase A 2 (PLA2) crystals
were collected using Rigaku FR-E generator (power 40 KV x 40 mA, focus size 70 x 800
J.lm 2 ) with a chromium rotating-anode (!,= 2.29 A at Cr Ka) and Rigaku R-AXIS VII IP
detector system at High Intensity X-ray laboratory, Nagoya University.
The crystals of Proteinase K from Tritirachium album belong to the tetragonal system ,P4 3 212, a=67 .78 , c=1 01 .92 A. A total of 168,650 reflections up to 2.3 A resolution werecollected and processed using the combination of DENZO/SCALEPACK, in which uniquereflections were 11 ,106 and Rmerge= 0.067 . The anomalous Patterson map clearly
showed the Ca-Ca peak. However S-S peaks , a primary objective , could not assigned in
the map.
The crystals of PLA2 from bovine pancreas belong to the trigonal system , P3 1 21 ,a=46 .2, c=1 01 .4 A. A total of 89 ,573 reflections up to 2.4 A resolution were processedusing the combination of OENZO/SCALA , in which unique reflections were 5,303 ,Rmerge= 0.041 and Ranom=0.030 . Owing to the relatively strong absorption effects,
scaling is essential for producing the best anomalous difference pairs. The performanceof DENZO/ SCALA seems to be better as considering Rmerge. The PLA2 structure wasrefined to Rc=0 .211 and Rfree=0.249 using CNS at 2.3 A resolution . The residues 62-67
are disordered as same as the other structures of bovine pancreatic PLA2 , except for the
monoclinic form [3] . The current model contains one Ca ion and 85 water molecules. The
search of S positions and phasing is underway.
References
M.S . Weiss et al. (2001) Acta Crystallogr. 057 , 689-695 .
1
2
U. A. Ramagopal , M. Dauter & Z. Dauter (2003) Acta Crystallogr. 059 , 1020-1027.
3
V . Rajakannan et al. (2002) J. Mol. Bioi. 324 , 755-762.

P0158FIRST DETERMINATION OF THE INHIBITOR COMPLEX STRUCTURE OF
HUMAN HEMATOPOIETIC PROSTAGLANDIN D SYNTHASE
Yuji Kado," Tsuyoshi lnoue ,"·b Yousuke Okano ," Kousuke Aritake ,c Daisuke lrikura ,cNobuko Uodome ,C Nobuo Okazaki," Shigehiro Kinugasa ," Hideyuki Shishitani ," Hiroyoshi
Matsumura ," Yasushi Kai ,a and Yoshihiro Urade ,c•Department of Materials Chemistry, Graduate School of Engineering , Osaka University,
Suita , Osaka 565-0871 , Japan ; bStructure and Function of Biomolecules Group ,PRESTO , Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi , Saitama ,Japan; and coepartment of Molecular Behavioral Biology, Japan Science and Technology
Corporation , Osaka Bioscience Institute, Osaka 565-0874 , Japan(kado@chem.eng .osaka-u .ac.jp ).

Hematopoietic prostaglandin (PG) D synthase (H-PGDS) is responsible for the
production of PGD 2 as an allergy or inflammation mediator in mast and Th2 cells [1 ,2] . We
determined the X-ray structure of human H-PGDS complexed with an inhibitor, 2-(2'benzothiazolyl)-5-styryl-3-(4 '-phthalhydrazidyl) tetrazolium chloride (BSPT) [3] at 1.9A
resolution in the presence of Mg2•.
The styryl group of the inhibitor penetrated to the bottom of the active site cleft, andth e tetrazole ring was stabilized by the stacking interaction with Trp1 04 , inducing large
movement around the a5-helix , which caused the space group of the complex crystal tochange from P2 1 to P1 upon binding of BSPT. The phthalhydrazidyl group of BSPT
exhibited steric hindrance due to the cofactor, glutathione (GSH), increasing the /C50 valueof BSPT for human H-PGDS from 36 .2 JJM to 98 .1 JJM upon binding of Mg 2•, because theKm value of GSH for human H-PGDS was decreased from 0.60 JJM in EDTA to 0 .14 JJM in
Mg2•.
We have to avoid steric hindrance of the GSH molecule that was stabilized byintracellular Mg 2• in the mM range in the cytosol for further development of structurebased anti-allergic drugs.
References
1
Lewis , R.A. , Soter, N.A., Diamond , P.T., Austen , K.F. , Oates , J.A. , andRoberts ,L.J., 2nd (1982) J lmmunol. 129, 1627-1631
2
Nagata , K, Tanaka , K. , Ogawa , K. , Kemmotsu , K., lmai , T ., Yoshie,
0. , Abe , H ., Tada , K. , Nakamura , M., Sugamura , K. , and Takano , S. (1999) J.
lmmunol. 162, 1278-1286
3
Kanaoka , Y ., Ago , H., lnagaki , E., Nanayama , T., Miyano , M., Kikuno , R. , Fujii , Y. ,Eguchi , N., Toh , H., Urade, Y., and Hayaishi , 0 . (1997) Ce//90
1085-1095

P0159
THE NEW MACROMOLECULE CRYSTALLOGRAPHY BEAMLINE 3W1A
AT BSRF
Peng Liu , YuHui Dong , Sheng Huang , DeQiang Yao , DingChang Xian
BeiJing Synchrotron Radiation Facility, Institute of High Energy Physics , Academia Sinica ,19 Yu Quan Lu Beijing 100039, People's Republic of China(liup@mail.ihep.ac.cn)

A new X-ray macromolecule crystallographic beamline is operational at the Beijing
Synchrotron Radiation Facility. The beamline has been built up in 2002 and used since2003 . The radiation source is a 1.42 multipole wiggler. The wavelength range is0.77-2 .07A with a measured flux of more than 10 11 photons s-' in 1mm x 0.5mm at the
sample position . The energy resolution is better than 4 x 1O-< and multi-wavelength
anomalous diffraction experiment can be done .. The station is currently equipped with a
Mar345 imaging plate and a MarCCD165 detector. Hundreds of protein samples havebeen measured and several important results have been attained .

P0160CRYSTAL STRUCTURE OF A DISSIMILATORY NITRITE REDUCTASE
FROM HYPHOMICROBIUM DENITRIFACANS
Yong Xie , Tsuyoshi Inoue, and Yasushi Kai
Department of Materials Chemistry, Graduate School of Engineering , Osaka University.
2-1 , Yamada-oka , Suita , Osaka , 565-0871 , Japan(xieyong@chem.eng.osaka-u.ac.jp)

Dissimilatory nitrite reductase (NIR) is catalyzing one electron reduction of nitrite tonitric oxide in the denitrification press , leading to a significant loss of fixed nitrogen fromterrestrial environment. NIRs isolated from some prokaryotic organisms are containing
type-1 Cu ion and type-11 Cu ion. In present, the nature of the catalytic copper and theconversion of N0 2· to NO into NIR molecule had been reported. However, NIR accepts
electron donated from its redox partner (pseudoazurin or azurin) to accomplish oneelectron reduction of N0 2• to NO . The interaction between NIR and its specific electrontransfer partner is still not established . A novel NIR from Hyphomicrobium denitrifacans(HdNIR) , the structure is homologue of complex of reported NIR and its electron transfer
partner was characterizedl11. The interaction between N-terminal domain and C-terminal
domain resemble known NIR and its electron transfer partner. In this study,
crystallographic studies of HdNIR are carried out to describe the interaction . HdNIR and amutation form C260A, which is loss a Cu ion in C-terminal was crystallized with same
conditions. Crystal of HONIR belong to tetragonal space group P4 1 (or P4 3 ) , with the cellparameter is a = 221.91 , c = 165.15 (A), 18 molecules per asymmetric unit. In contract,
two types crystals of C260A mutation were obtained , the one crystal of mutant HONIR
belong to tetragonal space group P4 , (or P4 3 ) , with the cell-parameter is a 221.32 , c
163.11 (A), 18 molecules per asymmetric unit, and the one belonged to cubic space group
P4 232 , with the cell- parameter is a = 154.55 (A), 1 molecule per asymmetric unit. MADdata from the cubic crystal were collected to 3.0 A. MAD method was used to solve thestructure of HdNIR. The first electron density map (Figure 1) was calculated using
program CNS. Molecule modeling is carried out based the electron density map.

=

Reference
1 Deligeer, et al. , (2002) J. lnorg. Biochem. 91 , 132-138=

P0161CRYSTAL STRUCTURE OF THE SHANK PDZ-LIGAND COMPLEXREVEALS A CLASS I PDZ INTERACTION AND A NOVEL PDZ-PDZ
DIMERIZATION
Y. J. lm , J. H. Lee , S. H. Park , S. J. Park, S. H. Rho, G. B. Kanq , E. Kim and S. H. Eom
Department of Life Science , Kwangju Institute of Science and Technology, Gwangju
500-712 , South Korea . (gbkang@kj ist.ac. kr)
The Shank/proline-rich synapse-associated protein family of multidomain proteins is
known to play an important role in the organization of synaptic multiprotein complexes . For
instance , the Shank PDZ domain binds to the C termini of guanylate kinase-associatedproteins , which in turn interact with the guanylate kinase domain of postsynaptic
density-95 scaffolding proteins. Here we describe the crystal structures of Shank1 PDZ in
its peptide free form and in complex with the C-terminal hexapeptide (EAQTRL) ofguanylate kinase-associated protein (GKAP1a) determined at 1.8- and 2.25-A resolutions ,respectively. The structure shows the typical class I PDZ interaction of PDZ-peptide
complex with the consensus sequence -X-(Thr/Ser)-X-Leu . In addition , Asp-634 within the
Shank1 PDZ domain recognizes the positively charged Arg at -1 position and hydrogenbonds , and salt bridges between Arg-607 and the side chains of the ligand at -3 and -5
positions contribute further to the recognition of the peptide ligand . Remarkably, whether
free or complexed , Shank1 PDZ domains form dimers with a conserved beta B/beta Cloop and N-terminal beta A strands , suggesting a novel model of PDZ-PDZ
homodimerization . This implies that antiparallel dimerization through the N-terminal beta A
strands could be a common configuration among PDZ dimers. Within the dimeric
structure , the two-peptide binding sites are arranged so that the N termini of the boundpeptide ligands are in close proximity and oriented toward the 2-fold axis of the dimer.
Th is configuration may provide a means of facilitating dimeric organization of PDZ-target
assemblies.
Reference
1
Sheng , M ., and Kim , E. (2000) J Cell Sci. 113, 1851-1856
2
Boeckers , T. M., Beckmann , J. , Kreutz, M. R., and Gundelfinger, E. D. (2002)
J Neurochem. 81 ,903-910

P0162

THE STRUCTURE OF IMPORTIN-f3 BOUND TO SREBP-2 : INSIGHTSINTO NUCLEAR TRANSPORT OF A TRANSCRIPTION FACTOR
Soo Jae Lee ,"b Toshihiro Sekimoto ,b Eiki Yamashita ," Emi Nagoshi ,b Atsushi Nakagawa ,"Naoko lmamoto ,b Masato Yoshimura ," Hiroaki Sakai ," Khoon Tee Chong ," Tomitake
Tsukihara•· and Yoshihiro Yonedab·•institute for Protein Research and bDepartment of Frontier Biosciences , Graduate Schoolof Frontier Biosciences, Osaka University Yamadaoka 2-2 , Suita , Osaka 565-0871 , Japan(tsuki@protein .osaka-u.ac.jp)
SREBP-2 is a member of the SREBP family of transcription factors that aresynthesized as precursor molecules , which are bound to the endoplasmic reticulum (ER)membrane and the outer nuclear envelope. When cells are deprived of cholesterol , SCAP
escorts SREBPs to the Golgi apparatus , where they are proteolytically processed toliberate a transcriptionally active N-terminal fragment of 480 residues . This fragment
enters the nucleus and activates the transcription of genes that control the synthesis anduptake of cholesterol and unsaturated fatty acids . Transport of molecules into and out of
the nucleus is mediated by the importin- ~ superfamily. lmportin- ~ plays a role intransporting both cargo that carries a classical nuclear localization signal and cargo withno obvious signal sequence . lmportin- ~ recognizes classical NLS-containing proteins via
the adaptor molecule importin-a. Crystal structures have been demonstrated for importincomplexed with cargo molecules [1 ,2], with RanGTP[3], with an FG repeat nucleoporin[4] ,and in the free form[5] . However, how importin- ~ directly recognizes the active form oftranscription factors such as Smad3 and SREBP-2 remained unknown.
We determined a 3.0 A resolution X-ray structure of the complex of full-length 876
amino acid importin- ~ and a dimer of the SREBP-2 HLHZ region comprising residues
343-403 [6] . The binding site for the SREBP-2 dimer is completely separated from thosefor importin-a . The SREBP-2 dimer binds between th e long heat repeats 7 and 17 ofimportin- ~ . whereas importin-a binds in the concave face of the importin- ~ C-terminal half.
The HLHZ dimer is inserted into the importin- ~ superhelix at an orientation perpendicular
to the central axis of the superhelix, while the importin-a IBB domain is parallel to thecentral axis.
References
1
G. Cingolani eta/., Nature 399 , 221-9 (1999).
G. Cingolani eta/. , Mol Cell 10, 1345-53 (2002).
2
3
I. R. Vetter et a/. , Cell 97 , 635-46 (1999) .
R. Bayliss eta/., Cell 102, 99-108 (2000).
45S. J. Lee eta/., J Mol Bio/302 , 251-64 (2000) .
6
S. J. Lee eta/. , Science 302 , 1571-1575 (2003).

P0163

MOLECULAR REPLACEMENT SOLUTION FOR AN ACYLPHOSPHATASEFROM PYROCOCCUS HOR/KOSH/1
Yuk-Yin Cheung and Kam-Bo Wong
Department of Biochemistry, The Chinese University of Hong Kong(kbwong@cuhk.edu.hk)

Acylphosphatase (AcP) catalyzes the hydrolysis of carboxyl-phosphate bond. We
have cloned the AcP gene from a hyperthermophilic archaean Pyro coccus horikoshii andexpressed the protein in E. coli. This thermophilic AcP is extremely thermostable , which
resists denaturation at > 90°C . To understand the structural basis of thermostability, we
aim to determine its structure by crystallography. Crystals for diffraction data collection
were grown using the sitting-drop vapor-diffusion method at 298K using sodium formate
as a precipitant. Hexagonal crystals grew to maximum dimensions of 0.3 x 0.3 x 1 mm in 2
days. An entire date set diffracting to 1.6 A resolution was collected from a single crystal
at 100 K. The crystals belong to the space group P3 2 21 , with unit-cell parameters
a=b=85.65, c=75.51 A. Molecular replacement was performed using the crystal structureof bovine AcP as the search model (pdb code = 2ACY). No obvious solution was obtained
when polyserine, polyalanine , and all-atom models were used. A clear solution was
obtained only when an improved search model based on sequence alignment was used .
An in-house written PERL script, ALIGN4MR , was used to create the improved searchmodel (http://smart.bch.cuhk.edu.hk/kbwong/align4mr.htm). Two molecules of AcP were
found in the asymmetric unit, with a corresponding crystal volume per protein mass of 3.9
A Da-1 and a solvent content 68.6 %.

P0164
CRYSTALLIZATION, DIFFRACTION AND MOLECULAR REPLACEMENT
OF A NOVEL ORANGE FLUORESCENT PROTEIN FROM CERIANTHUS
SP
Denis T.M. lp , David C.C. Wan , and Kam-Bo Wong
Department of Biochemistry , The Chinese University of Hong Kong(kbwong@cuhk.edu.hk)

A novel orange fluorescent protein , with excitation and emission maxima at 548
and 565 nm , from Cnidaria tube anemone Cerianthus sp. , has been cloned andoverexpressed in Escherichia coli. Hexagonal crystals of recombinant OFP was grown bysitting-drop vapor-diffusion method at 290K using 10% (w/v) polyethylene glycol PEG
3350 , 0.1M NH 4 F [1] . A complete set of diffraction data was collected to 2.0 A resolution at
1 OOK. The crystals belong to space group R3 , with hexagonal unit-cell parameters
a=b=216.947 , c=51.839 A. The crystal structure of the blue coral pigment protein (PDB
code 1mou [2]) was used as a search model for molecular replacement. A solution withfour protein molecules per asymmetric unit was obtained.
References
1
lp , D.T.M ., Chan , S.H ., Allen , M.D. , Bycroft, M., Wan , D.C.C., and Wong , K.B.
(2004) Acta Crystallogr. D 68 , 343-341.
Prescoll , M. , Ling, M. , Beddoe , T. , Oakley, A.J. , Dove , S., Hoegh-Guldberg ,20 ., Devenish , R.J ., and Rossjohn , J. (2003) Structure , 11 , 275-284.

P0165APPLICATIONS OF ACORN TO ATOMIC RESOLUTION DATA ITRUNCATED DATA AT 1.5 A RESOLUTION OF CATALASE (-57 kDa)
S. Selvanayagam ,a D. Velmurugan ,a and T. Yamane ,baDepartment of Crystallography & Biophysics , University of Madras, Guindy Campus ,Chennai - 600 025, India; bDepartment of Biotechnology and Biomaterial Science,
Graduate School of Engineering , Nagoya University, Furo-cho , Chikusa-ku, Nagoya
464-8603 , Japan (s_selvanayagam@rediffmail.com).

One of the main interests in the molecular biosciences is in understanding structure
function relations and X-ray crystallography plays a major role in this. ACORN program
can be used as a comprehensive and efficient phasing procedure for the determination ofprotein structures when atomic resolution data are available. This can also be used tolocate the heavy atoms when data at atomic resolution are available . Reliable phases canalso be developed from a fragment composed of a small percentage (less than 5%) of thescattering matter of the unit cell[1] . Attempts are here made in extending its applications tothe structure elucidation of Catalase[2] of approximately 57 kDa molecular weight using
atomic resolution data (for ab initio phasing) . With the truncated at 1.5 A resolution,different fragments of helices and sheets from the model solved by macromolecular
crystallographic means were used as input to ACORN program and the complete model
was arrived in all cases. The minimum input phasing requirement was about 15%. The
phases obtained from ACORN were of superb quality to allow automated model building
to be carried out by ARP/wARP[3] . Minimal manual model building was required and thestructure determination was completed using maximum likelihood refinement program
REFMAC[4]. At present we use only the fragments (helices and sheets) from the same
PDB (1gwe). In all the successful attempts the connectivity index was greater than 0.95
and R and Rfree were nearly 16 and 18%, respectively. The final model had an r.m.s
deviation of nearly 0.03 when the main chain atoms of the model are superposed with
PDB entry (1gwe). Data mining approach to feed the input fragments using the PDB
entries is in progress.
References
1
Yao , J. (2002). Acta Cryst. 059, 1941-1947
2
Murshudov, G. N. , Grebenko , A. 1. , Brannigan, J. A. , Antson , A. A.,
Barynin , V. V., Dodson , G. G., Dauter, Z., Wilson , K. S. & Melik-Adamyan,
W . R. (2002). Acta Cryst. 058, 1972-1982.
3
Perrakis , A ., Morris, R. M. & Lamzin , V. S. (1999). Nature Struct. Bioi. 6,
458-463.
4
Murshudov, G. N., Lebedev, A. , Vagin, A. A., Wilson , K. S. & Dodson , E.
J. (1999) . Acta Cryst. 055,247-255 .

