PREFACE
OCU-Advanced Research Institute for Natural Science and Technology (OCARINA)
have held the Annual meeting each year since 2008 as an international conference. This
year, we should complete the original project and develop to the second stage.
Last year, ReCAP (=Research Center for Artificial Photosynthesis) have newly
settled as the Industry-University cooperation organization. The research on natural andartificial photosynthesis is considerably activated. During the course of thisdevelopment, our proposal on COI stream was partially accepted as COI trial under theleadership of professor Kamiya of our institute collaborate with Dr. Ymamashita of Fuji
Chemical Industry Co., Ltd.. We strongly desire that this meeting becomes the good
opportunity to re-challenge the COI steam.
The buildings for scientific institutes are almost finished and remain only repairing
the old parts for earthquake proof. Accompanied with this establishment, OCARIA will
start the activity at this new building. Coming year, we need to develop and start novel
projects. On this meeting we requested the lectures for active concurrent researchers forthe purpose to introduce the new research field. We also invited overseas young
collaborating researchers, and very active young domestic researchers.
Even more the fully related Research Center for Artificial Photosynthesis (ReCAP)
for the purpose of active collaboration between industry and the University.
Our Institute, OCARINA and ReCAP will walk together with the Research
Organization for the 21th Century of Osaka-Prefectural University. The project ofArtificial Photosynthesis for practical achievement is so important and should be
co-worked with vicinal Universities. It is our great pleasure to collaborate OPU forcelebrating the future partnership.
Finally, we would like to express our sincere gratitude to Osaka City University forthe financial support to host this important conference.
The OCU Advanced Research Institute for Natural Science and Technology(OCARINA)
Director Prof. Dr. Isamu Kinoshita

̶1̶

ご挨拶

複合先端研究機構（以下OCARINA）では、平成２０年度以降定期的に年次総会を開催しております。平成２５年度年次総会は，初期のプロジェクトの集大成の年でもございます。
今年度６月に，姉妹組織とも呼べる人工光合成研究センターが開所し，光合成・人工光合成研究はますますの発展を迎える事になりました。人工光合成研
究を発展させる過程で申請してきたCOI（文部科学省 革新的イノベーション創出プログラム，COI STREAM）が，本研究機構教授神谷信夫・リサーチリーダ
ー（富士化学工業（株）山下栄次プロジェクトリーダー）の下で，COI-trialとして部分的に採択されました。本年会はこのプロジェクトを成功裡に進行し，本番のCOI STREAMに再度チャレンジしていく機会となればと願っております。
さて，理系学舍の新築部分がほぼ完成し，旧来の部分の耐震工事を残すのみになって参りました。これに伴って，複合先端研究機構もいよいよ新棟への入居が始まって参ります。次年度は新プロジェクトも立ち上げ，いよいよ当初の計画である，三プロジェクトの立ち上げを行わねばなりません。今回は，複合先端研究機構を支えてきていただく兼任の先生方，共同研究を進めていく若手の海外研究者，国内のアクティブな若手研究者を中心に討議を進めていきたいと存じています。御講演いただく各先生方，ご参加される方々の活発なご議論をお願いいたします。

大阪市立大学 複合先端研究機構・機構長
木下 勇

̶2̶

General Information
Date
4th March, 2014 (Tue.) 10:00-18:00
5th March, 2014 (Wed.)

9:00-12:00

Venue
10th Floor, Osaka City Univ. Media Center
Banquet
4th March, 2014 (Tue.) 18:30~20:30
at 1st Floor, Osaka City Univ. Media Center, Wisteria (Restaurant)
Organizer
The OCU Advanced Research Institute for Natural Science and Technology(OCARINA)
Supported by
Key Project of Osaka City University
COI-T hub for the "Realization of next-generation hydrogen-energy society"
Organizing CommitteeyHideki Hashimoto (Project Leader of OCARINA / Graduate School of Science,
Professor)yIsamu Kinoshita (Director of OCARINA / Graduate School of Science, Professor)yRitsuko Fujii (Associate Professor of OCARINA / Graduate School of Science)

Advisory BoardyRichard J. Cogdell (University of Glasgow, UK, FRS)y

Masakazu Anpo (Vice-President of Osaka Prefecture University)

Plenary speakeryHarue Masuda (Graduate School of Science, Professor / OCARINA)

̶3̶

Invited speakersy

Tim Storr (Simon Fraser University, CA, Associate Professor)yRudi Berera (Vrije Universiteit Amsterdam, NL, PD)yYasushi Nishihara (Okayama University, JP, Professor)yMasaki Ihara (Shinshu University, JP, Assistant Professor)yRyutaro Tokutsu (National Institute for Basic Biology, JP, Assistant Professor)yYasuhiro Funahashi (Osaka University, JP, Professor)

Invited speakers in OCARINAyTakaaki Asou (OCARINA, Tenure-track Specially Appointed Lecturer)yYasuyuki Tsuboi (Graduate School of Science, Professor / OCARINA)y

Masato Miyata (Graduate School of Science, Professor / OCARINA)yYoshikazu Nishikawa (Graduate School of Human Life Science, Professor /OCARINA)

̶4̶

Programme
Tuesday, 4th March, 2014
10:00~10:10

Opening remark

10:10~10:55<Invited Talk 1>“Mycoplasma, the smallest microorganism moves by
a novel mechanism”,
Masato Miyata (Osaka City University)

11:00~11:45<Invited Talk 2>“Optical Functions of Plasmonic Nano-Antenna:
Manipulartion of Nanopartciles and Photochemical Reactions”,
Yasuyuki Tsuboi (Osaka City University)

11:45~12:20

Lunch Break

12:20~13:20<Plenary Lecture>“Formation mechanism of arsenic contaminatedgroundwater in Ganga basin”,
Harue Masuda (Osaka City University)

13:25~14:25

Poster Sessions

14:30~15:15<Invited Talk 3>“Synthesis of Organic Molecules with the Extended
π-Conjugated System and Their Application to Electronic
Devices”, Yasushi Nishihara (Okayama University)

15:25~16:05<Invited Talk 4>“Construction of Biomimetic Model Compounds of theActve Sites in Metalloenzymes Working for Dioxygen
Reduction/evolution”,
Yasuhiro Funahashi (Osaka University)

16:05~16:20

Break

̶5̶

16:20~17:05<Invited Talk 5>“Electrophoretic adhesion for fabrication of 3D hydrogel
devices”, Takaaki Asou (Osaka City University)

17:15~18:00<Invited Talk 6>“Caenorhabditis elegans as a Model Host to Study
Immunonutrition for Healthy Ageing”,
Yoshikazu Nishikawa (Osaka City University)

18:30~20:30

BanquetWednesday, 5th March, 2014
9:00~9:40<Invited Talk 7>“Oxidized Metal Phenoxide Complexes - Correlation ofElectronic Structure and Reactivity”,
Tim Storr (Simon Fraser University, CA)

9:40~10:20<Invited Talk 8>“Identification of two quenching processes in thedissipative state of FCP antennas”
Rudi Berera (Vrije Universiteit Amsterdam, NL)

10:20~10:30

Break

10:30~11:10<Invited Talk 9>“Formation of PSII-LHCII-LHCSR supercomplex under NPQ
inducible conditions”,
Ryutaro Tokutsu (National Institute for Basic Biology)

11:10~11:50<Invited Talk 10>“Protein engineering for the creation of algae with highformate productivity”,
Masaki Ihara (Shinshu University)

11:50~12:00

Closing remark

̶6̶

開催概要
日時
2014 年 3 月 4 日（火） 10:00-18:00
2014 年 3 月 5 日（水） 9:00-12:00
会場
大阪市立大学学術情報総合センター 10 階
大阪市住吉区杉本 3 丁目 3 番 138 号 Tel:06-6344-9560
懇親会2014 年 3 月 4 日（火） 18:30~20:30
大阪市立大学学術情報総合センター 1 階 ウィステリア
主催
大阪市立大学複合先端研究機構
後援
大阪市立大学・重点研究プログラム
COI-T「次世代水素エネルギー社会の実現」拠点
組織委員y

橋本 秀樹（複合先端研究機構・プロジェクトリーダー／大学院理学研究科・教授）

y

木下 勇（複合先端研究機構・機構長／大学院理学研究科・教授）y藤井 律子（複合先端研究機構・准教授／大学院理学研究科兼担）

顧問委員
yRichard J. Cogdell (University of Glasgow, UK, 英国王立協会特別研究員)

y

安保 正一（大阪府立大学・理事・副学長兼地域連携研究機構長)

̶7̶

特別講演者y益田 晴恵（複合先端研究機構兼任／理学部地球学科・教授）

招待講演者
y

Tim Storr (Simon Fraser University, CA, Associate Professor)yRudi Berera (Vrije Universiteit Amsterdam, NL, PD)y西原 康師（岡山大学理学部化学科・教授）y

伊原 正喜（信州大学農学部プロジェクト研究推進拠点・助教）

y

得津 隆太郎（基礎生物学研究所 環境光生物学研究部門・助教）y舩橋 靖博（大阪大学大学院理学研究科・教授）

学内招待講演者y

麻生 隆彬（複合先端研究機構・テニュアトラック特任講師）

y

坪井 泰之（複合先端研究機構兼任／理学部化学科・教授）y宮田 真人（複合先端研究機構兼任／理学部生物学科・教授）y西川 禎一（複合先端研究機構兼任／生活科学研究科・教授）

̶8̶プログラム3 月 4 日（火）10:00~10:10

Opening remark

10:10~10:55＜招待講演 1＞“Mycoplasma, the smallest microorganism moves by
a novel mechanism”, 宮田 真人（複合先端研究機構兼任／理学部生物学科・教授）

11:00~11:45＜招待講演 2＞
“Optical Functions of Plasmonic Nano-Antenna:
Manipulartion of Nanopartciles and Photochemical
Reactions”, 坪井 泰之（複合先端研究機構兼任／理学部化学科・教授）

11:45~12:20

昼食

12:20~13:20＜特別講演＞“Formation mechanism of arsenic contaminatedgroundwater in Ganga basin”, 益田 晴恵（複合先端研究機構兼任／理学部地球学科・教授）

13:25~14:25

ポスター発表（企画：DISCO Party）

14:30~15:15＜招待講演 3＞“Synthesis of Organic Molecules with the Extended
π-Conjugated System and Their Application to Electronic
Devices”, 西原 康師（岡山大学理学部化学科・教授）

15:25~16:05＜招待講演 4＞
“Construction of Biomimetic Model Compounds of theActve Sites in Metalloenzymes Working for Dioxygen
Reduction/evolution”,
舩橋 靖博（大阪大学大学院理学研究科・教授）

16:05~16:20

休憩

̶9̶

16:20~17:05＜招待講演 5＞“Electrophoretic adhesion for fabrication of 3D hydrogel devices”,
麻生 隆彬（複合先端研究機構・テニュアトラック特任講師）

17:15~18:00＜招待講演 6＞
“Caenorhabditis elegans as a Model Host to Study
Immunonutrition for Healthy Ageing”, 西川 禎一（複合先端研究機構兼任／生活科学研究科・教授）

18:30~20:30

懇親会

3 月 5 日（水）9:00~9:40＜招待講演 7＞
“Oxidized Metal Phenoxide Complexes - Correlation ofElectronic Structure and Reactivity”,
Tim Storr (Simon Fraser University, CA, Associate Professor)

9:40~10:20＜招待講演 8＞
“Identification of two quenching processes in thedissipative state of FCP antennas”
Rudi Berera (Vrije Universiteit Amsterdam, NL, PD)

10:20~10:30

休憩

10:30~11:10＜招待講演 9＞“Formation of PSII-LHCII-LHCSR supercomplex under
NPQ inducible conditions”, 得津 隆太郎（基礎生物学研究所 環境光生物学研究部門・助教）

11:10~11:50＜招待講演 10＞
“Protein engineering for the creation of algae with highformate productivity”, 伊原 正喜（信州大学農学部プロジェクト研究推進拠点・助教）

11:50~12:00

Closing remark

̶ 10 ̶

Invited Lectures̶ 11 ̶

̶ 12 ̶

Tuesday,4th March̶ 13 ̶

̶ 14 ̶

Mycoplasma, the smallest microorganism
moves by a novel mechanism    
Makoto Miyata
1) The OCU Advanced Research Institute for Natural Science and Technology2) Graduate School of Science, Osaka City University
Mycoplasmas are the smallest group of bacteria about 1 µm long and cause various diseases
in animals and plants, including human pneumonia. Many Mycoplasma species form a
protrusion at a cell pole and glide around on the host surfaces. The gliding speed reaches up
to 4.5µm per s and the movements are impressive under optical microscopy. Many livingorganisms have motility. The motility looks divergent, but most mechanisms belong to only
two categories. However, the of Mycoplasma gliding mechanism cannot be assigned toeither of them.
We studied Mycoplasma gliding scince 1997, and clarified the gliding machinery,component proteins, binding target, energy source, mechanical characters, molecular
movements etc, and then proposed a working model, “The movements are generated by an
F1-ATPase homolog inside the cell, transmitted to a "leg" protein through a "crank" protein,
resulting in the repeated catch/pull/release of sialylated oligosaccharides, the common
structures on host surfaces [1, 2]. Interestingly, the recent advances in biological technology
have suggested other novel motility systems.
Since 2012, we encourage studies of those novel motility systems as a MEXT project,"Grant-in-Aid for Scientific Research on Innovative Areas", named "Harmonizedsupramolecular motility machinery and its diversity" [3]. In our university, we have
expanded our Mycoplasma research group and also established another group providing a
special technique to visualize molecules and cells with high spacial and time resolusions,"Rapid-freeze-replica electron microscopy" [4].

[1] Miyata, M. Annual Review of Microbiology, 2010, 64, 519.
[2] http://www.sci.osaka-cu.ac.jp/~miyata/index.html[3] http://bunshi5.bio.nagoya-u.ac.jp/~mycmobile/index.php[4] https://www.facebook.com/freeze.fracture̶ 15 ̶

Optical Functions of Plasmonic Nano-Antenna:
Manipulartion of Nanopartciles and Photochemical
Reactions
Yasuyuki Tsuboi1,2)
1)
Division of Moclecual Materails Science, Graduate School of
Science, Osaka City University, Sugimoto 3-3-138, Sumiyoshi-ku,
Osaka 558-8585, Japan.
2)JST, PRESTO
E-mail: twoboys@sci.osaka-cu.ac.jp

Plasmonic enhanced electromagnetic field is applicable not only to SERS but also tochemical reaction promotion, and also even to optical trapping. Plasmon-based opticaltrapping is quite intriguing and is currently attracting much attention in nano-photonics andrelated research fields, since optical trapping based on surface plasmon can potentiallyovercome several disadvantages of conventional optical trapping technique using a focusedlaser beam, i.e.; (i) the conventional technique requires an intense focused laser light and acomplicated optical set up to manipulate a small nanoparticle, and (ii) the spatial resolution in
the trapping is, as a matter of course, regulated to be more than several hundreds nanometers
by a diffraction limit of a incident light.
As has been predicted theoretically andverified experimentally, an electromagnetic
field of incident light should be considerably
localized and enhanced at a nano-junction or anano-gap between metal nanoparticles, so
called gap-mode excitation. A schematic
illustration for such plasmon-based opticaltrapping is displayed in the figure.

When photochemically-active species is trapped at such a plasmonic nan-gap, photon,
plasmon, and the photoactive species should be simultaneously coupled in the samenano-space. We consider that such situation is an ideal photochemical reaction field in which
they interact with each other with great efficiency to promote photochemical reaction yield.
The goal of our study is to incarnate such situation. We hace developed a plasmonic
optical tweezer system and succeeded in novel trapping so far.

̶ 16 ̶

(1) Plasmonic optical trapping for organic polymer system [1].
(2) Resonant optical trapping for polymer microsphere[2] and a protein [3].
(3) Micro-pattern formation (colloidal crystal formation) on a plasmonic nanostructure [4].
(4) Quantitative evaluation for radiation pressure and Soret force (temperature elevation at a
plasmonic nanostructure) [1, 5].
(5) Femtosecond plasmonic optical tweezer for biomolecules (DNA) [6].
Toward the final goal, we are currently challenging several experiments using a real
photosynthetic system (LH I). Plasmon-based optical trapping is potentially applicable to awide field of photochemistry.
Ackowledgements
The author would like to express his sincere thanks to all the collaboratores; Dr. Tatsuya Shoji(Osaka City Univ.), Dr. Mariko Toshimitsu (Hokkaido Univ.), Dr. Michiko Shibata, Prof.
Hajime Ishihara, Prof. Yuriko Matsumura (Tokyo Inst. Tech.), Dr. Fumika Nagasawa(Hokkaido Univ.), and Prof. Kei Murakoshi.

Reference (Selected publication)[1] M. Toshimitsu et al. and Y. Tsuboi, J. Phys. Chem. C Vol. 116, No. 27 (2012) 14610-14618.
[2] T. Shoji et al. and Y. Tsuboi, Jpn. J. Appl. Phys. Vol. 51, No. 9 (2012) 092001.(Spot Light Paper)[3] T. Shoji et al. and Y. Tsuboi, J. Phys. Chem. C Vol. 117, No. 20 (2013), pp. 10691–10697.
[4] T. Shoji et al. and Y. Tsuboi, J. Phys. Chem. C. Vol. 117, No. 6 (2013), pp 2500–2506.
[5] H. Yamauchi, Y. Tsuboi et al. and S. Ito, J. Phys. Chem. C Vol. 117, No. 16 (2013) pp. 8388–8396.
[6] T. Shoji et al. and Y. Tsuboi, J. Am. Chem. Soc. Vol. 135, No. 17 (2013) 135, pp. 6643−6648.

̶ 17 ̶

Formation mechanism of arsenic contaminatedgroundwater in Ganga basin
Harue Masuda
Faculty of Science, Osaka City University
Abstract: Arsenic contaminated groundwater is the one of world wide threats for the qualityof life especially in Asian countries. Numerous studies have been done for more than two
decades, however, formation mechanism of the contamination is still in debate.
Most of the As contaminated groundwater is in the Holocene aquifers, and the source(s) of
As is obviously geogenic. The most accepted hypothesis of formation mechanism until now is
as follows. Arsenic-bearing sulfide mienrals, derived from Himalayas, are decomposed via
chemical weathering and newly formed Fe-oxyhydroxides are precipitated on detrital mineral
grains, such as quartz and feldspars, with adsorbing the As. The mineral grains settle ingroundwater aquifer sediments, then those are reduced and decomposed in association with
infiltration of organic-rich surface water. Arsenic losts the host minerals and is released into
the groundwater. Throughout a series of studies in Sonargaon, Bangladesh, we found the earlystage of As dissolution process in the similar groundwater aquifer, which was against the
hypothesis described above.
The only source of As in our studied aquifer was chlorite (FeII-sheet silicate) [1]. This
mineral is chemically weathered in the uppermost part of the Holocene aquifer at 5 to 10 m
depths from the ground surface [2]. Chemical weathering occurs at and near the Earth’s
surface, where aerobic and wet condition can be attained. As(III):As(V) of the chlorite was
4:6, and the As plausibly substituted Si. When the chlorite was decomposed via
oxidation-hydration, the As was dissolved into the groundwater. Fe-oxyhydroxides wereformed at the same timing, while those could not be the host of As probably because the As
was expelled when ferryhydrite (Fe(OH)3) transformed into more stable goethite (FeOOH).
Although the previouls researchers who found As in silicate minerals did not think that thesilicates could not be a source of As since those would be insoluble in the groundwateraquifers, the chlorite must be easily dissolved in aerobic aqueous condition.
Adsorption-desorption of As onto Fe-oxyhydroxides may secondary control the Asconcentration of groundwater but is not essential to form the contaminated groundwater. Ourfindings would be applicable as a general process for the As contaminated groundwater in the
Ganga basin. Formation of As contaminated groundwater has started in 1960’s, while thecontaminated groundwater would have extended after 1980’s since irrigation pumping
became active.
References[1] Masuda H. et al., Geochemi.J. 2011, 130, 111. [2] Masuda et al., Geochim. Cosmochim.
Acta, submitted.
̶ 18 ̶

Synthesis of Organic Molecules with the Extended
S-Conjugated System and Their Application to Electronic
Devices1

Yasushi Nishihara
Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science andTechnology, Okayama University, 3-1-1 Tsushimanaka, Okayama 700-8530, Japan
2
Japan Science and Technology Agency, ACT-C, 4-1-8 Honcho, Kawaguchi, Saitama
332-0012, Japan

Organic thin-film transistors (OTFTs) with [n]phenacenes have attracted much attention
because of their superior organic field-effect transistors (OFETs) characteristics. The[5]phenacene (picene) and [6]phenacene (fulminene)-based OTFT have been fabricated andthe field-effect mobility, μFET, reached the value as high as 3.2 and 3.7 cm2/Vs under O2
atmosphere, respectively (Chart 1). From the synthetic point of view, there are several
critical drawbacks in the reported synthetic methods for [n]phenacenes. Therefore, a simple
and convenient strategy for the synthesis of various substituted [n]phenacenes is highly
desirable in order to promote further investigations into the ideal OFETs, which may besolution-processed and exhibit high carrier mobility and solubility in common organic
solvents.