P0166
STRUCTURAL BASIS OF NLS- BINDING SPECIFICITY OF IMPORTIN a
ISOFORMS
S. N.Y. Yang ,• J. Harrisb and B. Kobe• c•Department of Biochemistry, University of Queensland, St. Lucia 4072 , Australia
bSchool of Life Sciences , Queensland University of Technology, Brisbane 4001 , Australia<Institute for Molecular Bioscience , University of Queensland , St. Lucia 4072 , Australia(s4006004@student.uq.edu.au)lmportin a is a nuclear import receptor that recognizes cargo proteins, which containclassic nuclear localization sequence (NLS), and facilitates their transport into the nucleus.
Several isoforms of importin a exist in higher eukaryotes , which can be grouped into threesubfamilies. In order to investigate the structural basis of the NLS - binding specificity ofhuman importin a isoforms, representative proteins from three different subfamilies werestudied. The aims of this investigation is firstly to clone , express full length (importin a5
and a?) and truncated (importin a1 , a3 , a5 and a?) human importin a isoforms byrecombination and then purify to homogeneity. The purified protein will then be used toattempt to produce crystals followed by structure determination . The second aim is toanalyze the importina - NLS binding specificities using homology modeling, NLS peptide
library experiments and nuclear import assays.
Protein crystals of human importin a? have been successfully obtained. With theavailability of these crystals, further studies with single crystals of sufficient size for X- rayMoreover, the proteolytically stablediffraction experiments will now be possible .
fragments of human importin as were determined by limited proteolysis using the protease
Endopeptidase Glu- C (V8) from Staph. aureus and the truncated form of human importin
a isoforms was incorporated into the expression plasmid and purified for further structurestudies. Furthermore , the three - dimensional models of human importin a isoforms,
including a1 , 3, 4 , 5, 6,and 7, were successfully constructed based on homology with themouse importin a2 , which has a known crystal structure. The human importin as - NLS
binding specificity using the homology models will then be analyzed . In addition , we havedeveloped a new technique to study the substrate specificity of importin a protein , using adegenerate peptide library. The primary optimal NLS peptide for N - terminally truncatedmouse importin a2 has already been identified .

P0167
STRUCTURAL AND FUNCTIONAL INSIGHT INTO NONSPECIFIC
NUCLEASES INVOLVED IN CELL DEFENSE
Hanna S. Yuan ,• Chia Lung Li ,a Kuo-Chiang Hsia• and Woei-Chyn Chub•Institute of Molecular Biology, Academia Sinica , Taipei , Taiwan ; 0 lnstitute of Medical
Engineering , National Yang-Ming University, Taipei , Taiwan (hanna@sinica.edu .tw).

In prokaryotic organisms , a variety of nonspecific endonucleases involved inprotection of bacterial cells have been identified. But differ from the well-known restriction
enzyme these endonucleases cleave DNA in a sequence-independent manner. One of
the examples is Escherichia coli colicin , ColE? , which digests chromosomal DNA in target
cells , so that the host cell may have better survival advantage during times of stress . The
crystal structures of the endonuclease domain of ColE? and its complex with DNA
demonstrates for the first time how the HNH motif in ColE? mediates its functions in DNA
binding and degradation .
The Vvn from Vibrio Vulnificus is another example of a nonspecific endonucleaseinvolved in cell defense. Vvn is a periplasmic protein , capable of digesting nucleic acid inperiplasm to prevent the uptake of foreign DNA during transformation. The crystal
structure of Vvn and Vvn in complex with a duplex DNA were resolved both at 2.3 A
resolution. This structural study suggests that Vvn hydrolyzes DNA by a general singlemetal ion mechanism and indicates how nonspecific DNA-binding proteins may recognize
DNA.

References
1
Hsia, K.-C ., Chak , K.-F., Liang , P.-H. , Cheng , Y.-S ., Ku , W.-Y. andYuan , H. S. (2004) Structure 12, 205-214 .
2
Li , C., Ho, L.-1. , Chang , Z.-F. , Tsai , L.-C ., Yang , W.-Z . and Yuan , H. S.
(2003) EMBO J. 22 , 4014-4025.

P0168CRYSTAL STRUCTURE AND CONFORMATION ANALYSIS OF ATETRAPEPTIDE BOC-B-ALA-LEU-AIB-VAL-OME
R. S. Rathorea
aoepartment of Physics, Indian Institute of Science , Bangalore 560 012 , India(newdrugdesign@yahoo .com)

The crystal structure of a synthetic, terminally blocked tetrapeptide t-Boc-p-Aia-LLeu-Aib-L-Vai-OMe has been examined . The peptide was crystallized in space group C 2 .
Final R values were: R =0.075; wR2 =0.193. The tetrapeptide adopts an overall extended
backbone conformation. Conformational parameters are : p-Aia: <p = -78 .7 (6 t, 8 = 172.1(4 t, 4J = 103.3 (5 t; Leu : <p = -117.4 (4t, 4J = 153.7 (4 t; Aib : <p = 62.5 (6t , 4J = 38 .6 (5 t;
Val : <p =-115 .2 (9 t, 4J = 168 (1In the crystal , peptides are interlinked by intermolecularhydrogen bonds and intermolecular bridges formed by water. These networks ofhydrogen-bonds form an unusual type of anti-parallel p-sheet structure.

t.

References
1
Rathore , R. S. & Banerjee , A. (2003) Curr. Sci. , 85 , 1217-1220.

P0169CRYSTAL STRUCTURE OF THIAPYRAN REVEAL HERRING-BONE n ··· n
INTERACTIONS
T . Narasimhamurthy,a J. C. N. Benny,c K. Pandiarajanc and R. S. Rathoreb•Bioinformatics Centre; bDepartment of Physics, Indian Institute of Science , Bangalore
560012 , India; coepartment of Chemistry, Annamali University, Annamalai Nagar 608002 ,India , and , (taterao@physics. i isc.ernet. in)

The crystal structure of trans-2 ,6-diphenyl-2 ,3,5,6-tetra-hydrothiapyran-4-one has
been determined , which is primarily stabilized by T-shaped and parallel-displacedaromatic clusters . In the crystal packing , the molecules dimerize by means of .1\ ... rr
interactions of both face-to-face and edge-to-face types, and the aromatic rings associate
in a cyclic edge-to-face tetrameric arrangement of the herring.-bone type. These herringbone interactions appear to insulate hydrogen-bond interactions in the crystal structure
presumably due to the overwhelming presence of rr donors and acceptors.
References
1
T. Narasimhamurthy, T., Benny, J. C. N. , Pandiarajan, K. and Rathore , R. S. (2003)
Acta Cryst. C, 59 , 620-621 .
2
Narasimhamurthy, T. , Krishnakumar, R. V., Benny, J. C. N. , Pandiarajan , K. &Vishwamitra , M. A. (2000). Acta Cryst. C, 56 , 870-871.

P0170SINGLE-CRYSTAL NEUTRON DIFFRACTION STUDIES OF RUBREDOXINAND OTHER SMALL PROTEINS
Robert Bau
Department of Chemistry, University of Southern California, Los Angeles, CA 90089,
U.S.A (bau@usc.edu)

Since the first publication in 1969, the use of neutrons to study proteins has
gradually improved in sophistication. This discussion will focus on the main features thatthe neutron diffraction technique can provide , as compared with X-ray diffraction . We will
review the importance and unique role of neutrons in the determination of biologicalstructures of macromolecular crystals , including the protonation sites of various residues,hydrogen exchange , and solvent structure . Also discussed in this presentation will berecent results on the high-resolution (1.5A) single crystal neutron analysis of rubredoxinfrom the hyperthermophilic organism Pyrococcus furiosus.

P0171
WATER ENHANCED CRYSTALLINITY IN CYRTOPHORA SPIDERDRAGLINE
Hwo-Shuenn Sheu ,• Khin Win Phyu ,a Yung-Ping Chiang ,a Yuch-Cheng Jean•and 1-Min Tsob
•National Synchrotron Radiation Research Center, Hsinchu 30077 , Taiwan .
(hsheu@nsrrc.org .tw) bDepartment of Biology, Tunghai University, Taichung 407 , Taiwan .
Spider dragline is the strongest nature fiber, that even better than the best synthetic
fiber, Kevlar. The elasticity of Nephi/a clavipes dragline is known to be three times ofsynthetic Nylon fiber and its strength is five times as steel in weight. Nephi/a spiders build
orb web and recycle its silk almost every day, while Cyrtophora spiders build a threedimensional web which can sometimes be used for more than a month in tropical forests.
This phenomenon suggests that dragline silks produced by Cyrtophora can be better
endure environmental impacts such as rain , wind and temperature fluctuations than those
produced by Nephi/a and Araneus. Supercontraction phenomena of Nephi/a dragline bywater have been extensively studied recently. The length of Nephi/a dragline will be shankto half of its original length during water absorption , while no changed in length wasobserved in Cyrtophora dragline. It is not surprised that Cyrtophora dragline is not affectedby water for its longer duration in nature . Two kinds crystalline were found in spider
dragline. One is highly orientated ,B-sheet along the silk direction the other one is randomorientation ,B-sheet as known as "S" reflection . In this study we found that the crystallinityof random orientation ,8-sheet of Cyrtophora dragline was affected by water absorption
and desorption. The diffraction intensity of "S" reflection became stronger and sharper
during the water absorption that indicated crystallinity of isotropi~,B- sheet became moreordering. The same treatment was also employed to Nephi/a pilipes dragline but nosignificant changing was observed during water absorption and desorption. These
different properties between two spider's dragline maybe correlate to that stratagem ofusing silk in nature.

P0172TWISTING OF PEPTIDE BOND BY HYDRATION WATERS AND
LOCALIZATION OF DEUTERIUM ATOMS OBSERVED IN HUMAN
LYSOZYME BY NEUTRON CRYSTALLOGRAPHY
Kaori Chiba-Kamoshida ,a Takuro Matsui ,b Toshiyuki Chatake ,a Takashi Ohhara , a Andreas
Ostermann c. lchiro Tanaka •, Katsuhide Yutani d and Nobuo Niimura a•Neutron Research Center, JAERI , Tokai , Naka, lbaraki , 319-1195 , Japan ; bCenter forInterdisciplinary Research , Tohoku University;<Technische Universitat Munchen ,Germany; dRIKEN Harima Institute (kchiba@neutrons.tokai.jaeri.go .jp)

Structural biology challenging to reveal the relationship between structure andactivity of protein molecules in post-genome project has been struggling in researchgroups all over the world . X-ray crystallography and nuclear magnetic resonance (NMR)
are two great authorities for structural biology. Although those methods seem to havebeen already established , there still has been remained a space of discussion to deal withlarge molecules as proteins.
The most significant difference between structural
determination for protein and that for small organic molecule is that protein needs
structural restrains even for high-resolution structure refinement. Planarity of peptide
bond linking two amino acids is the most standard restrain . Usually in refinement
programs , ens or X-PLOR , a model structure satisfying the planarity has been selected.
These structure models had been deposited to the Protein Data Bank (PDB) and theatomic coordinates are utilized by the other research groups , for example in a field of bioinformatics.
We will present results from our neutron crystallography of human lysozyme.
Glu35 is known to be one of the most important residues for the activity. We first directly
observed a positive peak of nuclear density which is thought to be a localization of
deuterium atom beside the main chain carbonyl oxygen of Glu35. In order to examine theeffect of the deuterium atom , we calculated deviations of omega angles from 180 degree
meaning distortion of peptide bonds from plane structure with a high-resolution (1.15
Angstrom) x-ray crystallography data [1] refined by SHELX downloaded from the Protein
Data Bank, PDB (1 JSF). The result showed that the peptide bond including the carbonyl
oxygen had been twisted more than 10.8 degrees. Also at the carbonyl oxygen of Tyr54
where the additional nuclear density peak had been observed as a part of a hydrationwater, 15.5 degrees rotation of the peptide bond was obtained . Planarity of a peptide
bond is constructed by an electronic resonance structure between a carbonyl group andan amide nitrogen. Taking the data of nuclear magnetic resonance (NMR) spectra into
consideration it is indicated that deuterium atoms localized beside the main chain carbonyl
oxygen or hydration waters including such a localized deuterium atom affect the electronicresonance structure of the peptide bond and distort the respective peptide bond planarity.
References
1
Harata K., Abe Y, Muraki M. (1998) Proteins . 30, 232-43

P0173

DESIGN OF PEPTIDES WITH A, B - DEHYDRO-RESIDUES: SYNTHESES,CRYSTAL STRUCTURES AND MOLECULAR CONFORMATIONS OF TWOTETRAPEPTIDES : CBZ - t.VAL -VAL - t.PHE - ILE - OCH 3 AND CBZ t.VAL- LEU· t.PHE- LEU- OCH 3
V. K. Gael , A. P. Baxla , R. K. Somvanshi , R. Padma , S. Dey and T. P. Singh.
Department of Biophysics , All india Institute of Medical Sciences , New Delhi-110029(vijay2_55@rediffmail.com)

a, b -dehydro residues induce specific folded conformations in peptides . The
conformational preferences of branched b-carbon dehydro-residues and non-branched bcarbon dehydro-residues are different when introduced at (i+2) position in tetrapeptides.
The former produces a type Ill b-turn while the latter is accommodated in a type II b-turnconformation. In order to determine the effects of the combinations of the above two typesof dehydro-residues in the same peptide sequences, we have synthesized two peptides:(i) Cbz- OVal- Val- DPhe- lie- OCH 3 and (ii) Cbz- OVal- Leu- DPhe- Leu- OCH 3 . The
crystal structures of the two peptides were determined. The torsion angles f, y in the two
peptides were found to be (i) f 1 = -38.r, y, = -41.1 °, f2 = -73.0°, y2 = -3.8°, f3 = -62 .0°, y3 =-15S , f4 = -119T , y4 = -4.6° and (ii) f 1 = -36.8°, y1 = -46.8°, f 2 = -63S , y2 = -12.6°, f3 =-67.0°, y3 = -18 .2°, f4 = -61.5°, y4 = -136.4°. Both peptides form two intramolecular (i+3) ®
(i) hydrogen bonds in each structure. The torsion angles and hydrogen bonds indicate theformations of 3 10-helical conformations although the nature of non-dehydro-residues in thetwo structures is different. It shows that the presence of OVal and DPhe residues in
peptides induces 310-helical conformations irrespective of the nature of its side chain . A
definite result of this kind can be exploited for design of peptide structures for specificapplications.

P0174
EXPRESSION, PURIFICATION AND CRYSTALLIZATION OF MOB1 FROM
Sacchromyces cerevisiae
Shannon W. N. Au a, J. Wade Harperc and David Barfordb
aDepartment of Biochemistry, The Chinese University of Hong Kong , Shatin , Hong Kong .
(Shannon-au@cuhk.edu.hk)bSection of Structural Biology, Institute of Cancer Research, Chester Beatty Laboratories ,237 Fulham Road, London , SW3 6JB , United Kingdom .
cDepartment of Biochem istry and Molecular Biology, Baylor College of Medicine, One
Baylor Plaza , Houston , TX 77030 , USA.

Mps One binder (Mob) family comprises a group of highly conserved proteins , thefounding member, Mob1 , fun ctions in the mitotic exit network and is essential for mitotic
exit, cytokinesis and cell separation . Its association with protein kinase Dbf2 enhances
phosphorylation and activation of Dbf2 . Formation of Mob1-Dbf2 complex is prerequisite
for subsequent release of protein phosphatase Cdc14 from nucleolus in late mitosis .
The full-length eDNA of Sacchromyce cerevisiae encodes a protein of 314 aminoacid residues with no known structural motif. The protein sequence shows 50% identitywith the human homologue. It also shares sequence similarity with other members in thegene family , particularly with a nonessential gene, Mob2. However, there is no direct
genetic interaction between Mob1 and Mob2.
In our study, we have expressed and purified Mob1 from Saccharomyces
cerevisiae to homogeneity using pET expression system. Full length Mob1 has beentreated with limited proteolysis to identify a stable domain. A Mob1 fragment with Nterminus starts at residue 89 has been crystallized at 293K using lithium sulfate as theprecipitant. X-ray diffraction data has been col lected to 3.1 A. The crystal belongs to thehexagonal system , with unit-cell parameters a = 113.6 A, b = 113.6 A. c = 88 .3 A and one
monomer in the asymmetric unit.

P0175
THE C-TERMINAL REGION IN TRICHOSANTHIN IS IMPORTANT FOR
ACTIVITY AND CONFORMATIONAL STABILITY
Hiu-Mei Too•, Yi Dingb.c, Siu-Hong Chan•, Zhilong Wangc, Yiwei Liuc, Mark Bartlamc,
Yicheng Dongb.c, ,Kam-Bo Wong• Zihe Raob.c and Pang-Chui Shaw••Department of Biochemistry, Chinese University of Hong Kong , Hong Kong , China ,blnstitute of Biophysics , Chinese Academy of Science , Beijing 100101 , China andcLaboratory of Structural Biology and the MOE Laboratory of Protein Science , School ofLife Science and Engineering , Tsinghua University, Beijing 100084, China(priscillatoo@cuhk .edu.hk)
Trichosanthin (TCS) is a type I ribosome inactivating protein with multiple
pharmacological properties including immunomodulatory, anti-tumor and anti-HIV
activities. It has rRNA N-glycosidase activity and removes adenine-4324 on the 28s rRNA.
Trichosanthin can fold into an active conformation with the last seven residues deleted.
The deletion variant, C7-TCS has 2. 7-fold decrease in antigenicitiy, 10-fold reduction inboth in vitro ribosome-inactivating activity and in vivo cytotoxicity. Moreover, stability assay
shows that the deletion of these amino acids destabilizes the structure of TCS.
The crystal structure of C7-TCS has been determined to 0.2nm resolution. The
structure shows that hydrogen bonds between P35 and L240 , S196 and L240, and W192
and L239 play an important role in maintaining the structure of C7-TCS. Further analysis
shows that the hydrogen bonds related to Leu240 are important for maintaining therelationship between the N- and C-terminal domains of TCS . Besides , both thefluorescence spectra and crystal structure show that W 192 is more solvent exposed in C7TCS. By mutating this residue into phenylalanine , W192F-TCS gives a decrease in bothstability and ribosome-inactivating activity. The effects of the C7-TCS and W 192F-TCS are
accumulative , the ribosome-inactivating activity of W 192F-C7-TCS decreases by about 60
folds .
Work in Hong Kong was supported in part by a Strategic Grant from the Chinese
University.