Chart 1. Structures of picene, fuluminene, and PDT
In this presentation, the synthesis of a series of substituted picenes by sequential
Suzuki-Miyaura coupling and cyclization via intramolecular C−H bond functionalization id
reported [1]. This methodology is also applicable to the synthesis of other picene analogues,
for instance, other fused aromatic compounds such as unsymmetrical fulminene [2], andphenanthro[1,2-b:8,7-b’]dithiophene (PDT) with replacing terminal phenyl rings of picene
with thiophene rings [3].
References:[1] Chang, N.; Chen, X.; Nonobe, H.; Okuda, Y.; Mori, H.; Nakajima, K.; Nishihara, Y. Org.
Lett. 2013, 15, 3558.
[2] Chang, N.; Mori, H.; Chen, X.; Okuda, Y.; Okamoto, T.; Nishihara, Y. Chem. Lett. 2013,
42, 1257.
[3] Nishihara, Y.; Kinoshita, M.; Hyodo, K.; Okuda, Y.; Eguchi, R.; Goto, H.; Hamao, S.;
Takabayashi, Y.; Kubozono, Y. RSC Adv. 2013, 3, 19341.
̶ 19 ̶

Construction of Biomimetic Model Compounds of the Actve Sites in
Metalloenzymes Working for Dioxygen Reduction/evolution
Yasuhiro Funahashi
Department of Chemistry, Graduate School of Science, OsakaUniversity
Machikaneyama, Toyonaka, Osaka 560-0043, Japan
Abstract: In order to understand the dioxygenNHN
chemistry, we designed structures of biomimeticNH
metal complexes on the basis of the followingN
structural insights into the active metal centers in theNHprotein environments: (i) the coordinationN
geometries are structurally distorted, and (ii) the
Figure 1. Cage-type Ligands.
metal centers are asymmetrically assembled in thelimited shell with highly pre-organized ligands. From these viewpoints, we have been
studying two series of bio-mimetic model compounds, (I) structurally distorted metal complex
with a framed diamine ligand, and (II) multimetal complexes using a polyazacryptand as acage type ligand. (Fig. 1).
In the series (I) studies of copper complexes using D-isosparteine (DSp) as a supporting
ligand, we succeeded in controlling O-O bond formation and cleaveage reaction by
combination of distorted coordination geometry and extra-binding of a carboxylate ligand [1].
Since DSp has a preorganized shell structure to make the amine nitrogen atoms coordinating
less covalently, the metal center can be strongly perturbed by the axial coordination of anotheranionic ligand. In the manganese DSp complex system, the Mn(IV)=O species with acarboxylate ligand worked as an electrophilic oxidant for substrate.
In the series (II) studies using polyazacryptands [2], we synthesized multi-metal complexes
mimicking the active sites of metalloproteins. In nature, multicopper oxidases (MCO) andthe oxygen-evolving complex (OEC) of photosystem II catalyze 4e--reduction of dioxygen
and water oxidation, respectively. Using a cage type ligand with bis(aminomethyl)pyridyl
spacers, we synthesized tricopper complexes in various oxidation states. The tricopper cores
reacted with O2 and H2O2 to give the corresponding dioxygen adduct complexes, respectively.
Furthermore, using a cage type ligand with bis(imino)pyrrolyl spacers, we also succeeded insynthesizing Na-containing heterometallic trimanganse complex. The former has an
asymmetric Cu3 core structure composed of TypeII and Type III copper centers in the similarmode of MCO, and the latter has a Mn3Na cubane core structure analogous to OEC.
References:[1] Y. Funahashi, T. Nishikawa, Y. Wasada-Tsutsui, Y. Kajita, S. Yamaguchi, H. Arii, T. Ozawa, K. Jitsukawa, T. Tosha, S. Hirota, T.
Kitagawa, H. Masuda, J. Am. Chem. Soc. 2008, 130, 16444. [2] T. Higa, M. Fukui, K. Fukui, Y. Naganuma, Y. Kajita, T. Inomata, T.
Ozawa, Y. Funahashi, H. Masuda, J. Incl. Phenom. Macrocycl. Chem. 2010, 66, 171.

̶ 20 ̶Electrophoretic adhesion for
fabrication of 3D hydrogel devices    
Taka-Aki ASOH1, Akihiko KIKUCHI2
1Osaka City University, 2Tokyo University of Science Fabrication of microstructure-regulated three dimensional (3-D) hydrogels has
attracted much attention for scaffold in the field of tissue engineering, carrier of drugdelivery systems, and soft actuators. To develop functional hydrogel-devices, the"adhesion" of hydrogels is required.
Hydrogels are similar to the macromolecular-based components in the body, therefore,hydrogels have found numerous applications in tissue engineering, drug delivery systems.
Hydrogels with a large amount of water have attracted much attention as substitute material of
conventional plastics, artificial muscles and organs. Adhesion of soft materials includinghydrogels has therefore attracted attention because it is one of the most important processes
for building functional soft constructs. To develop functional and microstructure-regulated
devices using hydrogels, the "adhesion" of hydrogels is required. However, it is difficult toadhere hydrogel each other, because when any glue is applied to adhere two hydrogels, themotion of the adhesive coated surfaces or mass transfer between the two hydrogels will beencumbered by the presence of solidified glue. Therefore, we developed a novel adhesion
method utilizing electrophoresis.
Electrophoretic adhesion of hydrogels
 We recently reported a novel strategy for the adhesion of cationic and anionichydrogels.[1] During electrophoresis, cationic and anionic polymers move to the cathodeand anode, respectively. Then, polyions were diffused inside of the gels and adhesion wasachieved through the formation of a polyion complex at the interface of the two hydrogels.
The adhered hydrogels were quite stable in water, and detachment of the adhered hydrogels
was also possible by simply applying the inverse voltage. The same hydrogels re-adhered
when the ordered electric field was reapplied, adhesion and detachment of the hydrogels via
electrophoresis exhibited repeatability characteristics.[2] Polyion complexes composed of
weak polyions are not stable in high ionic strength water because of decomposition offormative ionic interaction by salts. However, we found that a deswelling/re-swelling
process of the adhered hydrogels
induced resistance against bending
stress, ionic strength, and inverse
voltage because of a rearrangementof the surface interdigitating chain
segments across the interface. We
then prepared adhered multi-layerhydrogelscomposedofthermoresponsive
andnon-thermoresponsive polymer gels,
which showed uniaxial movement inresponse to temperature without
detachment.[3]̶ 21 ̶

Fabrication of modulable and reconstructible hydrogels
To apply this electrophoretic
adhesion of hydrogels to build a3-Dmaterial,therapidfabricationofhydrogelconstructs will be achieved byelectric field impression to aprecursor. Cationic and anionicpoly(vinyl
alcohol)(PVA)
microbeads were used as thebuilding blocks of the hydrogel
constructs. The same amountsofcationic
andanionic
microbeads were mixed in water.
A pasty product was formed
when the mixed microbead powders were swelled in water, but dispersed in an excess amountof water. Amazingly, the microbead paste was gelled by electric field impression, and thishydrogel construct was stable in water after the removal of the electric field, and was elastic
and durable enough to handle with forceps. These results clearly indicate that the anionicand cationic polymers move to the anode and cathode, respectively, and concentrate at theinterface of the microbeads, thus forming a polyion complex to generate microbead networks
via electrophoresis. Hydrogel constructs which are built by the adhesion of microbeads as
the minimum constituent can form another network. Thus, the reversible preparation ofhydrogel constructs can be achieved by the reconstruction of microbead networks (Fig. 2a).
At first, the microbead paste moulded into a strip, and electrophoresis was carried out toprepare a hydrogel construct. Next, the hydrogel constructs turned back into a pasty material
by grinding to obliterate the adhesion interface of the microbeads (Fig. 2b[i]). After moulding
the pasty microbeads, the construct was gelled into a triangle shape by electrophoresis (Fig.
2b[ii]). Thereafter, a square-shaped hydrogel was prepared by electrophoresis after grinding
the triangle-shaped hydrogel (Fig. 2b[iii] and [iv]). In all steps, the pasty microbeads could be
moulded into any shape and dispersed in an excess amount of water, but the hydrogel
constructs were handled by forceps and were stable in water without leakage of the
microbeads.
Therefore, reconstructible hydrogel materials were prepared by theelectrophoretic adhesion of oppositely charged microbeads as building blocks.[4] These hydrogel materials will be useful for the fabrication of soft actuator, DDS carrier,and scaffold for tissue engineering.
References:[1] Asoh, T.; Kikuchi, A. Chem. Commun. 2010, 46, 7793.
[2] Asoh, T.; Kawai, W.; Kikuchi, A. Soft Matter 2012, 8, 1923.
[3] Asoh, T.; Kawamura, E.; Kikuchi, A. RSC Adv. 2013, 3, 7947.
[4] Asoh, T.; Kikuchi, A. Chem. Commun. 2012, 48, 10019.

̶ 22 ̶

Caenorhabditis elegans as a Model Host to Study
Immunonutrition for Healthy Ageing
Yoshikazu Nishikawa1 and Eriko Kage-Nakadai2
1
Department of Food and Human Health Sciences,
Graduate School of Human Life Science2
The OCU Advanced Research Institute for Natural Science and Technology
Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan
Caenorhabditis elegans is a small free-living soil nematode that feeds on bacteria; it has
been extensively used as an experimental system for biological studies because of its
simplicity, transparency, ease of cultivation, and suitability for genetic analysis.
Particularly for aging studies, the worm has the advantage of a short and reproduciblelife span. The organism has also been recognized as an alternative to mammalian models
of infection with bacterial pathogens [1]. In the field of innate immunity research, C.
elegans is becoming one of the most important experimental animals.
Age at infection is likely one of the most important determinants of diseasemorbidity and mortality. Because aging is accompanied by functional and metabolic
alterations in cells and tissues, senescence of the immune system results in an age-related
increase of infections, malignancy, and autoimmunity. Whether nutritional control canretard senescence of immune function and decrease mortality from infectious diseases
has not yet been established; the difficulty of establishing a model has made this achallenging topic to investigate. Although some studies have shown successful
improvement of biomarkers relating to immunological functions, few reports haveshown a beneficial influence of nutrition on immunity. Hence we have studied whether
the worms could be a model host in the fields of immunonutrition and senescence.
Feeding nematodes lactic acid bacteria (LAB) resulted in increases in average life
span of the nematodes compared to those fed Escherichia coli strain OP50, a standard
food bacteria [2]. The 7-day-old nematodes fed LAB from age 3 days were clearly
endurable to subsequent salmonella infection compared with nematodes fed OP50
before the salmonella infection. The worm could be a unique model to study effects offood factors on longevity and host defense, so-called immunonutrition. Then we
attempted to establish an immunosenescence model using C. elegans. We focused on theeffects of worm age on the Legionella infection and the prevention by immunonutrition[3]. No significant differences in survival were seen between 3-day-old worms fed OP50
and 3-day-old worms infected with virulent Legionella strains. However, when theworms were infected from 7.5 days after hatching, the virulent Legionella strains were
obviously nematocidal for the worms’ immunosenescence. In contrast, nematodes fed
with bifidobacteria prior to Legionella infection were resistant to Legionella.
̶ 23 ̶

C. elegans could definitely act as a unique alternative host for immunosenescenceand resultant opportunistic infection, and immunonutrition researches [4]. However,methods for quantitative oral administration of various substances to nematodes areneeded to explore compounds for the pro-longevity effect. We developed methods fororal administration of chemical substances to C. elegans [5,6]. We used liposomes fororal administration of water-soluble substances to C. elegans. Using liposomes, oral
administration of hydrophilic antioxidants (N-acetyl-cysteine, reduced glutathione, andthioproline) prolonged the lifespan of the nematodes, whereas the conventional methodof delivery showed neither fluorescence nor longevity effects. Our method efficiently andquantitatively delivers solutes to nematodes. γ-cyclodextrin (γCD), which delivers
hydrophobic chemicals, was used to make micro-particles of inclusion compounds thatcan be ingested by bacteriophagous nematodes, which do not distinguish thesemicro-particles from their food bacteria. The lifespan of the nematodes that ingested
γCD inclusion compounds containing tocotrienols [7] or sesamin [8] was longer than thatof control worms maintained on mNGM containing γCD alone.
Bifidobacteria or several chemicals enhanced the host defense of C. elegans against
variety of stressors such as hydrogen peroxide, cupper ion, UV irradiation, and infection
with the opportunistic pathogen Legionella pneumophila than control worms [7-9]. Our
ongoing project will clarify the mechanism how the lactic acid bacteria and the chemicalcompounds exerted pro-longevity effects in worms and contribute to the healthy aging.
References:[1] Hoshino, K.; Yasui, C.; Ikeda, T.; Arikawa, K.; Toshima, H.; Nishikawa, Y. Jpn. J. Food
Microbiol. 2008, 25, 137-147.
[2] Ikeda, T.; Yasui, C.; Hoshino, K.; Arikawa, K.; Nishikawa, Y. Appl. Environ. Microbiol.
2007, 73, 6404-6409.
[3] Komura, T.; Yasui, C.; Miyamoto, H.; Nishikawa, Y. Appl. Environ. Microbiol. 2010, 76,
4105-4108.
[4] Komura, T.; Ikeda, T.; Hoshino, K.; Shibamura, A.; Nishikawa, Y. Adv. Exp. Med. Biol.
2012, 710, 19-27.
[5] Shibamura, A.; Ikeda, T.; Nishikawa, Y. Mech. Ageing Dev. 2009, 130, 652-655.
[6] Kashima, N.; Fujikura, Y.; Komura, T.; Fujiwara, S.; Sakamoto, M.; Terao, K.; Nishikawa,
Y. Biogerontology 2012, 13, 337-344.
[7] Kashima, N.; Fujikura, Y.; Komura, T.; Terao, K.; Nishikawa, Y. In Tocotrienols: Vitamin
E beyond tocopherols, second edition; Tan, B., Watson, R. R., Preedy, V. R., Eds.; CRC Press:
Boca Raton, 2012, p 279-289.
[8] Yaguchi, Y.; Komura, T.; Kashima, N.; Tamura, M.; Kage-Nakadai, E.; Saeki, S.; Terao,
K.; Nishikawa, Y. Eur. J. Nutr. 2014 (in press).
[9] Komura, T.; Ikeda, T.; Yasui, C.; Saeki, S.; Nishikawa, Y. Biogerontology 2013, 14, 73-87.
̶ 24 ̶

Wednesday,5th March̶ 25 ̶

̶ 26 ̶

Oxidized Metal Phenoxide Complexes - Correlation of Electronic Structure
and Reactivity
Tim Storr, Linus Chiang, Ryan ClarkeaDepartment of Chemistry, Simon Fraser University, Burnaby, BC, V5A-1S6,
Canada *Corresponding author: tim_storr@sfu.ca

The interplay of redox-active transition metal ions and pro-radical ligands inmetalloenzyme sites is an area of considerable research interest. The mononuclear copper
enzyme galactose oxidase which functions via a Cu(II)-phenoxyl radical active oxidant, as wellas the Fe(IV)=O porphyrin radical intermediate of P450 enzymes are principal examples.
Both of these enzymatic systems have inspired efforts to develop small molecule mimics
capable of mild and selective oxidation chemistry. Recent developments show that ligands
serving as electron reservoirs offer opportunities to expand catalysis, especially by conferring
to first-row transition metals a “noble metal-like” reactivity.[2] In our research we continue toinvestigate the chemistry of a series of simple oxidized mono- and bis-phenoxide metal
complexes, which demonstrate that small variations of the ligand structure affect the locus ofoxidation.[3] Characterization of the oxidized complexes has afforded significant insight into
the electronic structure of these ligand radical systems [4].
We are currently investigating both monometallic andbimetallic ligand radical complexes (Figure 1). The oxidized forms arecharacterized by both experimental (low temperature UV-Vis-NIR
spectroscopy, electrochemistry, x-ray crystallography, resonanceRaman) and theoretical methods. DFT calculations provide insight into
the oxidation locus, providing further information of the electronic
structure. We have shown that small changes to ligand structure
influences ligand radical localization. We are now probing the effect ofradical localization on reactivity for a large number of mono- andbi-metallic systems.

Figure 1

References: [1] N. Ito, S. E. V. Phillips, C. Stevens, Z. B. Ogel, M. J. McPherson, J. N. Keen,K. D. S. Yadav and P. F. Knowles, Nature, 1991, 350, 87. [2] P. J. Chirik and K. Wieghardt,
Science, 2010, 327, 794. [3] L. Chiang, A. Kochem, O. Jarjayes, T. J. Dunn, H. Vezin, M.
Sakaguchi, T. Ogura, M. Orio, Y. Shimazaki, F. Thomas and T. Storr, Chem. Eur. J., 2012, 18,14117. [4] T. J. Dunn, L. Chiang, C. F. Ramogida, K. Hazin, M. I. Webb, M. J. Katz and T.
Storr, Chem. Eur. J., 2013, 19, 9606.

̶ 27 ̶

Identification of two quenching processes in the dissipative stateof FCP antennas
Md. Wahadoszamen1,3, Charusheela Ramanan1, Kathi Gundermann2,
Hande E. Cingil1, Artur Ghazaryan2, Ivo van Stokkum1, Anjue Mane Ara4,
Claudia Büchel2, Rienk van Grondelle1 and Rudi Berera1

1 Division of Physics and Astronomy, Department of Biophysics, VU University Amsterdam,
The Netherlands
2 Institute of Molecular Biosciences, Goethe University Frankfurt, Frankfurt, Germany
3 Department of Physics, University of Dhaka, Dhaka-1000, Bangladesh
4 Department of Physics, Jagannath University, Dhaka-1100, Bangladesh
Diatoms are characterized by a very strong response to excess light conditions, stronger thanin any terrestrial plant. We performed Stark and transient absorption spectroscopy on
fucoxanthin-chlorophyll proteins (FCPs) from the diatom cyclotella meneghiniana. Stark
spectroscopy revealed two quenching-induced emitting sites in the dissipative state of FCPs,
one of which is characterized by red-shifted emission above 700 nm, strong charge transfer
character and low fluorescence yield[1]. Transient absorption spectroscopy allowed us to put
quantitative basis on the quenching processes and to extract the transient spectra of thequenching species. More specifically we identified a faster quenching (kq1=16 ns-1), whosetransient spectrum is very similar to that of bulk chlorophylls in the unquenched sample and aslower quenching (kq2=2.7 ns-1) associated with a distinctive red-shifted feature in its transient
spectrum. I will discuss the results in the light of the different mechanisms proposed to be
responsible for photosynthetic energy regulation.
1.

Wahadoszamen, M., et al., Stark fluorescence spectroscopy reveals two emitting sites
in the dissipative state of FCP antennas. Biochimica et Biophysica Acta (BBA) Bioenergetics, 2014. 1837(1): p. 193-200.

̶ 28 ̶

Formation of PSII-LHCII-LHCSR supercomplex under
NPQ inducible conditions
Ryutaro Tokutsu and Jun Minagawa
National Institute for Basic Biology, Nishigonaka 38, Myodaiji,
Okazaki 444-8585
tokutsu@nibb.ac.jp
Abstract
Photosynthetic organisms have developed mechanisms to control dissipation of excess
light energy to avoid photodamage of the photosystems, including qE quenching inphotosystem II (PSII). Although qE quenching has been been developed in all
photosynthetic organisms, large differences exist in its amplitudes, kinetics and therelated proteins. We performed a detail biochemical analysis of the LHCSR protein,which has been identified as essential in qE quenching in the green alga
Chlamydomonas

reinhardtii.