P0176
PURIFICATION AND STUDY OF ITS EFFECT OF POLYTYPISM IN
SOLUTION GROWN CADMIUM IODIDE CRYSTALS USING X-RAY
DIFFRACTION
S. K. Chaudhary and Harjeet Kaur
UniversityCollege,M. D.University,Rohtak-124001 (India) (sunilkc2001 in@yahoo .com)

The Cadmium iodide has been purified using a zone-refining method fabricated byus. The crystals have been grown in two batches using unpurified and purified material. A
comparative study has been made on these batches for polytypism using x-ray diffraction
technique. Total number of polytypes involved are 360.
Formation of small period polytype 2H is governed by both temperature andimpurities contained in the starting material. 4H is the most stable polytype. Higher
occurrence of unidentified polytype in crystals of purified material has been attributed tofree movement of edge dislocations during growth. The results have been examinedagainst empirical considerations of earlier investigations.

P0177
PHENOMENON OF POLYTYPISM IN MELT-GROWN LAYERED CRYSTAL
OF Cdb , Pbb AND CdBr2
S.K.Chaudhary and Harjeet Kaur
University college ,M.D.University Rohtak-124001 (India) (Sunilkc2001 in@yahoo.com)

Polytypism has been observed in a large number of materials where the nearest
neighbor relationship between identical two-dimensional layers of atoms can be satisfied
in more than one way . The phenomenon has posed interesting problem for the Scientists ,since the nature of force that causes ordering over the scale ranging from few angstrom to
few thousands of angstrom units is not known.
The theoretical and experimental advancements made in the study of polytypism inmelt- grown crystals of Cd b ,Pbl2 and CdBr2 in the last few decades have been reviewed.
The past work done in this field by us ( using optical ,Lasers and X-ray diffraction
techniques) and update on the aspect of polytypism in the above crystals has beenoutlined with special reference to the role ofP0178CRYSTALLIZATION OF SOME ORGANIC CONSTITUENTS OF URINARYSTONES IN GEL AND CHARACTERIZATION
E. Ramachandran• and S. Natarajanb•Department of Physics , Thiruvalluvar College , Papanasam-627425 , India , bDepartmentof Physics , Madurai Kamaraj University, Madurai-625021 , India(esakkiramachandran@yahoo.co.in)

Organic acids viz .. uric acid , hippuric acid , and amino acids cystine , tyrosine , leucine
are some of the minor constituents of urinary stones [1] . The etiology of formation of uricacid in urolithiasis is still not very clear. References cite that there are increased levels ofurinary hippuric acid among toluene exposed industrial workers [2]. Excessive excretion ofcystine in urine - cystinuria - is a hereditary defect, causes cystine stones [3]. The
presence of amino acids , tyrosine cystine and leucine as constituents of urinary stones in
addition to their many biological roles , prompted the authors , to investigate the growth
characteristics and related studies.
Hippuric acid , L-tyrosine , and L-cystine were crystallized in silica gel under suitable
pH conditions by reaction method . Transparent, rectangular plates of hippuric acid of size
10.0 x 4.0 x 1.0 mm 3 , spherulitic needles of L-tyrosine of size 18.0 x 0.1 x 0.1 mm 3 andbunched hexagonal plates of L-cystine of size : 1.0 mm (across) and thickness 0.2 mm ,were crystallized.
The grown crystals were characterized by density measurement, and X-ray powder
diffraction . Fourier transform infrared spectroscopic studies and thermogravimetricanalysis were made on the powdered samples of the above .
The details of the crystal growth conditions and the characterization studies will bepresented .
References1
Oser, B. L. Hawk's Physiological Chemistry, 14<h edition , Tala McGrawHill Publishing Co . Ltd., New Delhi , 1976.
2'Toluene , Health and Environmental Effects", U. S. Environmental Protection
Agency, Office of Solid Waste , Washington . D.C. ,1980.
3"Lange Medical Book. Harper's Biochemistry", Prentice Hall , New Jersey,
1988. p 286.

P0179SOME AZIDO-BRIDGED COORDINATION POLYMERS: STRUCTURESAND MAGNETISMSong Gao. Hao-Ling Sun , Yuan-Zhu Zhang and Bao-Qing Ma
State Key Laboratory of Rare Earth Materials Chemistry and Applications , PKU-HKU Joint
Laboratory on Rare Earth Materials and Bioinorganic Chemistry, College of Chemistry andMolecular Engineering , Peking University, Beijing 100871 , China (gaosong@pku.edu.cn)

Azide has been widely used to synthesize molecule-based magnetic materials for its
efficient magnetic exchange coupling and diversity of coordination modes. We reported anazide-bridged 1D cobalt compound that is the first homospin single-chain-magnet; we also
obtained some mixed azide/L -bridged (L = pyrazine-dioxide , carboxylate , 4,5diazafluoren-9-one azine , cyanide) coordination polymers that show long-rang magnetic
ordering [1-5] .
Herein we report a novel 20 coordination polymer [Mn 3 (N 3 ) 6 (bpe) 3 ]1 (bpe = trans-1 ,2bis(4-pyridyl)-ethylene) . It contains rare 1 D F/AF/AF alternating chain bridged by ~~ 1.3-N 3 (end-to-end , EE) and ~ 1 . 1 -N 3- (end-on , EO); the chains are further connected by bpe toform 20 layer. It exhibits an antiferromagnetic ordering and metamagnetic behaviour
below 2.5 K.
12

~: ~
=EIT~

6 2
~ 1

O,\-- TI-K -;,;;0 -

0

0

50

100 150 200 250 300

TI K

Two-dimensional layer constructedby Pu -N 3· , ~ 1 . 1 -N 3 · and p bpe

xM T vs. T plot of 1 at 5 kOe(Inset: XM vs. Tat different fields).

References
1
Liu , T. F. , Fu , D., Gao , S., Zhang , Y. Z., Sun , H. L. , Su , G. and Liu, Y. J. (2003) J.
Am. Chem. Soc. 125, 13976-13977.
2
Ma , B. Q., Sun , H. L. , Gao , S. and Su , G. (2001) Chem .Mat. 13, 1946-1948.
3
Chen , H. J ., Mao , Z. W ., Gao , S. and Chen , X. M. (2001) Chern. Commun.
2320-2321 .
4
Liu , C. M. , Gao , S. , Zhang , D. Q. , Huang, Y. H., Xiong , R. G. , Liu , Z. L., Jiang , F. C.
and Zhu , D. B. (2004) Angew. Chem. Int. Ed. Engl. 43 , 990-994 .
5Zhang , Y. Z. , Gao , S., Sun , H. L., Su , G. and Zhang , S. W . (2004) Angew. Chern. Int.
Ed. Engl. submitted.

P0180BISMUTH DISORDER IN PYROCHLORE OXIDES
Brendan J Kennedy, Leqing Li and Qingdi Zhou
•School of Chemistry, The University of Sydney, Sydney, NSW 2006 Australia(bkennedy@chem.usyd.edu.au).
The structures of a number of Bi containing pyrochlores including the series Bi 2 _xYbxRup 7-d, Bi 2 1nNb07 and Bi 2 CrTa0 7 have been studied using a combination of highresolution powder synchrotron and neutron diffraction methods . The oxides all have the
cubic pyrochlore structure . In the ideal pyrochlore structure the Bi cations would occupy
the 16d sites at (Y.. Y, Y, ) and have a distorted 8-fold geometry. This geometry does notallow for the Bi 6s electrons to be sterochemically active . Careful examination of thediffraction patterns reveals that the Bi atoms generally do not occupy the 16d type sites
but rather are displaced onto a nearby 96h site at (Y,, Y,+y, Y,-y) , y "" 0.25. The resulting
disorder is apparently a consequence of both the sterochemical activity of the Bi 6s
electrons and the underbonding of the Bi cations in the ideal structure .
The structural studies of the series Bi 2_xYbxRu 2 0 7_d reveal a number of anomalies
that are apparently related to the metal-semiconductor transition . In particular themagnitude of the Bi displacement is progressively reduced as the Yb is added to thesystem . This and other trends will be discussed.
References
Li , L. and B.J . Kennedy (2003) Chem Mater. 15 4060-4067 .
1

P0181
XRD, FTIR AND TGAIDTA STUDIES OF GEL GROWN GLYCINE AND
DL-SERINE
E. Ramachandran • and S. Natarajanb•Department of Physics , Thiruvalluvar College , Papanasam-627425, India,
bOepartment of Physics , Madurai Kamaraj University, Madurai-625021 , India(esakkiramachandran@yahoo.co.in)

Glycine and serine are neutral , genetically coded amino acids, hydrophilic polar innature. Glycine (C 2 H5 N0 2 ) is a non-essential amino acid. It is the only protein-forming
amino acid without a center of chirality. Serine (C 3 H7 N0 3 ) can be synthesized in the bodyfrom glycine and is required for the metabolism of fat , tissue growth and the immune
system .
Crystallization of amino acids in gel is scarce in literature. Natarajan et al. , reported
the crystal growth of some amino acids and peptides from our laboratory earlier [1].
Glycine and DL-Serine were crystallized in silica gel under suitable pH conditions by
reduction of solubility method. Transparent, rhombohedral crystals of glycine, of size 10.0
x 4.0 x 4.0 mm 3 and rectangular plates with hexagona l edges of DL-Serine, of size 9.0 x
3.0 x 2.0 mm 3 were crystallized.
These crystals were characterized by density measurement, and X-ray powder
diffraction . Fourier transform infrared spectroscopic studies and thermogravimetricanalysis were made. The details of the crystal growth conditions and the characterization
studies will be presented .
References
1
Natarajan, S. , Alex Devadoss, H. and Alwan , K. , Cryst. Res. Technol. 23 (1988)
1243-1346.

P0182CRYSTAL GROWTH BY CHEMICAL TRANSPORT OF PEROVSKITETUNGSTEN BRONZES, LlxW0 3, AND THEIR OPTICAL PROPERTIES
K. R. Dey,a A. Hussain ,b and C. H. ROscher••Department of Mineralogy, University of Hannover, Welfengarten 1, 30167 Hannover,Germany; bDepartment of Chemistry, Dhaka University, Dhaka 1000, Bangladesh(C.Ruescher@mineralogie.uni-hannver.de).
Systematic attempts were made to grow crystals of perovskite tungsten bronzes (PTB)of Li,W0 3 of nominal compositions x = 0.1, 0.2, 0.25 , 0.3, 0.35 , 0.4 , 0.45 by chemical transport
methods . HgCI 2 was used as transporting agent and appropriate amounts of Li 2 W0 4 , W0 3
and W0 2 as reactants. A complete transport was achieved within 7 days with a temperature
gradient T , I T 2 = 700°C I 800°C revealing blue-blackish crystals of sizes up to a few tenth of amilimeter. X-ray powder (Guinier and diffractometer methods) and infrared absorption (KBr
method) investigations show a close analogy of the results also obtained in classical solid state
reaction methods, which , however, produces crystal powders of submicron sizes. According tothis we obtain single phase PTB products of cubic symmetry (PTBcub) for Li,W0 3 of nominal
composition x = 0.45, 0.4 , 0 .35 and mixed phase of PTBcub and PTB,.,, (PTB of tetragonal
symmetry) for x = 0.3, 0.25, 0.2 . The x = 0.1 sample reveal mixed phases of PTB,., and PTBo
of lower symmetry. These results are in good agreement with the phase diagram described by
Reau et al. [1] . It is interesting to note that Zhong et al [2] have determined the stability ranges
of using electrolytic cells as 0.36 < x < 0.5 for PTBcub and 0.082 < x < 0.13 for PTB,.,, during
intercalation whereas 0.21 < x < 0.5 for PTBcub and 0.078 < x < 0.12 for PTB,., during deintercalation .
Beside the investigations of the crystal growth conditions of these nonstoichiometriccompounds another aim was to study their single crystal optical properties. For this polarized
micro reflectivity measurements between 600 and 20000 em·' using a spot size of 80 ~m indiameter on polished crystal slices . The crystals from the batches with x = 0.45 all show Drude
free carrier type isotropic reflectivity with a minimum at about 14800 em·' . Crystals from thebatches with x = 0.4 slightly differ indicating a superimposition of an additional spectral
contribution in the range of the minimum . This contribution could
already be related to the influence of the tetragonal phase due tosubmicroscopical exsolution phenomena since this effectbecomes more significant for crystals with lower nominal x. For
these crystals there are brighter lamellars separated by sharp
interfaces (Fig . 1) due to a separation into PTBcub and PTB,.,,_ The
brighter lamellars become more significant in area for crystals of
the batches with x = 0.3, 0.25 and 0.2 and their reflectivity spectra
could be measured separately. The data imply that the properties
in the tetragonal part of the crystals are dominated by electron
localisation effects whereas the cubic parts are dominated by thefree electron gas effect.
Fig . 1: Li 035 W0 3 crystal
slice in reflexion mode
References
andReau , J-M ., Fouassier, C., Le Flem , G., Barraud , J-Y., Doumerc, J-P .,1
Hagenmuller, P. (1970) Revue de Chemie minerale,7 , 975-988.
Zhong , Q., Dahn , J. R., and Colbow, K. (1992-11) Phys. Rev. B, 46 , 2554-2560 .
2

P0183
3X3X1 SUPERSTRUCTURE OF LITHIUM MANGANESE SPINEL
Nobuo lshizawa .a Douglas du Boulay,a Kenji Tateishi ,b Katsumi Sudac, and Shuji Oishid
a Ceramics Research Laboratory, Nagoya Institute of Technology, Asahigaoka , Tajimi

507-0071 , Japan ; b Interdisciplinary School of Science and Engineering , Tokyo Institute ofTechnology, Nagatsuta Midori , Yokohama 226-8502 , Japan ; c Materials and Structures
Laboratory, Tokyo Institute of Technology, Nagatsuta Midori , Yokoh ama 226-8503 , Japan;
d Faculty of Engineering , Shinshu University, Wakasato , Nagano 380-8553, Japan(ishizawa@nitech .ac.jp ).

Lithium manganese spinels are attractive candidates for cathode materials of
rechargeable lithium ion batteries. Stoichiometric LiMn 2 0 4 is a mixed valence compoundcomprised of distinct Mn(lll) and Mn(IV) ions in equal proportions. Above the first orderphase transition temperature 310 (1) K on heating , Mn(lll) and Mn(IV) ions are randomly
distributed amongst the 16d sites of Fd-3m symmetry, while they are substantiallylocalized on five independent sites in Fddd symmetry below 294(1) K on cooling .
Our synchrotron X-ray single crystal diffraction study [1] at the beam line 14A,
Photon Factory, modestly confirms the orthorhombic Fddd symmetry containing 18
crystallographically independent atoms , with a= 24.7550(9), b=24.8832(9) and
c=8 .2003(3) A Z=72 at 297(1) K on heating , R/Rw =0 .038 for 1549 independent
reflections. Bond valence sums (BVS) determined for each Mn site were 3.06 for Mn1 ,3.34 for Mn2 , 3.12 for Mn3 , 3.89 for Mn4, and 3.88 for Mn5 , averaging to 3.50 over theunit cell. The evidence indicates that Mn 1-Mn3 and Mn4-Mn5 sites strongly include thecontribution of Mn(lll) and Mn(IV), respe ctively, with a minor reservation for Mn2. The
bond-lengths of Mn1-05 [2 .159 A] are about 10% longer than those of Mn1-04 [1.938 A]
and Mn1-02 [1.966 A], arising from the Jahn-Teller effect of high spin Mn(lll) ions . The
same arguments also apply to both Mn206 and Mn30 6 octahedra and they have longer
Mn-0 bond length along a and b axes, respectively. On the other hand these tendency do
not appear at Mn4 and Mn5.
Some structural anomaly around Mn2 and coordinating 09 atoms , that surround an
inversion centre, will be discussed in association with the imperfect charge ordering of thesystem.
References
K. Tateishi , K. Suda , D. du Boulay, N. lshizawa & S. Oishi , Acta Cryst. E60 , (2004)
1
i18-i21.

P0184
MICRO-STRUCTURAL STUDY ON THE ALLOY MINi 3 .75 Co 0 .75 Mn 0 . 3A1 0 .2 (MI:LA-RICH MISCH METAL) DURING THE HYDROGEN ABSORPTION AND
DESORPTION CYCLING
Guanqlie Lu and Zhiqing Yuan
Central Laboratory, XiXi Campus , Zhejiang University, Hangzhou 310028, P. R. China(gllu@zju.edu.cn)

X-ray diffraction microstructure of hydrogen storage alloy MINi3.7 5 Co 0 .75 Mn 0 .3A1 0 .2 (MI : Larich misch metal) during the hydrogen absorption and desorption cycling was studied byusing in situ X-ray diffraction method. Crystallite sizes along different (hk/) planes were
determined by applying an anisotropic diffraction-line broadening model in the Rietveld
refin ement. It had been indicated that the hydrides precipitate in the same domains withthe solid solution phase. Hydride precipitates are the combinations of the plate-like andthe needle-like crystallites, whose sizes are mainly affected by the dislocations formed in
the hydrogen absorption and desorption cycling.
References
1 Cerny, R. , Joubert, J. -M., Latroche, M., Percheron-Guegan , A ., Yvon , K. (2000) J.
Appl. Crystallogr. 33 , 997-1 005 .
2 Joubert, J. -M ., Latroche , M., Cerny, R. , Percheron-Guegan , A ., Yvon , K. (2002) J.
Alloys. Compd. 330-332 , 208-214 .
3 Kim , G. H., Chun , C. H. , S. G. , Lee , K. Y. , Lee , J. Y. (1994) Acta. Metal/. Mater. 42 (9),3157-3161 .
4 Popa , N. C. (1998) J. Appl. Crystallogr. 31 , 176-180.
5 Wu , E., Kisi , E. H. , Gray, E. MacA. (1998) J. Appl. Crystallogr. 31 , 363-368.

P0185RESIDUAL STRESS MEASUREMENT FOR GRANITE BY TOF NEUTRONDIFFRACTION METHOD
T . lshigaki ,a H. Obana ,a J. Kodama ," S. Harjob and T. Kamiyamab
aoepartment of Materials Science and Engineering , Muroran Institute for Technology,
Muroran 050-8585 , Japan; bNeurton Science Laboratory, IMSS, KEK , Tsukuba ,305-0801, Japan (ishigaki@mmm.muroran-it.ac.jp).

It is important, when using the rock, to know the pressure which rock had received
in underground. It is thought that the rock is maintaining the stress received inunderground as residual strain. It is possible to presume the pressure under the earth inorder to measure the residual stress for the rocks.
In this report, we have made an experimental study to measure the residual strainof granite block by neutron diffraction using Sirius diffractometer at KENS , KEK. The
maximum residual stress for quartz in granite used for this experiment is 19.5Mpa.

P0186HYDROGEN-BONDED CRYSTALLINE FRAMEWORK BASED ON
RESORCIN[4]ARENE AND 4,4'-BIPYRIDINEDIENE
Shu-Qun Liu ," Qian-Feng Zhang ,"* and Wa-Hung Leungb••Department of Chemistry and Chemical Engineering , Anhui University of Technology,
Maanshan , Anhui 243002 , China (E-mail: zhangqf@ahut.edu .cn)bDepartment of Chemistry, The Hong Kong University of Science and Technology,
Clear Water Bay, Kowloon , Hong Kong , China (chleung@ust.hk)
Seeking to develop further the use of large and sterically-demanding molecularbuilding blocks ,1 we proposed to use resorcin[4]arene , "molecular capsule ", as templates
for the synthesis of metal nanoparticles in order to control both the size and size
distribution of the resultant particles .z One of our interests is therefore to study the solidstate adducts of C-substituted calix[4]resorcinarene and 4,4'-bipyridinediene. We
reasoned that the addition of an aliphatic spacer group between the pyridine units in thelong 4,4'-bipyridinediene would lead to chain- and cavity-formation sufficient to control
templates for metal cluster nanoparicles. Herein we initially show two supramolecularsolids of 4,4'-bipyridinediene with C-methylcalix[4]resorcinarene (1) and C-isobutylcalix[4]resorcinarene (2) , respectively . Further photochemistry reactions and metalcoordination behaviors of two supramolecular multi-components will be reported later.

2
References
MacGillivray, L. R.; Atwood , J. L. Nature 1997 , 389 , 469-472 .
1Jasat, A. ; Sherman , J. C. Chem. Rev. 1999 , 99, 931-967 .
2

The support from the Key Scientific Research Foundation of State Education Ministry(grant no .204067) and Natural Science Foundation of China (grant no. 90301 005) is
acknowledged.

P0187OXYGEN-INDUCED FORMATION OF A NOVEL TETRA-NUCLEAR PCYMENERUTHENIUM COMPLEX WITH OXO BRIDGES
Lihua Liu ," Qian-Feng Zhang ,"* and Wa-Hung Leung"8

0epartment of Chemistry and Chemical Engineering , Anhui University of Technology,
Maanshan , Anhui 243002 , China (E-mail: zhangqf@ahut.edu.cn)
bOepartment of Chemistry, The Hong Kong University of Science and Technology,
Clear Water Bay, Kowloon , Hong Kong , China (chleung@ust.hk)

It is well known that ruthenium complexes are versatile compounds that can catalyze
various organic reactions. ' In recent years there has been an increasing interest in metal
complexes containing chloride ligand and a chelating ligand , because the labile chloride
can be readily displaced by small molecular such as H2, N2, 0 2, CO, C02 and CH2=CH2.
The coordination of such molecules is of interest with respect to their activation for
catalytic transformations. Because the arene-ruthenium complexes such as[RuCI 2(arene)]2 and [RuCI 2(PR3)(arene)] have been used as homogeneous catalysts, weseek to explore catalytic activity of the [(arene)Ru] species. In the course of our researchon ruthenium complexes with sulfur and selenium donor ligands , we have isolated highvalent arene-ruthenium complexes by oxidation reactions. Treatment of [( if-pcymene)Ru(acetone )3][BF. ]2 with 4,4'-bipyridine (4,4'-bipy) in CH2CI2 solution in air resulted
in the formation of a novel mixed-valance tetranuclear p-cymeneruthenium complex [ {(116p-cym en e) Ru } 2(~t-0) 2 (4 , 4 ' -b i py)]2[B F4]2 . The structural analysis reveals a macrocycle withalternating oxygen and 4,4'-bipy bridged between the ruthenium atoms . Electrochemical
studies showed th at the Rull- ( ~t-0 ) 2-Rulll moiety undergoes an initial one-electron oxidation to
Ruiii- ( ~J- 0)2-Rulll and the oxidation potential for a complex with the high-valent state has
been determined .

References
1
Noyori, J. Asymmetric Catalysis in Organic Synthesis, Wiley, New York, (1994).
The support from the Key Scientific Research Foundation of State Education Ministry(grant no. 204067) and Natural Science Foundation of China (grant no . 90301005) is
acknowledged.

P0188CRYSTALLOGRAPHY OF MICROSTRUCTURAL TRANSITIONS IN
COPPER BASED SHAPE MEMORY ALLOYS
0. Ad1guzel
Firat University, Department of Physics, 23119, Elazig, Turkey(oadiguzel@firat.edu.tr, oadiguzel@hotmail.com8
The behavior of many materials is evaluated by the microstructural changes in
microscopic scale depending on the external conditions. One particular group of suchmaterials are shape-memory alloys which exhibit a peculiar property called shapememory effect. The origin of this phenomena lies in the fact that the material changes its
internal crystalline structure with changing temperature.
Metastable b-phases of noble metal copper based ternary alloys are very sensitivefrom the 82(CsCI8 or
to the heat treatments and transform martensiticallyD0 3 (Fe 3AI8 type ordered structures to the long period layered structures on cooling. The
reactions calledhigh temperature bcc(q-phase undergoes two types of ordering
premartensitic transitions during cooling. The first transition is a nearest neighbour (nn8ordering reaction which results in a 82-type superlattice . However, bee to 00 3 transition
which induces the next-nearest neighbour (nnn8 orde-ing reaction is first order.
Martensitic transformations in shape memory alloys occur by two or more latticeinvariant shears on a {11 0} b plane of parent phase called basal plane of martensite. The
order of martensite structure is closely related to the order of parent due to the
diffusionless character of the transformation , and the martensite exhibits the order ofparent existing prior to the transformation . Martensite phase has the unusual layered
structures which consist of an array of close-packed planes with complicated stacking
sequences called as 3R , 9R or 18R martensites depending on the stacking sequences on
the close-packed planes of the ordered lattice. On the basis of austenite-martensite
relation , it is experimentally determined that the basal plane of 9R (or 18R8 martensites
originates from one of the {11 0} b planes of the parent phase , and an homogenous shear
occurs on the basal plane in either of two opposite directions during the transformation.
The {11 O}b type plane of parent which is the basal plane for martensite is subjectedto the hexagonal distortion with martensite formation on which atom sizes have important
effect. In case the atoms occupying the lattice sites have the same size , the hexagon
becomes regular hexagon otherwise the hexagon undergoes a distortion in case atom
sizes are different. Due to this distortion , the spacing differences between particularly
selected pairs of diffraction planes providing a special relation between miller indicesbecome different zero and can be a measure of the ordering degree in martensite . The
decrease in spacing difference leads to disordering in martensite.

P0189POSITIONAL DISORDER AND DIFFUSION PATH IN OXIDE-ION
CONDUCTORS
Masatomo Yashima ,a Katsuhiro Nomura ,b Daiju lshimura ,a Syuuhei Kobayash i,"
Hiroyuki Kageyama ,b Wataru Nakamura: Kenjiro Oh-uchi ,a and Kenji Ohoyamac•Department of Materials Science and Engineering , Interdisciplinary Graduate School of
Science and Engineering , Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku ,Yokohama , 226-8502 , Japan ; bSpecial Division of Green Life Technology, National
Institute of Advanced Industrial Science and Technology (AIST) - Kansai , Midorigaoka
1-8-31 , Ikeda, 563-8577 , Japan; clnstitute for Materials Research , Tohoku University,
Katahira 2-1-1 , Aoba-ku , Sendai , 980-8577, Japan (yashima@materia .titech .ac.jp).

Solid oxides with high ionic conductivity are attracted materials owing to their many
applications in solid oxide fuel cells , sensors , catalysts and batteries. The development ofbetter electrolyte materials requires a better understanding of the mechanism of ionic
conduction , and crucial to this is a comprehension of the crystal structure at hightemperatures where the materials work efficiently. Here we report the disorder anddiffusion path of oxide ions in Bip 3 [1], Ce0 2 [2], and (La 06 Sr02 )(Ga 06 Mg0 15Co 005 )0 26 [3] .
These were studied through the nuclear density distribution obtained by a combined
technique including Rietveld refinement and maximum-entropy method (MEM)-based
pattern fitting of neutron powder diffraction data measured with the HERMES
diffractometer at high temperatures. The cubic bismuth oxide li-Bip 3 with the fluorite-type
structure has the highest oxide ion conductivity in the known compounds. We found thatthe oxide ions have a complicated disorder spreading over a wide area and shift to the<111 >directions from the ideal fluorite site at 77WC [1]. This feature would be responsible
for the fast oxide-ion conduction of li-Bi 2 0 3 . Ceria (Ce0 2 )-based materials have high oxideion conductivity. Accurate nuclear density distribution of Ce0 2 has been studied between
1005 ' and 1497'C [2]. The results reveal that the oxide ions have a complicated disorderspreading over a wide area and shift to the <111 > directions from the ideal fluorite position[2]. This feature is more significant at higher temperatures , which is consistent with thehigher ionic conductivity [2] . Lanthanum gallate-based compounds with an A80 3
perovskite-type structure have high oxide-ion conductivity. Here we demonstrate that the
diffusion path of oxide ions is not along the straight line between the ideal positions , but
exhibits an arc shape away from the 8-site cation (Ga 06 Mg 0 15 C0 005 ) [3]. In the lowtemperature rhombohedral phase , the oxide ions are localized , while in the hightemperature cubic structure , they spread over a wide area [3]. We acknowledge verymuch Prof. Emeritus Y. Yamaguchi (Tohoku Univ.), Dr. Y. Miyazaki (AIST) , Dr. N. Chitose ,Mr. K. Adachi (Mitsubishi Materials Co.), Mr. K. Kawachi and Mr. T. Yasui (Dai-lchi
Kigenso Kagaku Kogyo Co.) for assistance and discussion.
References
1
Yashima , M. and lshimura , D. (2003) Chem. Phys. Lett. 378 , 395-399.
2
Yashima , M. and Kobayashi , S. (2004) Appl. Phys. Lett. 84, 526-528.
3
Yashima , M., Nomura, K., Kageyama , H., Miyazaki , Y. , Chitose , N. and Adachi , K.
(2003) Chem. Phys. Lett. 380 , 391-396.

P0190
HIGH-TEMPERATURE NEUTRON POWDER DIFFRACTION STUDY OF
CERIA UP TO 15QQoC
Syuuhei Kobayashi ." Masatomo Yashima ,a Daiju lshimura,a Kenjiro Oh-uchi·• Wataru
Nakamura ,a Kenji Ohoyama ,DKatsuhiro Kawachi ,c and Tadahi Yasuic•Department of Materials Science and Engineering , Interdisciplinary Graduate School of
Science and Engineering , Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku ,Yokohama , 226-8502 , Japan ; Dlnstitute for Materials Research , Tohoku University,
Katahira 2-1-1 , Aoba-ku , Sendai , 980-8577 , Japan; cDaiichi Kigenso Kagaku Kogyo ,Hirabayashi-Minami 1-6-38, Sumire-ku , Osaka 559-0025 , Japan(yashima@materia .titech .ac .jp ).

Solid oxides with high ionic conductivity are attracted materials owing to their many
applications in solid oxide fuel cells , batteries , catalysts and oxygen sensors. The
development of better electrolyte materials requires a better understanding of themechanism of ionic conduction , and crucial to this is a comprehension of the crystal
structure at high temperatures where the materials work efficiently. We have investigated
the temperature dependence of unit-cell and structural parameters of ceria (cerium
dioxide , Ce0 2 ) from room temperature to 1500°C by neutron powder diffraction and theRietveld method [1 , 2] . The neutron-diffraction data was collected using the multi-detector
system HERMES [3] and a furnace to heat the sample in the temperature range fromroom temperature to 1600°C [4]. The unit-cell parameter increases continuously withtemperature . It was confirmed that the Debye-Waller factor of oxygen B(O) is larger thanthat of cerium B(Ce) at any temperature from room temperature to 1500°C. Both B(O) andB(Ce) increase with an increase of temperature. We have also studied the anisotropic
thermal vibration of oxide ions in ceria by the combination technique of the Rietveld
refinement, the maximum-entropy method (MEM) and the MEM-based pattern fitting [2] .
This was studied through the nuclear density distribution obtained by a combined
technique including a Rietveld refinement (RIETAN-2000) and a maximum-entropy
method (MEM)-based pattern fitting (PRIMA [5]) of the neutron powder diffraction datameasured at high temperatures . The nuclear density distribution was plotted by acomputer program VENUS [5]. The results reveal that the oxide ions have a complicateddisorder spreading over a wide area and shift to the <111 > directions from the ideal
fluorite position [2] . This feature is more significant at higher temperatures , which isconsistent with the higher ionic conductivity [2].
References
1
Yashima , M. , lshimura , D., Yamaguchi , Y. , Ohoyama , K. and Kawachi , K. (2003)
Chem. Phys. Lett. 378 , 395-399.
2
Yashima , M. and Kobayashi , S. (2004) Appl. Phys. Lett. 84, 526-528 .
3
Ohoyama , K., Kanouchi , T., Nemoto, K., Ohashi , M., Kajitani , T. and Yamaguchi , Y.
(1998)Jpn. J. Appl. Phys. Part 137, 3319-3326.
4
Yashima , M. (2002 ) J. Am. Ceram. Soc. 85, 2925-2930.
5Izumi, F. and Dilanian , R. A. (2002) Recent Research Developments in Physics 3,699-726.

P0191STRUCTURAL CHANGE OF THE Li-DOPED LANTHANUM TITANATEPEROVSKITE La2t3-xLhxTi03
Wataru.Nakamura ," Masatomo Yashima ," Daiju lshimura ," Syuuhei Kobayashi ! Kenjiro
Oh-uchi ," Mitsuru ltoh , b Kenji Ohoyamac•Department of Materials Science and Engineering , Interdisciplinary Graduate School of
Science and Engineering , Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku ,Yokohama , 226-8502 , Japan ; bMaterials and Structures Laboratory, Tokyo Institute ofTechnology, 4259 Nagatsuta-cho , Midori-ku , Yokohama , 226-8503 , Japan; clnstitute forMaterials Research , Tohoku University, Katahira 2-1-1 , Aoba-ku , Sendai , 980-8577 ,Japan(yashima@materia. titech .ac.jp ).

Li-doped lanthanum titanate perovskites La2t3-xLbxTi03 have high Li ion
conductivity (10-3Scm·' at room temperature) and A-site deficient layered perovskite-type
structure with the ordered distribution of La ions on the A-sites along the c-a xis. But thedetailed crystal structure and the phase transition of La v3-xLbxTi03 have not been reported
yet. In this work, we have chosen the composition Laos2Lio.J2Ti0 294, because it has highest
Li-ion conductivity in La2/3-xli3xTi03 (O:>x:>0.15) . The tilt of the TiOs octahedron in layered
perovskite is the key to understand the crystal structure [1] . However, the tilt angle has notbeen known in Lao.s2Lio.32 Ti02.s•.The purpose of this study is to investigate the crystal
structure and phase transition in Laos2Lio32 Ti02.s•.
Lao.s2Lio.32Ti02.s• compound was studied by high-temperature neutron diffraction
technique . Neutron-diffraction data were collected in the temperature range from room
temperature to 1268K, using the multi-detector system HERMES and an electric furnace
to heat the sample . Crystal structure of Lao52Lio32Ti029• was refined by Rietveld analysis
of diffraction data. To confirm the position of Li ions, the nuclear density distribution wasstudied by the maximum-entropy method .
In the literature the Lao.s2Lio.32Ti0 2.s• has been assumed to belong to the spacegroup P4/mmm at room temperature. However, the P4/mmm could not explain theobserved 113, 133, 115, 315 , 533 , 117, and 355 reflection peaks where the hkl was
indexed based on the basic perovskite lattice. On the other hand , the space group Cmmm
yielded these reflection peaks . The lattice parameter increased continuously with thetemperature . The low-temperature orthorhombic phase has tilt of TiOs octahedron along b
axis . The tilt angle decreased with temperature and became 0 at 1098±59K. We foundthat the tetragonal-to-orthorhombic (P4/mmm-Cmmm) transition is induced by the tilt of
the TiOs octahedron . Similar P4/mmm-Cmmm phase transition was reported for
Lao64(TioszNbooa)03 [1] and LaosSro, Ti03[2] .
References
1
Yashima , M. , Mori , M. , Kamiyama , T., Oikawa , K., Hoshikawa , A., Saitoh , K. andTsuda , K . (2003) Chem. Phys. Lett. 375 , 240-246.
2
Howard , C. J. and Zhang , Z., (2003) J. Phys. Cond. Matt. 15, 4543-4553 .

P0192
AN ORGANICALLY TEMPLATED NICKEL GALLOPHOSPHATE WITH A
UNIQUE LAYER STRUCTURE
Chia-Her Lin. Yu-Lun Lai , and Sue-Lein Wang*
Department of Chemistry, National Tsing Hua University, Hsinchu 300, Taiwan(beaman113@ms4.hinet.net)

A new layered nickel gallophosphate (H 3 dien)[(Ni 05 Ga 35 (0H)) 4 Ga 2 P0 4 ) 3 (HP0 4 ) 4]
(dien) · 2Hp (1 ; dien= diethylenetriamine), has been synthesized under mild hydrothermal
conditions and characterized by single-crystal X-ray diffraction , thermogravimetric analysis ,electron paramagnetic resonance , electron probe microanalysis , and magnetic susceptibility
data. The layers in 1 are constructed from metal-oxygen clusters which involve four edgesharing M06 octahedra and two Ga0 5 trigonal bipyramids. The hexameric [Gap 28 ] unit has
not been observed in the gallophosphate. An isostructural gallophosphate containing nonickel , (H 3 dien)[(Ga 6(0H) 4 (P0 4 M HP0.)4 ] ·(dien)·2Hp (2), has also been prepared. Further
syntheses by exchanging other amine has resulted in another gallophosphate analogue ,(H 5tepa)[Ga 6 (0H) 4 (P0 4 ) 5 (HP0 4 ) 2]·2Hp (3 ; tepa , tetraethylenepentamine). Crystal data: 1,
monoclinic, C2/c, a = 20.8363(12) A, b = 11.9546(7) A, c = 16.4577(9) A, {3 = 117.285(1 )0 ,V = 3643.3(1) A3 , Z = 4, R = 0.0424 ; 2, monoclinic, C2/c, a = 20 .842(3) A, b = 11.968(2) A,
c = 16.512(3) A, {3 = 117.052(3)0 , V = 3667.8(1 0) A3 , Z = 4, R = 0.0419 ; 3, orthorhombic,
Pna2 ,, a = 16.4295(9) A, b = 11.9120(7) A, c = 18.7521 (11) A, v = 3667 .8(1 0) A3 , Z = 4, R
= 0.0377.