Wild-typestrainexhibited

theformationof

PSII-LHCII-LHCSR supercomplex in a sucrose density gradient under high light
conditions. Nickel column purification of the His-tagged PSII confirmed the stableassociation of LHCSR with PSII-LHCII supercomplex. We also found that the
PSII-LHCII-LHCSR supercomplex exhibited significant capacity of energy quenchingunder the NPQ inducible conditions. We discuss the correlation between NPQ
capability and stable formation of the PSII-LHCII-LHCSR supercomplex in C.
reinhardtii.

̶ 29 ̶

Protein engineering for the creation of algae with highformate productivityt
Masaki Ihara
Shinshu University, JST-PRESTO
Abstract:
One of the ultimate goals in artificial photosynthesis researches is to reengineer natural
photosystems into systems specialized for the production of the energy-carrier compounds.
By cultivating the cyanobacteria or algae having such engineered photosystems, we canmultiply them easily and will produce bioenergy at lower costs. We focus on formate as anenergy carrier because it can be easily converted to hydrogen energy, and its water-solubility
enables low-cost transport and storage. Formate can be produced from carbon dioxide andreducing powers generated by photosystems by using the catalytic activity of Formate
dehydrogenase (FDH). In our previous study, we successfully created an artificial light driven
formate production system by combining the newly engineered NADPH-dependent FDH andnaural photosystem, and demonstrated that cyanobacteria expressing the system in theirheterocyst cells can produce significantly higher formate [1].
As the next step, to achieve higher efficient system, we are trying to create the complex
constituted of cyanobacterial PSI and molybdenum-dependent FDH. We have reported thecomplexes of PSI and bacterial hydrogenase that catalyzes the reversible oxidation andevolution of hydrogen [2]. The hydrogenase-PSI complexes were self-assembled from PSI
deficient in PsaE subunit and hydrogenase fused with PsaE, and produce hydrogen gas byirradiation with visible light. This strategy is also applicable to the formate production. We
selected membrane-bound FDH encoded by fdo gene (FDH-O) of E.coli as a catalyst for the
carbon dioxide reduction. FDH-O is an enzyme which is composed of a catalytic domain
bearing a molybdopterin cofactor, an electron transfer domain carrying Fe-S clusters and atransmembrane domain. We first introduced a plasmid carrying fdo gene into the
FDH-deficient E.coli, and demonstrated that a recombinant FDH-O could be expressed as anactive form. Next, we deleted its transmembrane domain from fdo gene and fused a genecoding for PsaE and flexible linkers (5, 10 and 15 amino acids) into the fdo gene. Afterchanging the plasmid, optimizing the culture conditions and introducing amino subsutitutions,
we finally succeeded in the expression of the FDH-PsaE fusion proteins. Now, we are trying
to purify the fusion protein and will examine the in vitro assembly of FDH-PsaE and
PsaE-less PSI and the light-driven formate production by the FDH-PSI complex.
References:[1] M. Ihara et al., PLOS one 2013, 8, e71581.
[2] M. Ihara et al., Photochem. Photobiol. 2006, 82, 676-682.
̶ 30 ̶

Poster Presentations

̶ 31 ̶

̶ 32 ̶

Towards structural elucidation of PSII-LHCII supercomplex from
Chlamydomonas reinhardtii
Keisuke Kawakami
The OCU Advanced Research Institute for Natural Science & Technology (OCARINA),CREST-JST, Sugimoto, Sumiyoshi-ku Osaka 558-8585 JAPAN.
E-mail: keikawa@ocarina.osaka-cu.ac.jp
Abstract: On photoacclimation in higher plants, the transient macromolecular complexes areformed by association and disassociation of light harvesting complexes which absorb lightenergy. Recently, the crystal structure of PSII isolated from thermophilic cyanobacteria wasresolved at 1.9 Å resolution [1], and the crystal structures of light harvesting complex II(LHCII) was resolved at 2.5 Å resolution [2], however, structural information for the entire
PSII-LHCII supermolecular complex is limited, Thus, the interaction between membraneproteins on photoacclimation has not been elucidated. In order to elucidate photoacclimationin higher plants, I will crystallize and analyze PSII-LHCII supermolecular complex isolated
from Chlamydomonas reinhardtii, and construct the transient macromolecular complex
infrastructure.
Previous research:
In order to understand the mechanism of oxygen evolution in PSII, several research groups
analyzed the structures of PSII from thermophilic cyanobacteria by X-ray crystallography at
2.9 ~ 3.8 Å resolution, however, the detailed structure of the Mn4CaO5-cluster was not able tobe analyzed. This biggest reason was that all research groups were not able to obtain highquality PSII crystals. PSII is one of the membrane protein complexes embedded in thethylakoid membrane, consisting of 17 membrane spanning proteins, 3 extrinsic proteins, andover 100 cofactors with a molecular mass of 700 kDa for a dimer. Although X-ray
crystallography is the only way to analyze large membrane complexes such as PSII, it isnecessary to obtain high quality single crystals. We have studied the improvement of
purification and crystallization conditions of PSII, and we succeeded in obtaining the highquality PSII crystal which the structure of PSII can be analyzed at an atomic resolution in2009 (Figure 1).
In 2011, we reported the detailed structure of PSII, especially the structure of
Mn4CaO5-cluster, at a resolution of 1.9 Å [1]. The positions of 4 water molecules that aresubstrates were identified around the cluster, and several hydrogen-bonding networks fromthe cluster to the lumenal bulk phase were identified. Moreover, the accomplishment of X-ray
crystallography of PSII was chosen to one of the Breakthrough of the Year of Science in 2011.
The reason our accomplishment was chosen to this important news not only contributed to theelucidation of the mechanism of oxygen evolution, but also was because this achievement was̶ 33 ̶

expected to the solution of energy and environmental problems by using an artificial
photosynthesis system.

Figure 1: A PSII crystal and its X-ray
diffraction pattern. The diffraction pattern was
taken at BL44XU of SPring-8, Japan, with awavelength of 0.9 Å at 100 K. The lower panel
is an enlarged picture of the boxed area in theupper panel.

References:[1] Umena Y, Kawakami K, Shen JR, Kamiya N, Nature, 2011, 55-60.
[2] Standfuss J, Terwisscha van Scheltinga AC, Lamborghini M, Kühlbrandt W, EMBO J.,
2005, 24, 919-928.

̶ 34 ̶

Synthetic Study of Highly Oxygenated Tetramethylphloroglucinols
Eiji Nishimura, Yasufumi Ohfune, Tetsuro Shinada*
Graduate School of Science, Osaka City University
3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan
Several naturally occuring tetramethyl cyclohexatriones and cyclohexadiones classified
into monomeric polyalkylated phloroglucinols have been isolated. These are rich sources of
biologically active molecules exhibiting anthelmintic activity, anti bacterial activity against
methicillin-resistant Staphylococcus aureus (MRSA), vancomycin-resistant Enterococcus
faecalis (VRE) and multidrugresistant Mycobacterium tuberculosis (MDR-TB)[1], andpotent in vitro activity against humantumour cell replication. In this presentation, we would
like to report our efforts toward total synthesis of highly oxidized phloroglucinols 1 and 2
in which the total syntheses have not been reported[2, 3].

References[1] van Klink, J. W.; Larsen, L.; Perry, N. B.; Weavers, R. T.; Cook, G. M.; Bremer, P. J.;
MacKenzie, A. D.; Kirikae, T. Bioorg. Med. Chem. 2005, 13, 6651-6662.
[2] Weyerstahl, P.; Marschall, H. Flav. Fragr. J. 1994, 9, 333-337.
[3] Appendino, G.; Maxia, L.; Bettoni, P.; Locatelli, M.; Valdivia C.; Bellero, M.; Stavri,M.; Gibbons, S.; Sterner, O. J. Nat. Prod. 2006, 69, 251-254.

̶ 35 ̶

Synthetic Study of All-trans Type Long-chain Isoprenoids
Yusuke Totsuka, Tetsuro Shinada
Graduate School of Sci., Osaka City Univ.
3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Jpan
The long-chain isoprenoids are a unique class of secondary metabolites within theterpenoid natural product family. The isoprenoids which have C50C100 carbon chain wereisolated from mammalian tissues and bacteria.[1] These molecules contain many trisubstituted
cis olefin units and play an important role of membrane anchor. These are essential toconserved cellular processes including N-linked protein glycosylaltion, C- and O-protein
mannosylation, and bacterial cell wall biosynthesis.[2] Although these isoprenoids haveunique functions, mechanistic studies have not been progressed to date because of difficultyof isolation from natural sources. In this report, we describe the synthetic study of all-transtype C100 isoprenoids in order to elucidate the role of cis olefin units of natural long-chain
isoprenoids.

We synthesized all-trans type long-chain isoprenoids by means of repetitive
unit-linkage reaction[3] and sulfone coupling reaction. Although the molecule has simple
structure, it revealed difficult to synthesize the long carbon chain. As a result of various
investigations, C85 all-trans type isoprenoid was synthesized.

[1] Marczewski, A.; Ciepichal, E.; Canh, L. X.; Bach, T. T.; Swiezewska, E.; Chojnacki, T.
Acta Biochimica Polonica 2007, 54, 727-732.
[2] Hartley, M. D.; Barbara, I. Arch. Biochem. Biophys. 2012, 517, 83-97.
[3] Manabe, A.; Ohfune, Y.; Shinada, T. Synlett 2012, 1213-1216.