3

P0193
GRASS FORMIG AT THE LIMIT: HOW GLASS FORMS WHEN THERE IS
INSUFFICIENT NETWORK FORMER TO GO AROUND
Shinji Kohara ,• Kentaro Suzuya ,b Ken Takeuchi ." Chun-Keung Loong ,d Marcos
Grimisditch ,d J.K. Richard Weber,• Jean A. Tangeman ,• and Thoma s S. Key•
•Japan Synchrotron Radiation Research Institute, Mikazuki , Sayo , Hyogo 679-5198 ,Japan ; bJapan Atomic Energy Research Institute, Tokai , Naka, lbaraki 319-1195 , Japan ;cTokyo University of Science, Oshamanbe , Yamakoshi , Hokkaido 049-3514 , Japan ;dArgonne National Laboratory, Argonne , IL 60439-4814 , USA; •Containerless ResearchInc., 906 University Place, Evanston , IL 60201-3149 , USA (kohara@spring8 .or.jp).

Inorganic glasses normally exhibit a network of interconnected covalent-bonded
structural elements that has no long-range order. In silicate glasses the network formers
are based on Si0 4 -tetrahedra of which the interconnectivity is realized by sharing theoxygen atoms at the corners . Conventional wisdom then implies that alkaline and alkalineearth orthosilicate materials cannot be vitrified because they do not contain sufficient
network forming Si0 2 to establish the needed interconnectivity. The structure of a bulk
magnesium orthosilicate (Mg 2 Si0 4 } glass synthesised using containerless melting-andcooling technique was determined by a combination of high-energy X-ray and neutron
diffraction and reverse Monte Carlo computer simulation. We find that the role of network
former is largely taken on by corner- and edge-sharing ionic magnesium species that
adopt 4-, 5- and 6-coordination with oxygen [1].
References
1
Kohara , S., Suzuya , K. , Takeuchi , K. , Loong , C.-K ., Grimisditch , M., Weber, J. K.
R. , Tangeman , J. A ., and Key, T. S., (2003) Science 303 , 1649.

P0194
NEW RESULTS BY USING TEM TO STUDY OF THE MAGNETIC
MATERIALS NbFeB
V. Vong ,a D. M. Thuyb and N. V. Vuongc•Laboratory of Electron Microscopy, Vietnam Academy of Science , 18Hoangquocviet Str.
Caugiay Hanoi ; bQepartment of Physics, Quinhon University 170 Anduongvuong-Quinhon
city Vietnam ; clnstitute of Materials Science , Vietnam Academy of Science
18Hoangquocviet Str. Caugiay Hanoi. (vvemlab@ncst.ac.vn}

The NdFeB melt-spun powders were prepared by using ZGK-1 rapid quenchingfrequency furnace with differential revolution rates of the roller. Microstructure,
crystallization , the grain 's size of the finished products have been investigated by X-ray
diffraction and transmission electron microscope.AII alloying elements were found to be
distributed homogenneously as an amorphous solid solution in the as-quenched state.
We know that the magnetic property of permanent magnets depends strongly not
only on the microstructure but also on the grain size and the coupling between the grains.
The grain size of the material is from few tens of nanometers to the size of single domain(about 100 nm).
Our results shown that the preparation conditions as well as the quenching rate ,mass and conductivity of the roller, gas pressure the heat transfer between the roller, thewater cooling system ,etc ... influence directly on the quality of melt-spun powders .Our
experiments show also the revolution rate of roller is the most effective parameter toquenching rate.
In the work we present the new results ,which we recently received by studying the
NdFeB alloys. The materials are quenched rapidly with various velocities of roller. The
influences of the quenching rate on crystallization process were considered by using BHgraph , X-ray diffration (XRD) and high resolution transmission electron microscopy(HTEM).
For the preparation samples we used the rapid quenching furnace ZGK-1 .The
diameter of the rapid-quenching roller is 300 mm . The loop of the rapid-quenching roller ismade of a copper chrominium alloy. The velocities of roller were changed from 1000
round/min (15 ,70m/s) to 2900 round/min (45.53 m/s). The magnetic characterisingparameters were determined by BH-graph model NIM 200C. The measurement samples
were prepared by using the careful! milled melt-spun NdFeB powder put into a copper
cylinder tube of 8mm diameter, 1Omm height. The grain formation inside the quenched
powder was investigated by using the X-ray diffraction equipment of Siemen-5000 and thehigh resolution transmission microscope JEM-4000 EX.
References
1
Vuong N.V, Khanh N.V. Thuy D.M , Physica B, V.317 (2002) pp. 349-351.
2
Robert C. O 'Handley, "Modern magnetic material. Principles and application " (1999)
Wiley-lnterscience.

P0195
ROLE OF THE DOPED ELEMENTS IN MATERIALS FOR GAS SENSORS
V. Vong • and L. T. HungD•Laboratory of Electron Microscopy, Vietnam Academy of Science , 18Hoangquocviet Str.
Caugiay Hanoi Vietnam (vvemlab@ncst.ac.vn)
bOepartment of Physics , Vinh University , Nghean Vietnam

Gas sensors based on semiconductive oxides ,represented by tin oxide ,are very
important devices for detecting the leakage of toxic or inflammable gases .The addition ofsmall amounts of not only the noble elements as well as platinum ,paladidum ,silver ... but
also normal elements such as antimony,aluminium ,freon ... is known to enhance a qualityof the sensor.That means to enhance sensitivity,recovery and selectivity of the gas
sensors .
A few scientists presented the hyppothesis for interpreting the role of additiveelements in order to enhance sensor's quality. However ,a full explanation of thisphenomenon is to now still lacking.
In the work we present the results ,which indicated that a small amount of the dopetd
elements (noble materials or normal materials) will be created in tin oxide material not
only the clusters but also the untrafine grains ( untrafine islands). The size of the grains isabout a few nanometer or less.
The results demonstrated that a creation both the clusters and the ultrafine grains byaddition of small amounts of metals is main cause of the enhancement sensitivity,
selectivity of the gas sensor based on tin oxide.
References
1 V. Vong , Ng. T. Huang, Proc. XVIII Inter. Union of Crystallography Congress , Glasgow(1999) P06 .11 .016.
2 V. Vong , Proceedings of the 8'h Asia -Pacific Physics Conference , Taiwan (2000) pp.
670-673 .

P0196

CRYSTAL STRUCTURE X-RAY ANALYSIS OF TWO SPIRO-BIFLUORENECOMPOUNDS WITH REMARKABLE INTENSE SOLID-STATE RED
FLUORESCENCE
Ch in-Ti Chen, Chih-Long Chiang , Wei-Ching Wu , Yu h-Sheng Wen ,Institute of Chem istry, Academia Sinica , Taipei , Taiwan 11529 (cchen@chem.sinica .edu.tw)

Red fluorophores emitting strong fluorescence in sol ution are common , but it is rarethat strong red fluorescence sti ll remains in solid state. We want to report twocompounds,
spiro-bifluorene
substituted
donor-acceptor
and(pTSPDCV)
fluorene2-di( 4-tolyl)amino-7 -d icyanovinyl-9. 9'-(2 ,2'-biphenyl)
2-diphenylamino-7 -dicyanovinyl-9 .9'-(2 ,2 '-biphenyl) fluorene (PhSPDCV),

Q
N

~

p~
pTSPDCV

Q

r ""'

CN
NC

PhSPDCV

They show remarkable strong red fluorescence in solid state. We attribute theunusual solid-state fluorescence to the unique crysta l packing structure as well as thenon-planar rigid chemica l structure of two spiro-bifluorene th at prevents the close contact ofthe molecules in solid state . The single crysta l structures and crystal packing wi ll be
described and discussed in detail.

Crystal packing of pTSPDCV

Crysta l packing of pTSPDCVP0197CORRELATION BETWEEN CRYSTAL STRUCTURE AND
FERROELECTRIC PHASETRANSITION TEMPERATURE FOR KTP
MATERIALS
Stefan T . Norberg•, Joacim Gustafssonb, Nobuo lshizawa••Ceramics Research Laboratory, Nagoya Institute of Technology, Asahigaoka , Tajimi
507-0071 , Japan ; bMaterials and Surface Chemistry, Chalmers University of Technology,
SE-412 96 Gothenburg , Sweden . (stn@crl.nitech .ac.jp)

Potassium titanyl phosphate (KTiOP0 4 , KTP) (1] is a well known material for
nonlinear optical applications. The favourable properties of thermal stability, chemical
resistivity, high optical nonlinearity and high optical damage threshold , as well as a wide
optical transmission window extend too many isostructural materials. Most common are
ATiOB0 4 compounds with A = K, Rb , Cs or Tl , and B = P or As. However, not all of thepossible ATi0804 materials give a high nonlinear optical response ; some are evenparaelectric at room temperature. This diversity in properties of the KTP isostructuralcompounds is useful as it allows us to make structure-property related studies.
Accurate structural models of materials isostructural to KTP have been gained from10 K and room temperature measurements. Careful investigation of this data has led us tosuggest an improved model for the direct correlation between certain structural fragments
and the ferroelectric to paraelectric phase transition temperature (T c). The most significant
part is that the displacement of the alkali cations along the crystallographic c-axis could be
related to the Abrahams-Jamieson-Kurtz T c criteria for oxygen framework ferroelectrics . Itshould also be possible to make accurate estimations of the Tc for similar KTP
isostructural materials using structural models based on room temperature data.
X-ray intensities for sodium-doped KTP (Na 0 114 K0886 )K(TiOMP0 4 ) 2 were collected at
10.5 K using the Huber diffractometer at UWA. X-ray intensities were collected for two
germanium-doped rubidium titanyl phosphates (RTP) , Rb 2(Ti)(Ge 0 121 Ti 0879 )0 2(P0 4 ) 2 andRb 2 (Ge 0 125Ti 0875 )(Ge 0225 Ti 0 .775 )0 2 (P0 4 ) 2 at room temperature. Additionally, dielectricmeasurements were carried out over a wide temperature range for both RTP andgermanium-doped RTP.
References
1
Tordjman , 1. , Masse , R. & Guitel , J. C. (1974). Z. Kristallogr.139 , 103-115.
2
Norberg , S. T ., Sobolev, A. N. , Streltsov, V. A . (2003). Acta Cryst. B59 , 353-360 .
3
Norberg , S. T ., Gustafsson , J. , Mellander, B.-E. (2003). Acta Cryst. B59 , 588-595 .

P0198SYNTHESIS, STRUCTURE, AND PHASE RELATIONSHIP IN LITHIUM
MANGANESE OXIDE SPINEL
Masao Yonemura ," Atsuo Yamada, b Stefanus Harjo," Takashi Kamiyama ," and Ryoji
KannobaNeutron Science Laboratory, Institute of Materials Structure Science, High Energy
Accelerator Research Organization , Tsukuba , Japan ;bDepartment of Electronic Chemistry, Interdisciplinary Graduate School of Science andEngineering , Tokyo Institute of Technology, Yokohama , Japan (yone@post.kek.jp ).
Lithium manganese oxide spinels are promising candidates as cathodes inrechargeable lithium batteries. The spinels are usually discussed in the ternary phase
diagram, LiMn02 - Li2Mn03 - Mn02. The composition variety resulted from the synthesis
at various temperature and Li/Mn ratio could be interpreted in the triangle region of
LiMn20 • - Li. Mns0 12 - Li2Mn.Os[1-4] . Change in the Li/Mn ratio in the starting materials
leads to the composition varieties in the spinel from LiMn20 • to Li. Mns0 ,2 , and thedecrease in synthesis temperature gives compositions from LiMn20 • to Li2Mn.Os. The
structure is complicated due to the existence of Jahn-Teller trivalent manganese ions.
Furthermore , oxygen vacancies have also been reported[5-7] . Therefore , the structures
and the relation to the LiMn20 • - Li. Mn 50 ,2 - Li2Mn. Os phase diagram are still
ambiguous .
In this study, phase relationships , structures , and the phase transitions in thelithium manganese oxide spinels were studied using samples synthesized at various
conditions. Their structures were discussed based on the structure date determined by
TOF neutron and synchrotron X-ray Rietveld analysis. The oxygen vacancy wasconfirmed , and its amount varied with the synthesis condition . The relationship between
the composition , structure, and phase transition will be discussed .

References

1
2
3
4
5
6
7

M.M. Thackeray, W.I.F. David , P.G. Bruce , and J.B. Goodenough , (1983) Mater. Res.
Bull. , 18, 461
M.H. Rossouw, A. de Kock, L.A. Picciotto, M.M. Thackeray, W.I.F. David , and R.M.
lbberson , (1990) Mater. Res. Bull., 25 , 173.
C. Masquelier, M. Tabuchi , K. Ado , R. Kanno , Y. Kobayashi , Y. Maki, 0. Nakamura ,and J.B. Goodenough , (1996) J. Solid State Chern. , 123, 255.
A.I. Palos , M. Anne , and P. Strobel , (2001) J. Solid State Chern. , 160, 108.
A. Yamada , K. Miura , K. Hinokuma, and M. Tanaka , (1995) J. Electorchem. Soc.,
160, 108.
J. Sugiyama , T. Atsumi , T. Hioki , S. Noda, and N. Kamegashira , (1997) J. Power
Sources, 68 , 641 .
J. Sugiyama, T. Atsumi , A. Koiwai, T. Sasaki , T. Hioki, S. Noda , and N. Kamegashira ,(1997) J. Phys. Condens. Matter. , 9, 1729.

P0199CRYSTAL STRUCTURE ANALYSIS OF Ti-Cr-Mo HYDROGEN
ABSORBING ALLOYS
K.lwase•·, Y.Nakamurab, E.Akibaband T.Kamiyamac•Department of Material Structure Science, The Graduate University for Advanced
Studies , 1-1 , Oho , Tsukuba , lbaraki 305-0801 Japan (kiwase@post.kek.jp), DNational
Institute of Advanced Industrial Science and Technology, AIST Central-5 , 1-1-1 , Higashi ,Tsukuba , lbaraki 305-8565 Japan, cHigh Energy Accelerator Research Organization(KEK) , 1-1 , Oho , Tsukuba , lbaraki 305-0801 Japan

V-free Ti-Cr hydrogen storage alloys are promising for various applications .
Ti 40 Cr57 .5 Mo 25 bee solid solution alloys have hydrogen storage capacity of 3.6 mass % (1 .8
H/M ratio) 111. This is almost double to that of conventional intermetallic compounds . There
have been several reports concerning crystal structures of Ti-Cr-V 121 and Ti-V-Mn 13.41 bee
solid solutions , but few reports can be found for Ti-Cr-Mo151 alloys. In this study,
absorption-desorption properties of Ti-Cr-Mo bee hydrogen absorbing alloys and crystal
structures of the alloys and hydrides were investigated.
The lattice parameters and hydrogen absorption-desorption properties of Ti 45 Cr 55 .
xMox alloys changed with increasing Mo contents. The crystal structures were investigatedby X-ray and neutron diffraction combined with the Rietveld method , for the alloys beforehydrogenation and those in the full -hydride state. Results from X-ray diffraction indicatethat the alloys in full-hydride state have an fcc structure, and neutron ones indicate that it
is CaF 2 type structure .

References
1
A. Kamegawa , T. Tamura , H. Takamura and M. Okada , J. Alloys Comp.
356-357(2003)
447-451
2
E. Akiba and H. lba , lntermetallics 6 (1998) 461-470
3
Y. Nakamura and E. Akiba , J. Alloys Camp. 316(2001) 284-289
4Y. Nakamura and E. Akiba , J. Alloys Camp. 311(2000) 317-321
5
K.Kubo , H .ltoh , T.Takahashi , T.Ebisawa , T.Kabutomori , Y.Nakamura and E.Akiba , J.
Alloys Camp. 356-357(2003) 452-455

P0200CARBON MICRO-RODS IN LOW-TEMPERATURE HYDROGENATEDAMORPHOUS CARBON
Prabal Dasgupta•*, D.P. Bhattacharyya•, Nikhilesh Chowdhurib, Arup Banerjeec
aoepartment of Theoretical Physics
bDepartment of C.S .S.
coepartment of Spectroscopy
Indian Association for the Cultivation of Science , Jadavpur, Kolkata 700 032(prabaldasgupta@hotmail.com)

This work reports presence of carbon micro-rods measuring 30-40 microns insucrose char produced by the action of cone. sulphuric acid. Electron-diffraction and FTIR
studies reveal that at least two phases of amorphous carbon are present in sucrose charand one of them is hydrogenated amorphous carbon. The doo2 (2.306N & 2.20N) of bulk
and micro-rod differs considerably and hybridisation ratio was found to be sp 3 : sp 2 = 1:3
from the deconvolution of bands in the region of 2800 - 3000 em·' . Band gap (1 .04 eV)
and plot of energy vs absorption coefficient, strongly corroborated presence ofhydrogenated amorphous carbon.

P0201EVOLUTION OF GROWTH MODE, MICROSTRUCTURE, AND
PHOTOLUMINESCENCE IN Mg- DOPED GaN EPILAYERS ON Ab03
(0001)
Hsueh-Hsing Hung ," Chin-Pin Chuang ," and Ling-Yun Jang••National Synchrotron Radiation Research Center, Hsinchu Science Park , 30077 , Taiwan(hhh@nsrrc.org.tw)
Epitaxial GaN :Mg films grown by using MOVPE were studied . Magnesium canreduce the stacking fault energy difference between wurtzite and zinc-blende structures so
as to make coexistence of two phases. With much increasing flow rate of Cp 2 Mg, the roleof Mg ions changes from the p-typed dopant to nucleation center so as to generate
prismatic step fronts and thus inverse domain boundaries.
Th ese Mg-rich defect phases of 8.4° tilted to (10-11) orientation are coherent to thesubstitutional-interstitial model of Mg-complexes and well correlate to the prevailing ofyellow band in the photoluminescence spectrum.
In addition , according to OAFS results , apparent tensile strain and interstitial Mg
have been observed only in these orientation-tilted structures.

1.0-··-· - Total Fluorescence Yield- - OAFS of (2 0 -2 2)-tilted

~ 0.8

"iii

c

U)

~ 0.6
U)

> 0.4

~

Qj

a:: 0.2
00

I

10200

10400

10600

10800

11000

11200

11400

11600

9

10

hv [eV]- 1.0..-...
~'";::; 0 .8"'.......
-"'
f-

lL
"0
U)

0.6
0.4

.!::!
ro

E
0

0 .2

z 00
0

2

3

4

5 0

R [A]

6

7

8

P0202
STRUCTUAL ANALYSIS OF SLIDE-RING GEL BY SMALL ANGLE X-RAY
SCATTERING AND CONTROL OF THE PULLEY EFFECT
Kentaro Kayashima ,• Yuya Shinohara ,a Eiji Takeuchi ,a Yoshiyuki Amemiya a.b, Yasushi
Okumura a.b, and Kohzo Ito a,b•Graduate School of Frontier Sciences University of Tokyo , 5-1-5 Kashiwanoha , Kashiwa ,Chiba 277-8561 , Japan ; bCREST, JST

Slide-ring gel (topological gel)[1] is a new type of gel which is synthesized by crosslinking a-cyclodextrins contained in the sparse polyrotaxanes in solution . It consists ofpolymer chains with bulky end groups which are topologically interlocked by figure-of-eightcross-links of a-cyclodextrins. In the slide-ring gel , it is assumed that the polymer chainsfreely pass through the cross-links acting like pulleys , which would results in equalizing thenanoscopic heterogeneity in structure and stress. We call this "pulley effect".
In this study, we have measured small-angle X-ray scattering (SAXS) of slide-ringgel to investigate and confirm the "pulley effect". It is known that usual chemical gels which
are cross-linked by covalent bond shows so-called "abnormal butterfly pattern", in which
X-ray intensities are enhanced in a stretched direction , when they are stretched uniaxially.
This indicates that the heterogeneities of uniaxially stretched chemical gels become
increased along the stretched direction.
We have measured SAXS of uniaxially stretched slide-ring gels in good (NaOH
aqueous) and poor (NaCI aqueous) solvents . The experiments were carried out at
BL-15A, KEK-PF , in Tsukuba , Japan. SAXS from slide-ring gels in poor solvents showed
the abnormal butterfly pattern , but SAXS from slide-ring gels in good solvents showed anormal butterfly pattern in which X-ray intensities are enhanced perpendicular to thestretched direction . This indicates that the behavior of the cross-links of the slide-ring gelin good solutions are quite different from that of usual chemical gels and that theaggregation in poor solvent suppresses the sliding of cross-links considerably, whichenables us to control the pulley effect freely by varying the solvent.
References
1
Y. Okumura , K. Ito, (2001) Adv. Mater. , 13, 485.

P0203METAL-BASED MOLECULAR FUNCTIONAL MATERIALS OF
FLUORENES
Wai-Yeung Wong
Department of Chemistry and Centre for Advanced Luminescence Materials, Hong Kong
Baptist University, Waterloo Road , Kowloon Tong , Hong Kong , P.R. China(rwywong@hkbu.edu.hk)

The design of metal acetylide complexes and polymers with unusual optoelectronic
and photovoltaic properties has aroused growing research interests. An identified problem
in OLEOs is the ratio of 3:1 for the generation of non-emissive triplet to emissive singlet
excitons on the basis of spin statistics . In view of this , conjugated polymers containing
transition metal atoms such as platinum have been widely studied as model systems to
explain aspects of the photophysics of excited states in such polymers and obtain a clear
picture of the spatial extent of the singlet and triplet manifolds. The strong spin-orbit
coupling associated with these heavy metals renders the spin-forbidden triplet emission(phosphorescence) partially allowed . Very recently , a comprehensive program waslaunched in our laboratory on the investigations and development of some novel
organometallic polyyne polymers incorporating fluorene-based auxiliaries. One of themerits here is that the 9-fluorenyl positions can be functionalized easily so that thesolubility, the emission and electronic properties as well as the bandgaps of the resulting
materials can be chemically tuned . In this talk , we present our work on the synthesis ,characterization , structural and photoluminescent properties of a series of transition metal
polyyne polymers containing 9-functionalized fluorene spacer units.
References
1
Wong , W .-Y., Liu , L. and Shi , J.-X. (2003) Angew. Chem. Int. Ed. 42 , 4064- 4068 .
2
Wong , W .-Y. , Lu , G.-L. , Choi , K.-H. and Shi , J.-X. (2002) Macromolecules 35 ,

3506- 3513 .

P0204
CRYSTAL STRUCTURES OF MOLECULAR COMPLEXES BETWEENSURFACTANTS AND HYDROQUINONE
Akiko Sekine ,a Yuko Fujimura ,a Hidehiro Uekusa ,a Yuji Ohashi ,a and Nahoko limurab•Department of Chemistry and Materials Science , Tokyo Institute of Technology,
Ookayama , Meguro-ku Tokyo 152-8551 , Japan (asekine@chem .titech .ac.jp).
bDepartment of Pharmaceutics, Niigata University of Pharmacy and Applied Life Sciences ,Kamishin 'ei-cho , Niigata , 950-2081 , Japan
It has been reported that several cationic surfactants and aromatic compounds
make crystalline complexes. Their structures analysed by X-rays revealed the commonpacking pattern of the component molecules in the crystals . In this paper, we made morestable complexes of surfactants and hydroquinone , which have high whitening
effectiveness and investigated interaction between the surfactant and hydroquinone
molecules .

¢OH

Scheme Chemical formula of surfactants and hydroquinone
Several surfactants , that is , hexadecyltrimethylammonium bromide (CTAB),
bromidetetradecyltrimethylammonium bromide (MTAB) , dodecyltrimethyl-ammonium
hexadecyl
and(DTAB),
bromidedecyltrimethylammonium(L TAB) ,dimethylbenzylammonium chloride (BCDAC) were selected . The crystallization was
performed from aqueous and methanol solutions under the nitrogen atmosphere . The Xray data were collected using RAPID (Rigaku) diffractometer at low temperatures. The
structures were analyzed with SHELXS97 and were refined with SHELXL97 . For eachsurfactant, two crystal forms were obtained with or without solvent water molecules . The
crystals obtained from an aqueous solution include one water molecule in an asymmetricunit. Their crystals show the common packing pattern . On the other hand , the crystals
obtained from a methanol solution include no solvent molecule but has a half ofhydroquinone molecule in an asymmetric unit. These crystals showed the new packing
pattern , that is, one hydroquinone is included in the common packing pattern like thecomplex from an aqueous solution and another hydroquinone occupies the inversion
center between the common packing patterns . These new complex crystals from amethanol solution show more thermally stable than those with water solvent and thestability depends on the alkyl chain length of the surfactant molecules.

P0205LITHIUM DIFFUSION IN LITHIUM MANGANESE SPINEL
Kenji Tateishi ,• Douglas du Boulay,b and Nobuo lshizawab•Interdisciplinary School of Science and Engineering , Tokyo Institute of Technology,
Nagatsuta Midori , Yokohama 226-S502 , Japan ; bCeramics Research Laboratory, Nagoya
Institute of Technology, Asahigaoka , Tajimi 507-0071 , Japan(tateishi@r3401 .msl.titech.ac.jp)

Lithium manganese spinels are attractive candidates for cathode materials of
rechargeable lithium ion batteries. The high-temperature form of stoichiometric LiMnp 4 is
known to be a mixed valence compound in which distinct Mn 3• (t2/ e9 1 ) and Mn•• (t293e 9°)ions are randomly distributed among the 16d sites of Fd-3m symmetry. The electricaltransport properties are dominated by a hopping process of nonadiabatic small polarons
involving e9 electrons, so the Mn valences change with respect to time . Previous molecular
dynamics (MD) simulations reported the correlation of Mn valence changes and Li
migration [1 ,2) .
In this study MD simulations were carried out to obtain a more detailed
understanding of Li diffusion mechanisms . The figure shows a view of coordinating 0 and
Mn atoms around the Sa (Li) tetrahedral and the 16c (vacancy) octahedral sites . The Sasite is coordinated by 12 Mn atoms at 3.42 A and the 16c site is coordinated by 6 coplanar
Mn atoms at 2 .91 A. From the viewpoint of the Li-Mn Coulomb repulsive energy, it ispredicted that the 16c site is more strongly affected by the change of Mn valences.
Indeed , prior to Li migration the mean Mn valence around the 16c site was +3.5, whereas
in instances in which Li occupied the 16c octahedra , the mean Mn valence was reduced to+3.3. These numbers suggest that a typical change in Mn coordination around the 16c site
occurs from (3 Mn 3• + 3 Mn 4 • ) to (4 Mn 3 • + 2 Mn 4 • ). For the Sa tetrahedral sites , the mean
Mn valences of 12 Mn atoms scarcely changed from +3.5 (i.e ., 6 Mn 3• + 6 Mn 4 • ) before
and after the Li diffusion into the adjacent 16c site . From these results , we concluded that
Li migration to the 16c site and the addition of an extra electron on the 6 coplanar Mn
atoms are strongly coupled.
References
1
K. Tateishi , D. du Boulay, and N. lshizawa , J. Solid State Chem.174, (2003),
175-1S1.
2
K. Tateishi , D. du Boulay, and N. lshizawa , Applied Physics Letters 84[4], (2004),
529-531.

P0206NUMERICAL CONVERSION BETWEEN THE PEARSON VII AND THE
VOIGT FUNCTIONS
H. Wang," J. Zhoub•x-ray Laboratory , School of Earth and Space Sciences, Peking University, Beijing 100871 ,P. R. China; bChinese Academy of Geological Sciences , Beijing 100037, P. R. China(hjwang@pku.edu.cn).
The Pearson VII (P-VII) and the Voigt (V) functions are two important peak shapefunctions and have been widely used in X-ray powder diffractometry. It is sometimes
needed to convert a V curve into a P-VII curve or vice verse. However algebraically it isunsolvable. Starting from the geometric characteristics of two equal curves this study
derives a numerical model for converting a V curve into a P-VII curve or vice verse.
According to an XRD peak consisting of position , shape (Sc) , height (/max) . full widthat half maximum (B) and asymmetry five elements[1] and the expressions of the P-VII[2]and the V[3] functions , two full equal curves must possess the same Sc, B, lm ax. integral
width (fJJ and the same area (//) . This produces five equations of Sc, B, lmax. f3 and II for
both P-VII and V functions and leads a final equation 1 that allows us to exactly convert
the characteristic u of the P-VII function into the k of the V function with the conditions k= fJ
J f3 9 rr112 and Re{w[,I;Bv I 2f39 + ik]} = 0.5 exp(k 2)erfc(k) and vice verse . Subscript c
renders the Cauchy function and g the Gaussian function.
B lfJ = 2(2""- 1)"2 [r(u)f /ex (k 2)erfc(k)v
g
2 2(1- u ) m (2u - 1)p

5 ,...--- - - - -4.5
4
3.5
"'

- --,

A

3

2.5

2

1.5
1L---=====~_._

0

2

k

3

_

_J

4

(1)

Figure A shows the relationsh ip
between the shape characteristic
value k of the V function and theexponent u of the P-VII function .
Relationship between Sc and u andthat between f39 /f3 and u are derived
therefore. It shows from the numericalsolutions that these peak parametersof the P-VII curve can exactly coincidewith those of the V curve , and thus ,the Voigt function can be welldescribed by the Pearson-VII function
with this model , and vice versa.

References

1
2
3

Wang , H. and Zhou , J. (2000) J. Appl. Cryst. 33 , 1128-1135.
Smith , O.K. (1989) Reviews in Mineralogy Vol. 20 , 183-216.
Langford , J.l. (1978) J. Appl. Cryst. 11 , 10-14.

P0207
ON EQUIVALENCE OF COLORINGS OF PATTERNS ASSOCIATED WITH
DECOMPOSITIONS OF THEIR SYMMETRY GROUPS
Rene P. Felix• and Maria Veronica P. Quilinguinb•Department of Mathematics, University of the Philippines Diliman , Quezon City,
Philippines (rene@math01.cs.upd.edu .ph)bDepartment of Mathematics, University of Asia and the Pacific Pearl Drive, Ortigas Center
Pasig City 1605, Philippines (vquilinguin@uap .edu .ph)In this paper, we explore the theory of colorings by considering when two coloringsof a given pattern are equivalent in the sense that one may be obtained from the other (1)by a change or permutation of the colors and/or (2) by a symmetry of the underlying
uncolored pattern . In connection with this, we derive a formula for counting the coloringsof a pattern which are equivalent to each other. We also show how to list all colorings
equivalent to a given coloring and among these, those which have the same set ofsymmetries permuting the colors and the same set of symmetries fixing the colors.
The symmetry group of a pattern refers to the set of isometries that send thepattern to itself. For this paper, we assume that we are given a pattern on the Euclidean
plane whose symmetry group G is a plane crystallographic group or a subgroup of a plane
crystallographic group , i.e., G is a plane crystallographic group , a frieze group or a finitegroup which is cyclic or dihedral. The results in this paper may be extended to
crystallographic groups of higher dimensions.

P0208
THE AUSTRALIAN REPLACEMENT RESEARCH REACTOR
R. A. Robinson and S. J. Kennedy
Bragg Institute, Australian Nuclear Science and Technology Organisation , Menai , NSW
2234 , Australia (rro@ansto.gov.au)
The 20-MW Australian Replacement Research Reactor represents possibly thegreatest single research infrastructure investment in Australia 's history. Construction of
the facility has commenced , following award of the construction contract in July 2000 , andthe construction licence in April 2002 . First fuel will go into the reactor in November 2005,
with the facility at full power in early 2006 and fully commissioned in July 2006. The
project includes a large state-of-the-art liquid deuterium cold-neutron source andsupermirror guides feeding a large modern guide hall , in which most of the instruments
are placed . Alongside the guide hall , there is good provision of laboratory, office andspace for support activities. While the facility has "space" for up to 18 instruments , theproject has funding for an initial set of 8 instruments , which will be ready when the reactor
is fully operational. Instrument performance will be competitive with the best researchreactor fa cilities anywhere. Staff to lead the design effort and man these instruments
have been hired on the international market from leading overseas facilities , and fromwithin Australia , and 7 out of 8 instruments have been specified and casted. At present
the instrumentation project carries >1 0% contingency and 50% of procurements havebeen placed. An extensive dialogue has taken place with the Australian user communityand our international peers, via various means including a series of workshops over thelast 2 years covering all 8 instruments , emerging areas of application like biology and theearth sciences, and computing infrastructure for the instruments.
In December 2002 , ANSTO formed the Bragg Institute, with the intent of nurturingstrong external partnerships, and covering all aspects of neutron and X-ray scattering ,including research using synchrotron radiation .

P0209IMPROVEMENT OF SPATIAL RESOLUTION OF IMAGES TAKEN WITH XRAY CCD DETECTOR BY MAXIMUM LIKELIHOOD METHOD
Y. Shinohara ,a E. L. Kosarev,b Y. Ueji ,a K. Uesugic, Y. Suzukic, N. Yagic, andY . Amemiyaa
aoepartment of Materials Science , The University of Tokyo , Kashiwa , Chiba , Japan ; bp _ L.
Kapitza Institute for Physical Problems , Kosygina , Moscow, Russia ; cJASRI , Mikazuki-cho ,Hyogo, Japan (amemiya@k.u-tokyo.ac.jp).

We have developed polarization-contrast imaging systems (X-ray polarization
imaging microscopy). It is expected as a powerful tool for two-dimensional imaging of bulk
magnetic structure. Previous studies have shown the need for improvement of theresolving power (now the order of microns) of the system . There are two ways to improve
the resolving power of X-ray microscopy. One is with hardware : the refinement of the
optical devices and experimental arrangement. Although there are great improvements ,their abilities are limited by the fabrication technique at the moment . Therefore anotherapproach is needed for the progress of the ability of X-ray microscopy: the improvement ofsoftware.
Usually an output image which we actually measure is expressed as a convolutionof an instrumental function and an input image which we really want to measure .
Knowledge of the instrumental functions allows us to reconstruct the signal to a certain
extent without a priori parameterizations. One-dimensional signal recovery using
Maximum Likelihood Method (MLM) has been already reported[1] but two-dimensional
one has not been yet. Recently, we have developed a two-dimensional signal recovery
program .
Fig .1 shows the result of the two-dimensional MLM program. The left figure is theimage of three pinholes and the right figure is the image recovered by MLM program after
200 iterations. It shows that the images of individual pinholes are resolved clearly.
Although the program recovers images successfully, there are some problems to be
overcome . First, it is difficult to know the precise instrumental function. Another problem isa sampling effect by CCD pixels. Detail of these problems and their solution will bereported .

Fig.1 An example of the recovered image with the signal recovery program
References1
Kosarev, E. L. , (1990) Inverse Problems, 6, 55-76 .

Aagard , A.
Abe , E.
Adachi , S
Ad1gOzel, 0 .
Ahn , H. J.
Aitipamula , S.
Akiba , E.
Akimitsu , J
Alshahateet , S. F.
Amemiya , Y.
Amemiya, Y.
Amemiya , Y
Anitha , K.
Anitha , K.
Araki , N.
Arata , Y.
Aritake , K.
Bai, T.
Baker, E. N.
Baker, E. N.
Baker, H. M.
Banerjee, A.
Bansal , M.
Barford, D.
Bartlam, M.
Basri , M.
Batchelor, A. H.
Batten , S. R.
Bau , R.
Baxla, A. P.
Baxla, A. P.
Begum, N. S.
Begum, N. S.
Benny, J.C .N.
Bernal, I.
Betzel, C.
Bhattacharya , S.
Bhattacharyya , D. p
Shushan , A.
Bilgrami , S
Bilgrami, S
Binder, A.
Bishop, R.
Biswas, S.
Boulay, D.
Boulay, D.
Brink, F.
Bull, M. J.
Bunge, H. J.
Cai , J.
Cai , J.
Cai , J
Cai , J
Cai , J.
Ca i, J.
Carpenter, M. A.
Carson , M.
Cha , J. A.
Chai , Z. G.
Chaichantipyuth , C .
Chaichit, N.
Chaichit, N.
Chainok , K.