̶ 36 ̶

Coordination Behavior of D-Penicillamine-Derived Schiff-Bases
toward Manganese Ion
Naoto Kuwamura,1 Shuntaro Kodera,1 Asako Igashira,1 Takumi Konno1,2
1
Department of Chemistry, Graduate School of Science, Osaka University, 2CREST-JST
Amino acid coordination chemistry was widely studied in 20th by the motivation of thebiochemical importance such as the metalloenzymatic mimic. Despite the Mn containing
protein active site with high-valent state was found by biochemists, the amino acidcoordination chemistry toward high-valent Mn ion is not well-defined probably due to thepoor solubility of the product, where the amino acid functions as a metal-bridging ligand to
make an insoluble polymer structure. Therefore, a chemical modification of amino-acid
structure was inspired and used for the study of the coordination behavior.
Our continuous work is the construction of multinuclear
supramolecular structure by using imino-thiol type ligands(H3salpen) prepared from the condensation of
sulfur-containing amino acid, D-penicillamine, (D-H2pen),and salicylaldehyde (sal) derivatives (Figure 1). Herein,
this poster shows the investigation of the coordination
behavior of the H3salpen derivatives toward Mn(III) ion and introduce the obtained
multinuclear and high-valent Mn complex architectures.
The mixture of chlorine-atom-substituted sal derivative (5-chloro-sal), D-H2pen, Et3N, and
MnIII(OAc)3·4H2O in MeOH was stirred at room temperature under aerobic condition to givea green solution, from which dark green block crystals (1) were appeared in 2 weeks. The
single-crystal X-ray diffraction study of 1 shows a discrete 13-nuclear Mn structure, in which
the thiol group of 5-chloro-salpen ligands were oxidized to form a new imino-disulfide ligand,5-chloro-salpends. This oxidation would be performed by the dissolved oxygen molecules in areaction solution because the control experiments under N2 atmosphere did not afford the
crystals of 1. In crystal, the three salpends ligands bridge
two Mn(III) ions and one Mn(II) ion via the fac-O,O,N
atoms to form a ring-shaped trinuclear Mn(III)2Mn(II)structure and further one Mn(II) ion is incorporated into thering structure by the coordination of two carboxylate andtwo phenoxide groups resulting in the mixed-valenttetranuclear Mn(III)2Mn(II)2 unit. The carboxylate groupfacing outward from the ring-shaped tetranuclaer unit
coordinates to one additional Mn(II) ion to complete thediscrete 13-nuclear Mn structure (Figure 2).

̶ 37 ̶

Synthesis and Bioactivity of Kaitocephalin Analog Bearingan Alkyl Side Chain on the Aromatic Ring
Yuya Yoshida, Yoko Yasuno, and Tetsuro Shinada
Graduate School of Science, Osaka City University
3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan
Kaitocephalin (1), isolated from thefilamentous fungus Eupenicillium Shearii PF1191
by Seto and Shin-ya et al., is known to be a potent
antagonist of ionotropic glutamate receptors(iGluRs).[1] Antagonists of iGluRs are regarded
as a potent drug lead to develop therapeutic
agents for the treatment of neurological diseases.

R
HO

H
N

Cl

H
CO2 H

O

CO2 H
NH2

N
H
HO

CO2H

1: R = Cl (Kaitocephalin)
2: R =We have reported efficient total synthesis of 1[2],structure activity relation study[3], and X-ray crystal structure of 1 bound to the ligand
binding domain of the AMPA receptor subtype of iGluRs.[4] These results led us to design a
new analog 2, where a chloro group on the aromatic ring is replaced with a n-propyl group. In
this presentation, we would like to report the synthesis of 2 by means of coupling reaction of
three fragments 35.
OTBS
OHC

CO2Me
N
Boc
3

NHCbz
O
OO

4

9 steps

HO

H
N

Cl

BnO

H
N

Cl

O
P(OPh)2

O

CO2H
NH2

H N
CO2H H
HO
2

CO2H

CO2Me

O

5

[1] Shin-ya, K.; Kim, J.-S.; Furihata, K.; Hayakawa, Y.; Seto, H. Tetrahedron Lett. 1997, 38,
7079-7082.
[2] Hamada, M.; Shinada, T.; Ohfune, Y. Org. Lett. 2009, 11, 4664-4667.
[3] 51th Symposium on the Chemistry of Natural Products 2009, 401.
[4] Ahmed, A. H.; Hamada, M.; Shinada, T.; Ohfune, Y.; Weerasinghe, L.; Garner, P. P.;
Oswald, R. E. J. Biol. Chem. 2012, 287, 41007-41013.

̶ 38 ̶

Synthetic Study of Phomopsin A
Yoko Yasuno and Tesuro Shinada
Graduate School of Science, Osaka City University
3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan
Phomopsin A (1) is a family of mycotoxins produced by the fungus Diaporthe toxica.
The natural product is a hexapeptide consisted with highly unsaturated and functionalized
non-proteinogenic amino acids, which binds with high affinity to tubulin and disrupts
microtubular functions.[1] According to the interesting biological activities and the novel
structural feature, 1 has attracted attention as a synthetic target. Although several groups havedevoted many efforts, the total synthesis of phomopsin B (2) has only been reported.[2] In thispresentation, we would like to report our synthetic efforts toward total synthesis of 1.
One of the keys to achieve total synthesis of 1 is a setereoselective method to prepare
E-'Ile and E-'Asp in tripeptide side chain. To this task, we adopted a new synthetic routeusing D-(diphenylphosphono)glycine ester 3 (eq. 1).[3] E-'Asp ester was synthesized in one
step by the condensation of ethyl glyoxalate with high E-selectivity. Stereocontrolled
synthesis of 'Ile ester was accomplished in three steps: (i) stereoselective synthesis of
E-E-Et-dehydroamino acid ester; (ii) the Z-selective E-iodination; and (iii) Negishi
cross-coupling reaction in a highly stereoselective manner (eq. 2).
Me
MeHN

HN
O O Et
Me
O

HO

R
O
(PhO)2P

O

NH

Me

N
O

OH

(i)

CO2H

O
N
H

CO2H
O
(PhO)2P

Et

CO2R1
3

CO2Me
Et

NHBoc

Z-selective
E-iodination(ii)

base-additive

CO2Me
Et

NHBoc
I

CO2R1

R2CHO

NHP

Phomopsin A : R = Cl (1)Phomopsin B : R = H (2)NHBoc EtCHO
CO2Me

H
N

R2

NHP

(1)

E-Dehydroaminoacid ester
Negishicoupling
(iii)

CO2Me
Et

NHBoc

(2)

Me

[1] (a) Culvenor, C. C. J.; Beck, A. B.; Clarke, M.; Cockrum, P. A.; Edgar, J. A.; Frahn, J. L.;
Jago, M. W.; Lanigan, G. W.; Payne, A. L.; Peterson, J. E.; Petterson, D. S.; Smith, L. W.;
White, R. R. Aust. J. Biol. Sci. 1977, 30, 269-277. (b) Mackay, M. F.; Van Donkelaar, A.;
Culvenor, C. C. J. J. Chem. Soc. Commun. 1986, 1219-1221. c) Culvenor, C. C. J.; Edgar, J.
A.; Mackay, M. F. Tetrahedron 1989, 45, 2351-2372.
[2] Grimley, J. S.; Sawayama, A. M.; Tanaka, H.; Stohlmeyer, M. M.; Woiwode, T. F.;
Wandless, T. J. Angew. Chem., Int. Ed. 2007, 46, 8157-8159.
[3] Yasuno, Y.; Hamada, M.; Yamada, T.; Shinada, T.; Ohfune, Y. Eur. J. Org. Chem. 2013,
1884-1888.
̶ 39 ̶Development of Catalytic Asymmetric Diels-Alder Reactionof Nitro Olefin Using Chiral Thioura Catalyst
Shota Ueda, Atsushi Manabe, and Tetsuro Shinada
Graduate School of Science, Osaka City University
3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan
Nitro olefins are electron deficient olefins that smoothly react with a variety of
nucleophiles to give the corresponding 1,4-adducts. Nitro olefins are also known to bereactive dienophiles in Diels-Alder (DA) reactions. In this presentation, we would like todescribe a catalytic asymmetric DA reaction using highly reactive E-nitro acrylate 1 andhighly reactive furan 2 with a chiral thiourea catalyst.
DA reaction of 1 and 2 in presence of thiourea catalyst 5[1] proceeded smoothly toafford the desired DA product 3 as a hemiaminal. However, the competition reaction to
produce the conjugate addition product 4 was observed. After the extensive study, we foundthat the product yield and selectivity (3 vs 4) were improved by using catalyst 6 in toluene.
O
NO2 +

EtO2C

1

O

+

O
o

CO2Et

OH
NHBoc

solvent, 40 C, 24 h

NHBoc

O2N

CO2Et

O2N

catalyst (5 mol%)

NHBoc

3

2
yield

4

ee

entry

catalyst

solvent

3

4

3

4

dr

1

5

CH2Cl2

12%

28%

2%

7%

8:1

2

6

CH2Cl2

<58%

18%

58%

59%

-

3

6

THF

16%

35%

9%

2%

4.6 : 1

4

6

CH3CH2CN

27%

26%

21%

14%

3.6 : 1

5

6

toluene

38%

15%

81%

72%

6:1

t-Bu
N
CF3

N

O

N
H

S
N

N
H

S
N
H

N

HO
N
H

CF3
t-Bu

5

t-Bu

6

[1] Tripathi, C. B.; Kayal, S.; Mukherjee, S. Org. Lett. 2012, 14, 3296-3299.

̶ 40 ̶

Synthetic Study of Cirratiomycin A
Akito Nishimura, Yoko Yasuno, and Tetsuro Shinada
Graduate School of Science, Osaka City University
3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan
Cirratiomycin A (1) exhibiting a characteristic antibiotic spectra was independently
isolated from Streptomyces cirratus 248-Sq2 by Seto et al.[1a], and Streptomyces
xanthocidicus MG125-CF1 by Umezawa et al.[1b]. The natural product 1 is consisted withfour nonproteinogenic amino acids and three proteinogenic amino acids. The key to the total
synthesis relies on the synthesis of these nonproteinogenic amino acids. Among them, only alittle attempt to the stereoselective synthesis of E-dehydroisoleucine (E-'Ile) has beenreported. In this report, we describe the stereoselective synthesis of the tripeptide chain of 1.
D-Diphenylphosphonoglicinate 3 was synthesized from diazocompound 2 by a
Rh-catalyzed N-H insertion reaction. E-selective olefination[2] of propionaldehyde with 3
gave E-ethyl substituted dehyrdroamino acid ester 4 with E-selectivity. Then, treatment of 4
with Z-selective E-iodination followed by Negishi coupling[3] provided 5 possessing E-'Ilemoiety. The stereoselective synthesis of 6 was accomplished by a condensation reaction with
L-serine.

[1] (a) Shiroza, T.; Ebisawa, N.; Kojima, A.; Furihata, K.; Shimazu, A.; Endo, T.; Seto, H.;
Otake, N. Agric. Biol. Chem. 1982, 46, 1885-1890. (b) Shimada, N.; Morimoto, K.;
Naganawa, H.; Takita, T.; Hamada, M.; Maeda, K.; Takeuchi, T.; Umezawa, H. J. Antibiot.
1981, 34, 1613-1614.
[2] Yasuno, Y.; Hamada, M.; Shinada, T.; Ohfune, Y. Eur. J. Org. Chem. 2013, 1884-1888.
[3] 93rd Annual Meeting of The Chemical Society of Japan, 4D1-44 (2013).