MS10-2MS09-2
P0112
P0188
P0151
P0029
P0199
PL1
MS06-3P0202
P0209
MS02-5
P0001
P0002
MS11-3MS05-4P0158
P0141
MS01-5
P0147
P0147
P0200
MS12&13-2
P0174
P0175
P0154
P0141
P0054
P0170
P0173
P0149
P0080
P0073
P0169
P0024
P0149
P0014
P0200
P0142
P0139
P0149
MS15-4MS06-3
P0134
P0183
P0205
MS08-2
P0015
MS02-2MS03-3
P0113
P0114
P0115
P0116
P0033
MSOS-2
MS12&13-3
P0098
P0020
P0023
P0023
P0119
P0064

Chakrabarti , C
Chan , A. S. C.
Chan , E. Y. Y.
Chan , N. L.
Chan , S. H.
Chan , S. L. F.
Chang , C K.
Chang , C H.
Chang , J. L.
Chang , J. R.
Chang , J. R.
Chang , S L.
Chang , S. L.
Chang , W. F.
Chang , W. J.
Chao , T. C.
Chatake , T.
Chatake , T.
Chatterji , D.
Chaudhary, S. K.
Chaudhary , S K.
Chauhan , V. S.
Che, C. M.
Chen , C. J.
Chen , C. S.
Chen , C. T.
Chen , C. Y.
Chen , C. Y.
Chen , H. H.
Chen , H. H.
Chen , H. H.
Chen , H. H.
Chen , H. H.
Chen , H. H.
Chen , J. M.
Chen , J. R.
Chen , K. W.
Chen , L. Q.
Chen , M. H.
Chen , S.
Chen , S. M.
Chen , X.
Chen , X. D.
Chen , X. M.
Chen , X. M.
Chen , Y.
Chen , Z. X.
Cheng , R. H.
Cheng , K. Y.
Cheng , P
Cheng , S. Y.
Cheung , Y. Y.
Chiang , C. L
Chiang , M. Y
Chiang , Y. P.
Chiba-Kamoshida , K.
Chien , K. Y.
Chimsook, P.
Chitnumsub , P.
Chiu , W. C.
Choi , K. H.
Chong , K. T.
Chopra , D.

P0134
P0084
P0059
MS07-3
P0175
P0129
P0104
P0102
MS07-3
P0110
P0106
P0022
P0122
P0061
P0075
P0156
P0172
MS12&13-8
P0137
P0176
P0177
P0085
P0129
P0150
P0077
P0196
P0152
P0135
MS15-5
P0022
P0047
P0048
P0049
P0050
P0121
P0018
P0040
P0155
P0155
P0123
P0037
P0117
P0035
P0118
MS06-1MS07-3
P0056
MS04-3P0090
MS06-2
P0122
P0163
P0196
P0102
P0171
P0172
MS04-4
P0023
P0128
P0135
P0082
P0162
P0005

Chopra , D.
Chor, L. T.
Chou , C. C.
Chowdhuri , N.
Chowdhury, K.
Chu , W . C.
Chuang , C. P.
Chui , S. S. Y .
Chui , S. S. Y.
Chun , Y.
Chyi , J. I.
Colman , P. M.
Connare , S.
Courville, D. A.
Cowan, J. A .
Cowieson , N.
Craig , D. C.
Cramer, W . A.
Das , S.
Dasgupta , P.
Dattagupta , J. K.
David , W. I. F.
Deng , D. S.
Dey, K. R.
Dey, S.
Dey , S.
DineshDing , Y.
Dittrich , B.
Dittrich , B.
Dong , Y.
Dong , Y. H.
Duax , W. L.
Duriska , M. B.
Eom , SH .
Ethayathulla , A. S.
Etc , S.
Fan , H. F.
Fan , H. F.
Fan , H. F.
Fan , H. F.
Fan , H. F.
Ferrara , J. D.
Forouhar, F.
Fujii , T .
Fujii , Y.
Fujimoto , Z .
Fujimura , Y.
Fujishiro , Y.
Fujiwara , H.
Fu kuda , Y .
Fukuda , T .
Fukuyama , K.
Furie, B.
Furie, B.
Gall , J . L.
Gao , S.
Gao , S.
Garbe , U.
Ge , M. H.
Ge , M. H.
Ge, M. H.
Ge, M. H.

P0008
P0154
P0152
P0200
P0014
P0167
P0201
P0100
P0129
P0124
MS02-3
P0136
MS12&13- 1
P0138
MS03-1
MS10-2MS06-3MS04-2
P0137
P0200
P01 34P0015
P0116
P01 82
P0149
P0173
P0012
P0175
MS03-2
P0068
P0175
P0159
MS12&13-1
P0054
P0161
MS07-1MS01-1
MS02-1
P0016
P0017
P0018
P0132
P0138
MS04-4
P0145
MS05-1
MS04-3
P0204
MS14-1MSOB-1
MS11-1
P01 33
P0144
MS07-2MS07-2
P0150
P0179
P0081
MS02-2
P0047
P0049
P0050
MS15-5Gilbert , E. P.
Girija , C. R.
Girija , C. R.
Gj0nnes , J.
Goel , V. K.
Goossens , D. J.
Govindarajan , S.
Govindarajan , S.
Govindarajan , S.
Gowda , K. V. A.
Gregory , A.
Grimisditch , M.
Gu , J.
Gu , J.
Gu , Y. X.
Gu , Y. X.
Gu , Y. X.
Gu , Y. X.
Gupta , A.
Gupta , M.
Gupta , M. N.
Gupta , S.
Gustafsson , J .
Gutmann , M. J.
Habegger, L.
Hagiwara, K.
Hall, S. R.
Hailer, K. J.
Hailer, K. J.
Hailer, K. J.
Hailer, K. J.
Hailer, K. J.
Hanash ima, T .
Hanash ima , T .
Hanashima , T .
Hanashima, T .
Hanashima, T .
Harjo, S.
Harjo, S.
Harjo, S.
Harper, J. W .
Harris, J.
Hart, R.
Hashizume, D.
Hata, Y.
Hatakeyama, T .
Hayashi , R.
Hayashida, M.
He, F.
He, G.
Heerdegen , A. P.
Hewat, A. W .
Higashi, T .
Higemoto, W.
Hikage, T .
Hiraki, M.
Hirano , A.
Hirose, F.
Hodgson, K. O.
Hosh ikawa , A.
Hosh ikawa , A.
Hosoya , T .
Howard , C. J.

P0013
P0080
P0073
MS09-1
P0173
P0015
P0027
P0028
P0058
P0011
MS11-4
P0193
P0032
P0072
P0016
P0017
P0018
MS02-1
P0141
P0085
P0149
P0137
P0197
P0015
MS12&13-1
MS04-3
MS12&13-5
P0064
P0065
P0066
P0067
P01 30
P0003
P0004
P0007
P0006
P0009
MS05-4
P0198
P0185
P0174
P0166
MS14-3
P0103
P0145
MS01-1
P0145
P0145
P0118
P0089
P0015
MS14-2
MS04-3MS05-4
P0157
MS10-4
P0060
MSOB-4
PL5
P0071
MS05-4
P0071
P0019

Howard, C J.
Howard , C. J.
Howard , J. A. K.
Hsia , K. C.
Hsiao , C D.
Hsieh , C. H.
Hsieh , Y. C.
Hsieh , Y. W .
Hsu , C. H.
Hsu, I. J.
Hsu , I. J.
Hsu, I. J.
Hsu, W. H.
Hu , N. T.
Hu , Q.
Hu, X.
Hu, X.
Huang , C.M.
Huang , C. Y.
Huang , H. M.
Huang , J. H.
Huang , M.
Huang , P. J.
Huang , S.
Huang , S.
Huang , W . N.
Huang , X. C.
Huang , Y. X.
Huang , Y. X.
Huang , J. Q.
Huber, T.
Huether, R.
Hume, D. A.
Hung , H. H.
Hung , H. H.
Hung , L I.
Hung , LT.
Hung , W. Y.
Hursthouse , M. B .
Hussain , A.
Huyen , P. T.
Ibrahim, B. S.
lchiro, T.
Igarashi, R.
Igarashi, N.
li mura , N.
Ikeda, S.
lm, Y. J.
lmamoto, N.
Inoue, A.
Inoue, M.
Inoue, T.
Inoue, T.
Inoue, T.
lp, D. T. M.
lp, N. Y
lrikura , D.
lsh igaki , T.
Ish ikawa, T.
lshimura , D.
lsh imura , D.
lshimura, D.
lshitobi, S.

MS05-2
MS1 1-4
MS03-1
P0167
MS04-4P0121
P0150
MS02-3MS02-3
P0053
P0052
P0121
P0135
MS07-3
P0087
P0072
P0032
MS02-3
P0156
P0156
P0115
MS07-2MS05-3
P0017
P0159
MS04-4MS06- 1
P0050
P0048
MS06-5MS 10-2
MS12&13-1
MS10-2
MS1 1-2
P0201
MS15-1
P0195
P0086
PL6
P0182
P0130
P0153
P011 1
P0140
MS 10-4
P0204
P007 1
P0161
P0162
MS05-4MS04-5
P0158
P0160
P0154
P0164
P0105
P0158
P0185
PL5
P0189
P0190
P019 1
P0144

lshizawa, N.
lshizawa , N.
lshizawa , N.
Ito , N.
Ito, K.
ltoh, M.
lvanovic , I.
Iwasaki , F.
Iwasaki , W.
lwase, T.
lwataki, T.
Jabeen, T.
Jabeen , T .
Jabeen , T.
Jabeen, T.
Jabeen , T.
Jaish ankar, S p
Jang, L Y.
Jaskolski , M.
Jasti, J.
Jasti, J.
Jean, Y. C.
Jeyaprakash A. A.
Jia, G.
Jia, G.
Jia, G.
Jia, G.
Jia, G.
Jiang, F.
Jiang, F.
Jiang, Y. C.
Johmoto, K.
Johnson , B.
Johnson , D. H.
Ju, J.
Kado, Y.
Kageyama , H.
Kagomiya , I.
Kai , Y.
Kai, Y.
Kai , Y.
Kakimoto , K.
Ka metaka, S.
Kamiyama , T.
Kamiyama , T.
Kamiyama, T.
Kamiyama , T.
Kamiyama , T.
Kanaya , S.
Kang , G. B.
Kanhere , A.
Kan no, R.
Kao, S . T.
Kao, S T.
Kar, M.
Kasuga , Y.
Kato, R.
Kato , R.
Kaur, H.
Kaur, H.
Kaur, P.
Kaur, P
Kau r, P.

P0183
P0197
P0205
P0 140P0202
P0 191P0 147P0103
P0 143
P0199
MS11-3
P0148
MS01-3P0 149MS07-1
P0139
MS12&13-6
P0201
P0029
P0 142MS01-3
P0 171MS01-2
P0088
P0086
P0087
P0089
P0090
P0016
P00 18
P0075
P0039
PL5
MS12&1 3-3
MS15-3
P0158
P0189
MS11-1P0 160P0 154
P0158
MS11 -3
MS04-5MS05-4
P0199
P0071
P0198
P0185
P0154
P0161
MS12&13-2
P0198
P0 106
P01 10MS14-4
P00 10MS10-4MS04-5
P0 176
P0 177
P0 139MS07-1
P0148

Kawachi , K.
Kawasaki , M.
Kawa saki, M.
Kawasaki, N.
Kayashima , K.
Ke , S. C.
Kengaku , Y.
Kennedy, B. J.
Kennedy , B. J.
Kennedy , B. J.
Kennedy, S. J .
Khongsuk , P .
Khosavithitkul , N.
Kim , E.
Kimura , H.
Kimura , H.
Kinugasa , S.
Kittaka , K.
Klein , H.
Kloooste r, W . T .
Klooster, W . T.
Knight, K. S .
Ko , T . P.
Kobayashi , I.
Kobayashi , A.
Kobayashi , H .
Kobayashi , H.
Kobayashi , K.
Kobaya shi , S .
Kobayashi , S .
Kobayash i, S .
Koba yashi, S .
Kobe , B.
Kobe , B.
Kodama , J.
Kohara, S.
Kohmura , Y .
Kohn , K.
Kongsaeree , P.
Kongsaeree , P.
Koon , N.
Kosada , T.
Kosarev, E. L.
Kowiththaya , J.
Krachodnok , S.
Krishnaiah , M.
Krishnakumar, R. V.
Krishnaku mar, R. V.
Krishnaku mar, R. V.
Kulkarn i, M. V.
Kumar, C . K .
Kumar, J.
Kumar, J.
Kumar, J.
Kumar, J.
Kumar, N. J.
Kurihara , K.
Kurisu , G .
Kurisu , G .
Kurisu , G .
Kurmoo , M.
Kusaka , K.
Kusawake , Y .

P0190
MS 10-4
MS04-5MS02-5
P0202
P0121
P0140
P0180
P0019
MS14-5
P0208
P012 8P0066
P01 61MS05-4MS11-1
P0158
P0133
MS02-2MS06-4MS05-5MS05-2
P01 52MS02-5
MS14-1
MS14-1MS08-1
P0140
P0190
P0189
P0191
MS11-1
P0166
MS10-2
P0185
P0193
PL5
MS11-1
P0128
P0023
MS01-5
P0140
P0209
P0119
P0067
P0120
P0031
P0046
P0057
P0011
MS12& 13-4
P0142
MS07-4MS01-3
P01 39P0120
MS12&1 3-8
MS04-2
P0146
MS01-1MS08-1
P0131
P0010

Ku su noki , M.
Kusunoki, M.
Kusunoki, M.
Kwan , W . K.
Lai, Y. L.
Lai, Y L.
Lam , C . K.
Lam , K. C.
Lam , T. C . H.
Lam , W. H.
Lau , I. C. P
Lau , J. P. K.
Law, T. S.C.
Leartsakulpanich , U.
Lee, H. Y.
Lee , C. R.
Lee , C. Y.
Lee , G. H.
Lee , G . H.
Lee , G . H.
Lee , G . H.
Lee , G. H.
Lee , J. F.
Lee , J. J.
Lee , J. J.
Lee , J. J.
Lee , J. H.
Lee , S . J.
Lee , Y. R.
Lee , Y. R.
Leung , A . L. F.
Leung , H. Y.
Leung , W . H.
Leung , W . H.
Leung , W . H.
Li ,C . L.
Li , G .
Li , G . W .
Li , J. R.
Li , L.
Li , M.R.
Li , M. R.
Li , M. R.
Li , R. W .
Li , R. W .
Li , W . H.
Li , X. Y.
Li , Y.
Li , Z
Liang , K. S.
Liang , L.
Liao , C . H.
Liao , F. L.
Liao , Y. C .
Liaw , W. F.
Lii , K. H.
Lii , K. H.
Lii , K. H.
Lii , K. H.
Lii , K . H.
Lin , C. C.
Lin , C. H.
Lin, C. H.

MS0 1-1
P0146
P0140
P0084
P0192
P0125
P0036
P0127
POD 59P012 7
P0094
P0069
P0097
P0128
MS02-3
P0074
P0074
POD 53
P0063
P0121
POD 52
P0040
P0121
P0121
POD 52
MS15-2
P0161
P0162
P0022
P0122
P0095
P0090
P0186
P0187
POD 59P0167
P0107
P01 32
P0081
P0180
P0049
POD 50MS15-5
P0091
P0095
MS05-3
P0126
P012 3
P0107
MS02-3
P0117
P0063
MS03-4MS03-4
P0 121
P0076
P0077
P0078
P0075
MS15-1
MS06-5
P0 192
P0076

Lin , C. Z. J.
Lin , C. Z. J
Lin , G.
Lin , H. M.
Lin , H. M.
Lin , H. W.
Lin , J.
Lin , J.
Lin , J W.
Li n, K. J
Lin , S
Lin , T. W.
Li n, W .
Lin , Y. C.
Lin , Y. C.
Lin , Z.
Listwan , P.
Liu , H. Y.
Liu , J. H.
Liu , J. S.
Liu , J. T. Z. W.
Liu , L.
Liu , L.
Liu , L. K.
Liu , M. Y
Liu , P
Liu , S.
Liu , S. Q.
Liu , W .
Liu , W.
Liu , W.
Liu , W.
Liu , W. S.
Liu , Y.
Liu , Y.
Liu , Y.
Liu , S. X.
Lo, S. M. F.
Lo , S M. F.
Lo , S. M. F.
Lo , S. M. F.
Loong , C. K.
Lu , G.
Lu , G.
Lu , G. L.
Lu, T.
Luger, P.
Luger, P.
Lumpkin, R.
Luo, M .
Lynn , J. W .
Ma, B. Q.
Ma, Z. S.
Machida, Y.
Madauss, K. P.
Maeda, M.
Mahendiran , R.
Mak, T. C. W.
Mak, T. C. W.
Mak, T. C. W.
Mak, T . C. W.
Manivannan , V.
Manivannan , V.

P0092
P0098
P0117
P0106
P0110
P0063
MS15-3
P0107
P0102
P0037
MS06-5
P0152
P0117
P0053
P0052
P0127
MS10-2
P0104
MS04-4
P0135
P0050
P0187
P0109
P0061
P0150
P0159
P0155
P0186
MS 15-5
P0048
P0047
P0049
MS02-3
P0175
MS08-2MS09-3MS06-5
P0100
P0093
P0099
P0101
P0193
P0184
P0072
P0082
P0123
P0068
MS03-2
MS11 -4
MS10-3MS05-3
P0179
P0132
P0004
P0138
MS12&13-8
MS09-4
P0051
P0034
P0035
P0036
P0058
P0028

Mao, J. G.
Marder, T . B.
Marti , J . L.
Mason , S. A.
Matsugaki , N.
Matsuhata, H.
Matsui , T.
Matsui , Y.
Matsumoto, S.
Matsumoto, T.
Matsumura, H.
Matsumura, H.
Matsuyama , S.
McAdam, C. J.
Mcintyre, G. J.
Messerschmidt, M.
Miao, J . W.
Miki, K.
Miki, K.
Mima, J.
Min, Z D.
Mitsumori , T .
Miyata, Y
Miyatake, H.
Miyatake, H.
Miyazaki, N.
Mizuno, H.
Mohan , S.
Mohanty, A. K.
Mohire, C. S.
Mondal , S.
Morgan , J. L.
Mori , K.
Mori, T .
Morikoshi, H.
Morita, Y.
Muangsin , N.
Muangsin, N.
Mukherjee, m .
Mukhopadhyay, U.
Murakami , S.
Nagai , K.
Nagai , T .
Nagoshi , E.
Naitow, H.
Nakagawa, A.
Nakagawa, A.
Nakagawa, A .
Nakagawa, T.
Nakajima, M.
Nakamura, H.
Nakamura, M.
Nakamura, W .
Nakamura, W .
Nakamura, W .
Nakamura, Y .
Nakash ima , R.
Nakayama , K.
Nandhini, M. S.
Nangia, A.
Nangia , A.
Narasimhamurthy, T.
Natarajan, S.

P0026
P0127
MS10-2MS03-1
MS10-4MS09-1
P0172
MS09-4
P0079
MS04-1
P0154
P0158
MS01-4P0030
MS06-4MS03-2
PL5
MS01-4
P0143
P0145
P0105
P0044
P0131
MS01-4
P0143
MS04-3MS04-3
P0008
MS01-3
MS12&13-4
MS12&13-6
P0030
MS08-4
P0003
MS11-3
P0140
P0062
P0023
P0014
P0024
MS04-1
P0146
P0133
P0162
MS04-3MS04-3
P0162
MS01-1
P0131
MS02-5
P0140
MSOB-4
P0191
P0190
P0189
P0199
MS04-1
MS04-5
P0057
MS03-1
P0029
P0169
P0046

Natarajan , S.
Natarajan, S.
Natarajan , S.
Natarajan, S.
Ng, N. C.
Ngamrojnavanich , N.
Ngumviriyakul, V.
Niimura, N.
Niimura, N.
Nirmala, K. A.
Nirmala, K. A.
Nishibori , E.
Nishino, Y.
Nobuo, N.
Noda, I.
Noda, Y.
Nogi, T.
Noh , D. Y.
Noman , A.
Nomura, K.
Norberg, S. T.
Noren, L.
Noren, L.
Norman , N. C.
Obana , H.
Ogawa , A.
Ohashi , Y.
Ohashi , Y
Ohashi , Y
Ohashi , Y
Ohashi , Y.
Ohashi, Y.
Ohashi , Y.
Ohashi , Y.
Ohashi , Y
Ohashi , Y
Ohhara , T.
Ohhara , T.
Ohkubo , K.
Ohoyama, K.
Ohoyama , K.
Ohoyama , K.
Ohsato , H.
Ohshima , K.
Ohsumi , H.
Ohsumi , K.
Oh-uchi , K.
Oh-uchi , K.
Oh-uchi , K.
Oikawa , K.
Oishi , S.
Okano, Y.
Okazaki , N.
Okazaki , S.
Okumura , N.
Okumura , Y.
Omura , T.
Osawa , T.
Ostermann , A.
Otani , H.
Otsuka, T.
Ozaki , Y.
Ozawa , Y.

P0178
P0181
P0057
P0031
P0104
P0023
P0119
P0172
MS12&13-8
P0008
P0005
MS14-1
PL5
P0111
MS08-4MS11-1
MS04-5
MS11 -5
MS06-3
P0189
P0197
MS08-2MS09-3
P0127
P0185
MS04-3MS03-5
P0060
P0039
P0043
P0044
P0045
P0055
P0111
P0204
P0071
P0071
P0172
P0004
P0190
P0191
P0189
MS11 -3
P0010
MS02-4
P0131
P0190
P0191
P0189
P0071
P0183
P0158
P0158
P0157
P0146
P0202
MS04-3MS11-1
P0172
P0146
MSOB-1MSOB-4
P0052

Ozeki , T.
Padma , R.
Paehler, A.
Pandiarajan , K.
Park , S. H.
Park , S. J.
Park , Y. J.
Pattabhi , V.
Peng , S. M.
Perbt , M.
Petsom , A.
Pflugrath , J. w.
Phurat, C.
Phyu , K. W.
Pletnev, V.
Poon , S. Y.
Praphairaksit, N.
Premkumar, T.
Premkumar, T.
Pring , A.
Puschmann , H.
Que , D.
Quilinguin , M. V. p
Radhakrishnan , K. R.
Radhakrishnan , K. R.
Rae , A. D.
Rae , A. D.
Rahman , M. M.
Rahman, R. N. Z. R. A
Rajagopal , K.
Rajakannan , V.
Rajaram, R. K.
Rajaram , R. K.
Rajnikant
Ramachand ran , E.
Ramachandran , E.
Ramakumar, S.
Ramakumar, S.
Rao, Z.
Rao , Z.
Rath , N. p
Rathore , R. s.
Rathore , R. S.
Ravasi , T.
Ravi , S.
Ravikumar, K.
Ravikumar, K.
Rene, P. F.
Rho , S. H.
Richard-Weber, J . K.
Robinson , B. H.
Robinson , R. A.
Robinson , R. A.
Row, T. N. G.
Roy, I.
Roy, S.
RudreshROscher, C. H.
Saeki , K.
Saeki , S.
Saha , M.
Saitoh , K.
Sakai , H.

P0112
P0173
P0140
P0169
P0161
P0161
P0083
P0153
PL3
P0149
P0023
P0138
P0062
P0171
MS12&13-1
P0108
P0062
P0027
P0028
P0021
MS03-1
P0123
P0207
P0058
P0028
P0065
MS12&13-7
MS06-3
P0154
P0031
P0157
P0001
P0002
P0012
P0178
P0181
P0085
MS12&13-6
MS10-1
P0175
P0027
P0168
P0169
MS10-2
MS14-4
P0025
P0031
P0207
P0161
P0193
P0030
P0013
P0208
P0011
P0149
P0137
P0085
P0182
P0144
P0140
P0024
MS09-5
P0162

Sakata, M.
Sakurai, S.
Salleh , A. B.
Saravanan , J.
Saravanan , K.
Sarvanan , K.
Sasaki, S.
Sasaki , S.
Sasaki , S.
Sasaki , S.
Sasaki , S.
Sato, H.
Schaber, J.
Scheins , S.
Schmid , S.
Schneider, J. R.
Scudder, M. L.
Sekar, K .
Sekar, K.
Sekar, K.
Sekimoto, T .
Sekine, A.
Sekine, A.
Selvanayagam , S.
Selvarani , P.
Senda , K.
Seo , S. H.
Shannon , W. N. A.
Shanthi , V.
Sharma, S.
Sharma, S.
Sharma, S.
Sharma , S.
Sharma , S.
Sharma, S.
Sharma , S.
Shaw, P. C.
Shek , F. L. Y.
Shek , F. L. Y.
Shen , H. H.
Sheu , C. F.
Sheu , C. F.
Sheu , H. S.
Shi , H. M.
Shi, N. C.
Shiba , T .
Shiba , Y.
Shibata, M.
Shimizu , N.
Shimizu , N.
Shimizu , N.
Shimizu , N.
Shinohara, Y.
Shinohara, Y.
Shinohara, Y.
Shishitani, H.
Shivaprakash , N. C.
Shyu , S. G.
Shyu, S. G.
Simpson , J.
Singh , B.
Singh , N.
Singh , N.

MS14-1
P0009
P0154
P0008
P0058
MS0?-4
P0003
P0004
P0007
P0009
P0006
MS08-4
MS12&13-1
MS03-2
MS15-4MS02-2MS06-3
P0137
P0157
MS12&13-4
P0162
P0204
MS03-5
P0165
MS12&1 3-4
MS08-4MS11-5
P0174
MS12&1 3-4
MS01-3
P0148
P0142
P0149
MS0?-1
MS0?-4
P0139
P0175
P0099
P0101
P0038
P0052
P0040
P0171
P0105
P0132
MS04-5MS04-5MS04-5
P0007
P0006
P0003
P0009
MS02-5
P0209
P0202
P0158
P0011
P0106
P0110
P0030
P0142
P0149
P0148

Singh , N.
Singh , R. K.
Singh , R. K.
Singh , T. P
Singh , T . P.
Singh , T . P.
Singh, T. P.
Singh , T. P
Singh , T. P.
Singh , T . P.
Singh , T . P.
Singh , T. P
Siripisarnpipat, S.
Siu , A. W. H.
Smith, J. L.
Smith, R.I.
Somphon , W.
Somvanshi , R. K.
Spackman, M.
Spadaccini , N.
Squire , C. J.
Sridhar, B.
Sridhar, B.
Srinivasan , A.
Srinivasan , A.
Srivastav , A.
Srivastava , D. B.
Steed , J. W.
Stefanovic, A.
Stence, C. N.
Stetsko, Y. P.
Stirling , D.
Su , Q.
Suda , K.
Suematsu , H.
Sugawara , H.
Suh , S. W.
Sukvinich , S.
Sun, H. L.
Sun , H. L.
Sun , J.
Sun , W. C.
Sun , W. H.
Sun , W. S.
Sun , Y. J.
Sung, H. H. Y.
Sung , H. H. Y.
Sung , H. H. Y.
Sung , H. H. Y.
Sung , H. H. Y.
Sung , H. H. Y.
Sung , H. H. Y.
Sung , H. H. Y.
Sung , H. H. Y.
Sung , H. H. Y.
Sung , H. H. Y.
Sung , H. H. Y.
Sung , H. H. Y.
Surolia, A.
Suzuki , A.
Suzuki, H.
Suzuki , M.
Suzuki , Y.

MS07-4
MS0?-1
P0148
PL2
MS01-3
P0142
P0148
P0173
MS0?- 1
MS0?-4
P0139
P014 9P0119
P0098
MS04-2MS11-4
P0065
P0173
P0068
MS12&13-5
MS01-5
P0001
P0002
MS0?-4
MS0?-1MS01-2
MS0?-4
P0028
MS08-3
P01 38MS02-3MS14-3P0117
P01 83MS02-4MS01-1
P01 51
P011 9P0081
P017 9
P0107
P0122
P0122
P0022
P0156
P0086
P0087
P0089
P0090
P009 1
P0094
P0096
P0097
P0098
P0099
P0101
P0105
P0092
MS01-2
P01 57
P0055
MS10-4
P0209

Suzuya , K.
Swamy ,G. Y. S. K.
Syed , A .A.
Szeto , L.
Tack, N. M.
Taiyaqupt, M.
Taka, J.
Takaaki , H.
Takahashi , I.
Takano , K.
Takashi, 0.
Takata , M.
Takata , M.
Takeda, K.
Takeoka , H.
Takeuch i, E.
Takeuchi , K.
Takino , K.
Tanaka , I.
Tanaka , I.
Tanaka , I.
Tanaka , M.
Tanaka , M.
Tanaka , M.
Tanaka , M.
Tang , M. F.
Tang , M. T.
Tangeman , J. A.
Tanizawa , H.
Tateishi , K.
Tateishi , K.
Tenai lleau , C.
Terauchi , H.
Thaimattam , R.
Thakurta , P. G.
Thomas, S. K.
Thushari, S
Thuy, D. M.
Tian , Y. Q.
Ting , V.
Ting , V.
Tokuda , H.
Tokura , Y.
Tomar, S.
Tomioka , Y.
Tomoji , 0
Tong , M. L.
Too, H. M.
Toriumi , K.
Tsai , A. P
Tsao , F. C.
Tsao , J.
Tse, C. H. W .
Tse , C. H. W .
Tso , 1-M.
Tsukiha ra , T .
Tsukihara , T.
Tu , X.
Uchida , M.
Uchida , T .
Uchida , Y.
Uchiyama , Y .
Ueda , Y.

P0193
P0025
POOBO
P0070
MS06-4
P0062
MS04-3
P0111
MSOB-4P0154
P0111
MS02-4MS14-1MS01-4
P0045
P0202
P0193
P0103
MS12&1 3-8
PL4
P0172
P0003
P0004
P0006
MS09-5
P0078
MS02-3
P019 3
P0157
P0205
P0183
P0021
MS08-4
P0029
P0134
P0193
P0096
P0194
P0056
MS09-3MS08-2MS01-4MS09-4
P0139
MS09-4P0111
MS06-1
P0175
P0052
MS09-5MS05-3
MS12&13-3
P0093
P0095
P0171
MS04-3
P0162
P0072
MS09-4MS01-1
P0079
MS04-5
P0145

Ueji , Y .
Uekusa , H.
Uekusa , H.
Uekusa , H.
Ueku sa , H.
Uekusa , H.
Uekusa , H.
Uekusa , H.
Uekusa, H.
Uekusa , H.
Ueno, S
Uesugi , K.
Uodome, N.
Urade , Y.
Uratani , H.
Vasa nthakumar, B.
Vasu
Vasu
Velmurugan , D.
Velmurugan , D.
Vijayan , M.
Vijayan , M.
Vishwas , M.
Vishweshwa r, P.
Vithana , C.
Vittal , J. J.
Vittal , J. J.
Vong , V.
Vong , V.
Vuong , N. V.
Waguri , S.
Wakatsuki , S.
Wakatsuki , S.
Wallwork, K . S.
Walter, S.
Wan, D. C. C
Wang , A. H. J.
Wang , C .
Wang , C . C.
Wang , C. C
Wang , H.
Wang , J. W.
Wang , J. W.
Wang , J. W
Wang , L.
Wang , L.
Wang , S. L.
Wang , S. L.
Wang , S. L.
Wang , S. L.
Wang , S. L.
Wang , T . Y.
Wang, W . C.
Wang , X. S.
Wang , X. Y.
Wang , Y.
Wang , Y.
Wang , Y.
Wang , Y .
Wang, Y .
Wang , Y .
Wang , Y .
Wang , Y.

P0209
P0055
MS03-5
P0039
P0043
P0044
P0045
P0111
P0060
P0204
MS02-5
P0209
P0158
P0158
P0010
MS12&13-6
POOOB
P0005
P0165
P0157
MS01-2
P0137
P0005
MS03-1MS03-5
MS06-4
P0058
P0194
P0195
P0194
MS04-5MS04-5MS10-4
P0021
P0048
P0164
P0152
P0117
P0063
PL3
P0206
P0016
P0017
P0018
P0115
P0033
MS03-4MS15-1
P0124
P0125
P0192
P0121
P0135
P0041
P0081
MS15-2
P0037
P0038
P0040
P0052
P0053
P0074
P0121

Wang , Z.
Wang , Z.
Wang , Z. R.
Wasa , K.
Watanabe, T.
Watanabe, Y.
Wcislak, L.
Welberry , T. R.
Wells , C.
Wen , T. B.
Wen , T. B.
Wen , T. B.
Wen , Y. S.
Weng , L. H.
Weng , S. C.
Wi lliams, D.
Williams , D.
Williams , D.
Williams , D.
Williams, D.
Williams , D.
Williams , D.
Williams , D.
Williams , D.
Williams , D.
Williams , D.
Wi lliams , D.
Williams , . D.
Williams , I. D.
Williams, I. D.
Williams , I. D.
Wil liams, I. D.
Williams, I. D.
Wi lliams, S. P.
Withers, R. L.
Withers, R. L.
Wong , G. K. L.
Wong , K. B.
Wong , K. B.
Wong , K. B.
Wong , K. S.
Wong , W. B.
Wong , W. T.
Wong , W. T.
Wong , W. Y.
Wong , W. Y.
Wong , W. Y.
Wong , W. Y.
Wong , W. Y.
Wong , W. Y.
Woodward , R.
Woolfson , M. M.
Wu , C. L.
Wu , H. H.
Wu , M.
Wu , R. Q.
Wu , W. C.
Wu, W. G.
Wu , W. S.
Wu , Y. S.
Wu , Z. P.
Xia , H.
Xian , D. C.

MSOB-1
P0175
P0155
MS11-5
P0006
MS04-3MS02-2
P0015
MS10-2
P0086
P0088
P0089
P0 196P0056
P0 122
P0059
P0086
P0087
P0089
P0090
P0091
P0092
P0093
P0094
P0095
P0096
P0097
P0098
P0099
P0 100P0 101P0105
P0 126
P0138
MS08-2MS09-3
P0087
P0163
P0164
P0175
P0096
P0090
P0069
P0070
P0082
P0101
P0203
P0099
P0108
P0109
P0013
P0017
P0135
P0022
P0117
P0123
P0196
MS04-4MS06-5
P0113
MS14-3
P0089
P0017

Xian , D. C.
Xian , D. C.
Xie , Y.
Xiong , M.
Xiong , R. G.
Xiong , R. G.
Xu , N.
Xue , G. Q.
Xue , P.
Yadav, S.
Yadav, S.
Yagi, N.
Yam , F.
Yamada , A.
Yamada , Y.
Yamaguchi , A.
Yamamoto , T.
Yamanaka , T.
Yamane, T.
Yamane, T.
Yamasaki , T.
Yamase , T.
Yamash ita , E.
Yamashita , E.
Yamashita , T.
Yamaura , S.
Yamawaki , K.
Yamawaki , K.
Yamawaki , K.
Yamawaki , K.
Yamawaki , K.
Yamazaki , T.
Yanagita , M.
Yang , C.
Yang , C. C.
Yang , C. H.
Yang , H. D.
Yang , S. N. Y.
Yang , X.
Yang , X. X.
Yang , X. X.
Yang , X. X.
Yang , X. X.
Yang , X. X.
Yang , Y. Y.
Yang , Y Y.
Yao, D. Q.
Yao, DQ.
Yashima , M.
Yashima , M.
Yashima, M.
Yasuda , M.
Yasui , M.
Yasui , T.
Ye , C. H.
Yeh , N. T.
Yen , Y. F.
Yeung , C. H.
Yeung , L. L.
Yi , X. Y.
Yokosawa , T.
Yokota , N.
Yoneda , Y.

P0018
P0159
P0160
P0132
P0041
P0042
P0117
P0126
P0090
MS11-5
P0139
P0209
P0104
P0198
MS04-5MS04-1
P0154
P0133
P0157
P0165
MS01-1
P0112
P0162
MS04-1
P0146
MSOS-4
P0003
P0004
P0006
P0007
P0009
MSOS-4
P0079
P0138
MSOS-3
P0063
MS05-3
P0166
P0117
MS15-5
P0047
P0048
P0049
P0050
P0118
P0070
P0018
P0159
P0189
P0190
P0191
P0010
P0103
P0190
P0081
MS02-3
P0095
P0084
P0104
P0059
MS09-5MS01-4
P0162

Yonemura , M .
Yoshida , K.
Yoshimura , M .
Yoshimura , M.
You , L.
You , X . Z .
Yu , D. H.
Yu , Y .
Yu , Y .
Yuan , H . S .
Yuan , Y. P.
Yuan , Z .
Yuan , Z .
Yutani , K.
Yuthavong , Y .
Zhang , B.
Zhang , H.
Zhang , H.
Zhang , J. P.
Zhang , Q. F.
Zhang , Q. F.
Zhang , Q. F.
Zhang , X . X .
Zhang , Y . Z .
Zhang , Z
Zhao , B.
Zhao , D . Y .
Zhao, H.
Zhao, J. T.
Zhao, J. T.
Zhao , J. T .
Zhao , J. T .
Zhao , L.
Zhao , X . L.
Zheng , C . D .
Zheng , C . D .
Zheng , C . Q .
Zhou , J.
Zhou , J.
Zhou , J. S .
Zhou , Q .
Zhou , Q .
Zhou , Z . Y .
Zhou , Z . Y .
Zhu , H . X .
Zhuang , X .
Zolensky, M . E.

P0198
P0043
P0006
P0162
P0107
P0056
P0013
P0097
P0094
P0167
P0026
P0184
P0072
P0172
P0128
MS08-1
P0089
MS04-2MS06-1
POD 59
P0186
P0187
P0098
P0179
MS11 -4
MS06-2
POD 56
P0042
P047
S15-5
P0048
P0049
P0051
P0034
P0016
P001 8
P0114
P0033
P0206
MS03-3MS14-5
P0180
P0084
P0088
P0105
P0123
P01 31이 문서의 이용권리는아래의 도서 소유가에 한함윤지영
010-8897-3635
bandij@hanmail.net