̶ 41 ̶

Synthesis of Novel Peptide Analogs by Incorporation of
Squaric Acid-containing Amino Acid
Kentaro Maeda and Tetsuro Shinada
Graduate School of Science, Osaka City University
3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan
Incorporation of the non-natural amino acid into peptides to create the new peptide
analogs have been employed as a useful tool in the research areas of bioorganic and medicinal
chemistries. To date, several D-amino acid analogs in which the carboxylic acid moiety isreplaced with other acidic functional groups, such as sulfonic acid, phosphonic acid, boronic
acid, and tetrazole etc., have been developed. However, a few examples of the incorporationof these analogs into the middle position of the peptide have been reported due to theirinstability of the corresponding amide-like bonds.
Recently, we have developed a novel amino acid analog 1 bearing a 4-hydroxy-2,3dioxocyclobut-1-enyl (Sq) group (D-amino squaric acid, D-Asq) [1, 2]. The Sq group ischaracterized by its planar structure, acidic OH group, and electron deficient property. So, we
anticipate that D-Asq could be employed as the flexible peptide incorporation unit to prepare
the chemically stable peptide analogs.
In this presentation, we will report the synthesis of novel D-Asq-containing peptides
on both of liquid-phase and solid-phase. Various peptide analogs, enkephalin analogs 2 [3]and caspase-3 inhibitor 3 and the novel peptide library 4 were prepared. Biological activitiesof these new peptides will be discussed.

[1] Ishida, T.; Shinada, T.; Ohfune, Y. Synthesis 2005, 2723-2729.
[2] Ishida, T.; Shinada, T.; Ohfune, Y. Tetrahedron Lett. 2005, 46, 311-314.
[3] Shinada, T.; Ishida, T.; Hayashi, K.; Yoshida, Y.; Shigeri, Y.; Ohfune, Y. Tetrahedron Lett.
2007, 48, 7614-7617.

̶ 42 ̶Development of Bifunctional C5 Unit for the Synthesis of Carotenoids:
Synthetic Study of Paracentron
You Yano,1) Naoto Kinashi,1) Hideki Hashimoto,2) Daisuke Kosumi,2)Kazuhiko Sakaguchi,1) Tetsuro Shinada,1) Shigeo Katsumura,2)
1) Graduate school of Science, Osaka City University,
3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan2) Osaka City University Advanced research Institute for Natural Science & Technology(OCARINA), Japan
Carotenoids are biologically important natural products consisted of eight isoprene units
with poly conjugated double bonds. Structure of carotenoids is characterized by their all-transconjugated polyenes, which are responsible for their remarkable biological functions.
Therefore, the development of new method for the stereoselective synthesis of all-transcarotenoids has received considerable attention in this research area. In this presentation, wewish to report our efforts for the construction of all-trans conjugated polyene system using a
new bifunctional C5 building block 1, i.e., the isoprene unit having iodide and pinacolborane
in its each terminal. The synthetic study toward a total synthesis of naturally occurring marine
apocarotenoid, paracentron, using 1 will be also described.

̶ 43 ̶

Regulation of the Receptor Ability of Znporphyrin with Sterically Bulky
Shielding Units by the Formation of Fe Complexes
Yoshikazu Ninomiya, Masatoshi Kozaki, Shuichi Suzuki, Keiji Okada
Graduate School of Science, Osaka City University
3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan
Abstract: Recently artificial allosteric systems have been attracting considerable interest as
smart catalysts, molecular machines, and targeted drug delivery reagents. We previously
found the Fe(II)-induced allosteric suppression for the ligand binding ability of the Zn
porphyrin unit in artificial allosteric system 1 with sterically bulky ligand [1]. In this work, we
prepared artificial allosteric system 2 that expresses remarkable enhancement of the degree ofallosteric suppression.
Allosteric system 2 was synthesized according to the method similar to the report of 1.
UV-vis titration indicated the quantitative formation of Fe-complex 2•Fe (K2•Fe > 106 M1) intoluene/acetonitrile (1/1 (v/v)). The degree of allosteric suppression for the binding of
3, 5-bis(3, 5-di-tert-butylphenyl)pyridine (L) with the Zn-porphyrin unit in 2 was estimatedby the comparison of the binding constants before and after the complexation. The binding
constants K2•L and K(2•Fe)•L were determined to be 3.29 ± 0.10 × 104 M1 and 0.348 ± 0.018 ×
104 M1, respectively. The degree of the allosteric suppression (K2•L/ K(2•Fe)•L) was evaluatedas 9.5 times. The variable temperature titrations were carried out to obtain thermodynamic
parameters for the ligand binding reaction before and after the complexation. As a result, thereaction of 2•Fe and L has smaller enthalpy change ('H = 28 kJ mol1) than the reaction of
2 and L ('H = 35 kJ mol1), suggesting that the coordination bond between nitrogen atom of
L and zinc atom of 2 in (2•Fe)•L is weakened due to steric congestion between shielding
units in 2 and L.

[1] Kozaki, M.; Ninomiya, Y.; Suzuki, S.; Okada, K. Tetrahedron Lett. 2013, 54, 36583661.

̶ 44 ̶

Synthetic Study of Tetrodotoxin
Atsushi Manabe and Tetsuro Shinada
Graduate School of Sci., Osaka City Univ.
3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan
Tetdorotoxin(1), originally isolated from the puffer fish, is well-known marin toxins, andattracts much attention from scientists because of its unique chemical structure and potent
biological activities. Biological mechanism of 1 was reported to be a specific inhibition ofvoltage dependent Na+-channels. Since this finding, 1 has widely used as an importantbiochemical tool to investigate neurophysiological studies. The first total synthesis of rac-1
was reported by Kishi, Goto, et al. in 1972. [1] After that, the total synthesis of optically
active 1 have been reported by three groups, Isobe and Nishikawa, Du bois, and Sato groups,
independently. [2]
HO
H
H2N
N
H N
O
H

O
H O
O
O
OH
OH

Tetrodotoxin (1)In this presention, we would like to describe our recent efforts toward the total synthesisof 1 via Diels-Alder (DA) reaction as a key step. Oxabicyclo[2,2,1]heptanes derivative 3 wassynthesized by DA reaction of a nitro olefin 2 and 3-siloxyfuran in one step. The quaternaryamino carbon-center was constructed by a palladium-catalyzed allylation reaction to give 4.
Heteroatom manipulation of 4 provided 5 possessing the same carbon skeleton as that of 1
except for the hydroxymethyl moiety on the cyclohexane ring.
O
O2 N

O2 N
OTIPS
CO 2Et

CO 2Et
O

TFA

2

3

O

OH

O2 N

Pd

4

1

O

O
OAc

OTBS

NsHN

OH

5

O

[1] (a) Kishi, Y.; Aratani, M.; Fukuyama, T.; Nakatsubo, F.; Goto, T.; Inoue, S.; Tanio, H.;
Sugiura, S.; Kakoi, H. J. Am. Chem. Soc. 1972, 94, 9217. (b) Kishi, Y.; Fukuyama, T.; Aratani,
M.; Nakatsubo, F.; Goto, T.; Inoue, S.; Tanio, H.; Sugiura, S.; Kakoi, H. J. Am. Chem. Soc.
1972, 94, 9219.
[2] (a) Ohyabu, N.; Nishikawa, T.; Isobe, M. J. Am. Chem. Soc. 2003, 125, 8798. (b)Nishikawa, T.; Urabe, D.; Isobe, M.; Angew. Chem. Int., Ed. 2004, 43, 4782. (c) Hinman, A.;
Du Bois, J. J. Am. Chem. Soc. 2003, 125, 11510. (d) Sato, K.; Akai, S.; Shoji, H.; Sugita, N.;
Yoshida, S.; Nagai, Y.; Suzuki, K.; Nakamura, Y.; Kajihara, Y.; Funabashi, M.; Yoshimura, J. J.
Org. Chem. 2008, 73, 1234.
̶ 45 ̶

Polyfunctional Carotenoid Synthesis via One-pot Strategy:
Toward Elucidation of Energy Transfer Processin Marine Photosynthesis
Naoto Kinashi,1) Takayuki Kajikawa,2) Kouki Yano,2) Shouhei Hananoki,2)
Shinji Hasegawa,2) Daisuke Kosumi,3) Hideki Hashimoto,3) Harry A. Frank,4)Kazuhiko Sakaguchi,1) Tetsuro Shinada1) and Shigeo Katsumura3)
1) Graduate School of Science, Osaka City University, Japan
2) School of Science and Technology, Kwansei Gakuin University, Japan3) Osaka City University Advanced Research Institute for Natural Science & Technology(OCARINA)
4) Department of Chemistry, University of Connecticut
We have reported the total synthesis of peridinin that is characterized by thestereo-controlled construction of the polyene chain-conjugated J-ylidenebutenolide via the
Pd-catalyzed carbon-carbon bond formation followed by intramolecular lactonization.[1] In
this presentation, we would like to report the successful synthetic application to the synthesisof a peridinin analogue having the ylidenbutenolide moiety at the different position.[2] The
ICT energy level of these analogs that is responsible for the excellent energy transfer
efficiencies from peridinin to chlorophyll a will be discussed.

References:[1] N. Furuichi, H. Hara, T. Osaki, H. Mori, S. Katsumura, Angew. Chem. Int. Ed. 2002, 41,1023-1025.
[2] Kajikawa, T.; Furuichi, N.; Katsumura, S. Yuki Gosei Kagaku Kyokaishi, 2010, 68,
625-637.

̶ 46 ̶

Synthetic Study of Substituted Pyridone Carboxylates
Kumi Misaki, and Tetsuro Shinada
Graduate School of Science, Osaka City University,
3-3-138, Sugimoto, Sumiyoshi, Osaka 558-8585, Japan
Substituted pyridone carboxylates are often found in biologically active molecules as theirheteroaromatic moiety. Acromelic acid A (1)[1], B (2)[2] and acromelobinic acid (3)[3]
having depolarizing effects in the mammalian central nervous system are theirrepresentatives.
HO2C

H
N

O
O

H
N

CO2H

CO2H
N
H

HO2 C

CO2H

CO2H

N
H

Acromelic acid A (1)

H
N

O

NH2
CO2H

CO2H

Acromelobinic acid (3)Acromelic acid B (2)Herein, we report an efficient method to access to varying pyridone carboxylates by crosscoupling reactions of 3-iodo-2-pyridone-6-carboxylate 4 prepared from α,β-dehydroaminoacid derivative.
Heck Reaction

MeO 2CHN

MeO 2C

H
N

O

a

R

Sonogashira
Cross Coupling

MeO 2 CO

MeO 2CN

9HN

MeO 2Ce
Suzuki-Miyaura
Cross Coupling

d

OBn

8a-d

TMS
O
Ar

g

O

MeO 2CPh

7b : R =8a : Ar = Ph

NO2

N

OBn
8c : Ar =StilleCross CouplingR

7a : R = H

8b : Ar =

f

I

N

Ph
6

low yield

I
4

MeO 2 COor

b or cHN

5a : R = CO2 Et
5b : R = Ph

10a-d

Ar

8d : Ar =

OMe
S

8a

h

o
Conditions : (a), Pd(PPh 3) 2Cl2 , Et3N, CuI,
R , Pd(OAc) 2 , Et3N, CH 3CN, MW 100 C, 62-94%; (b) TMS
THF, rt, 56%; (c) Ph, Pd(PPh 3) 2Cl2, Et3N, CuI, THF, rt, 77%; (d) BnBr, Ag2 CO3, THF, reflux, 95%; (e)PhB(OH) 2, Pd(OAc) 2 , SPhos, Et3N, DMF, 100 oC, 49%; (f) ArB(OH) 2 , Pd(OAc) 2 , SPhos, Et3N, DMF, 100 oC, 76-96%;(g) H2 , AcOEt/MeOH, rt or TFA, neat, rt, 0-100%; (h) PhSnBu 3, Pd2(dba) 3・ CHCl3 , AsPh3 , CuI, NMP, 60 o C, 88%.

[1] Konnno, K.; Shirahama, H.; Matsumoto, T. Tetrahedron Lett. 1983, 24, 939-942.
[2] Konnno, K.; Hashimoto, K.; Ohfune, Y.; Shirahama, H.; Matsumoto, T. J. Am. Chem. Soc.
1988, 110, 4807-4815.
[3] (a) Yamano, K.; Hashimoto, K.; Shirahama, H. Heterocycles 1992, 34, 445-448.
(b) Yamano, K.; Hashimoto, K.; Shirahama, H. Tetrahedron 1993, 49, 2427-2436.
̶ 47 ̶

Syntheses and Structures of Bis(diarylamino)borane Derivatives
in Neutral and Cationic States
Kohei Yoshida, Shuichi Suzuki, Masatoshi Kozaki, and Keiji Okada
Department of Chemistry, Graduate School of Science, Osaka City University
Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan
S-Conjugated compounds containing p-block elements such as B, P, and Si other than C,N, and O have attracted much attention because of their unique electronic structures andphotophysical properties. We have recently been interested in redox active π-conjugatedmolecules containing B–N bonds, because they could generate radical cation species by one
electron oxidation at the nitrogen center. In our previous study, we synthesizedtris(N-phenothiazynyl)borane (1) and its radical cation species, and clarified that thesecompounds have certain stabilities against air andmoisture [1]. In addition, we also challenged togenerate bis(radical cation) species. However, thebis(radical cation) species could not be generated bychemical oxidation because of their instability. For
further elucidation of the B–N bond character andfor further synthetic challenge of the bis(radical
cation) species we extended our work to bis(N-phenothiazinyl)borane 2,bis(N-dihydrophenazinyl)borane 3, and bis(N-phenoxazinyl)borane 4.
Neutral compound 2, 3, and 4 were prepared from lithium diarylazanide and i-Pr2NBF2. In
addition, we succeeded in the isolation of radical cation species 2•+, 3•+ and 4•+ by chemical
oxidation. The molecular structures in neutral and radical cationic states were determined by
X-ray crystal structure analyses (Figure 1). The details of attempts to generate the bis(radical
cation) species will be reported in the presentation.

Figure 1. Molecular structure of 2•+ (a), 3•+ (b), and 4•+ (c). Hydrogenatoms and counter anion were omitted
for clarity.

[1] Suzuki, S.; Yoshida, K.; Kozaki, M.; Okada. K, Angew. Chem., Int. Ed. 2013, 52,
2499–2502.

̶ 48 ̶

Synthetic Study of DE-Cyclopropyl Amino Acid
Using Cyclopropanation Reaction with Furan derivative
Ryotaro Matsumoto and Tetsuro Shinada
Graduate School of Science, Osaka City University, 3-3-138 Sugimoto Sumiyoshi, Osaka
558-8585, Japan
Cyclopropanes are often found in biologically active natural products and used asbuilding blocks in pharmaceutical chemistry and agrochemistry. Taking advantage of theirhigh reactivities, cyclopropanes are widely utilized in organic synthesis. To date, various
synthetic methods for cyclopropanes have been reported.
CH2I2 , Zn-Cu
Simmons-Smith Reaction
R

N2

R
Rh2(OCOR)4 , hQ or '
O
S

CH2

Corey-Chaykovsky Reaction

In this presentation, we will report a mild cyclopropanation reaction ofelectron-deficient olefin and 2-methoxy furan or substituted siloxy furan without any catalyst
and solvent. The synthesis was successfully applied to the synthesis of novel DE-cyclopropyl
amino acids. The scope and limitation of the novel cyclopropanation reaction will be
discussed.
O
EWG

OMe

EWG
R

EWG = ketone, ester

EWG
R3

R2
O

R3

OTIPS
R1

R2

R1

̶ 49 ̶R
EWG

CO2Me(TIPS)

Activation mechanism elucidated from crystal structure ofserine palmitoyltransferase; a key enzyme of sphingolipid biosynthesis
Asuka Katayama1, Hiroko Ikushiro2, Hideyuki Hayashi3,
Nobuo Kamiya1,4, Ikuko Miyahara1
1
Grad School of Sci, Osaka City Univ,
2
Dept of Biochem, Osaka Med College, 3Dept of Chem, Osaka Med College,
4
OCARINA, Osaka City Univ
Serine Palmitoyltransferase (SPT) catalyses the pyridoxal 5’-phospheate (PLP) -dependent
decarboxylative condensation reaction of L-Ser with palmitoyl-CoA to generate
3-ketodihydrosphingosine (KDS). SPT catalyses the first and late-limiting step of thesphingolipid biosynthsis, and regulation of the SPT reaction directly influences cellularsphingolipid homeostasis. The molecular mechanism of the SPT reaction has been attracting
attention, since it has been shown that sphingolipids play crucial roles in signal transduction,differentiation, and apoptosis.

Figure. 1. The reaction catalysed by SPT
Recently, the structures of bacterial SPTs considerd as prototype of eukaryotic SPT wererevealed[1], but the structure of the ternary complex of SPT is not revealed. So, we tried to
crystalize enzyme-substrate complex of SPT to provide the reaction mechanism and substrate
recognition mechanism of SPT.
We isolated SPT genes from the sphingolipid-containing bacteria, Sphingomonas
paucimobilis. This bacterial SPT is water-soluble homodimer and shows high identity witheukaryotic SPTs. We report here the crystal structures of Sphingomonas paucimobilis
SPTΔ22(SpSPTΔ22) and L-Ser binary complex at 1.96 Å, and SpSPTΔ22 and L-Ala binary
complex at 1.80 Å.
In SpSPTΔ22-Ser binary complex structure, PLP and L-Ser formed PLP-Schiff base atactive site. In SpSPTΔ22-Ala binary complex structure, PLP converted into PMP. Becauselack of hydrogen bond between Lys265 and L-Ala allowed rotational freedom around theCα-N bond of the L-Ala moiety, Cα-H bond of the L-Ala moiety is perpendicular toimine-pyridine plane, and as a result, α-deprotonation can occur. As a result of these structure
analysis, it was cleared that the hydrogen bond between active site amino acids andsubstrate amino acids prevent PLP from converting into PMP.
[1]D. J. Campopiano et al. Journal of Biological Chemistry 2009, 284, 17328-17339

̶ 50 ̶

Optical Properties of 3,7-Diphenyl Phenothiazine Derivatives
Ayumu Karimata, Shuichi Suzuki, Masatoshi Kozaki, Keiji Okada
Department of Chemistry, Graduate School of Science, Osaka City University, Sumiyoshi-ku,
Osaka, 558-8585, Japan
Abstract: Phenothiazine derivatives have attracted as components for donor moiety ofphoto-induced charge-separated molecular system, charge conducting materials, andphotovoltalic cells. Recently, we found that N-methy-3,7-diphenyl phenothiazine derivatives
show relatively intense emission, though phenothiazine derivatives usually are poorly
emissive. We have reported on substituent effects of optical properties for
N-methyl-3,7-diphenyl phenothiazine derivatives (Scheme 1).
N-methyl-3,7-di(R-phenyl)phenothiazine derivatives 2–8 (R = MeO, F, CF3, Ac, and CN)
were prepared from 1 and
2: R = H, ()= 48%)
S
R
R
S
3: R = p-OMe ()= 33%)
their optical properties suchN
4: R = p-F ()= 39%)N
CH3
5:
R = p-CF 3 ()= 63%)
as absorption and emission
CH3
6: R = p-Ac ()= 62%)1
7: R = p-CN ()= 63%)
properties were investigated.
8: R = m-CN ()= 58%)
The emission spectra of
Scheme 1. The structure of compounds 1–8
these
phenothiazine
derivatives in solution were found to be red-shifted when R were electron withdrawing
substituents. Their emission colors changed from blue to green. Emission quantum yields ofthese derivatives in toluene were determined to be 33–63% (Scheme 1), demonstrating theirhighly emissive properties compared to the parent N-methylphenothiazine 1 (0.7%). In
addition,p-acetophenone-substitutedTol
CH2Cl2DMF
CH3CN

Normalized Intensity

N-methylphenothiazine derivative 6 showeda solvatochromic fluorescent property: alarger Storks’ shift was observed in higher
polar solvent (Figure 1). Moreover, we foundthat compound 2, 4, 5, 6, and 8 show
fluorescent emission in the crystalline states.

500

550 600 650 700
Wavelength / nm

750

800

Figure 1. emission spectra of compound 6
in various solvents

̶ 51 ̶

Photoelectric Conversion System Based on Dyads Platinum Complexes
Linked with Electron Donor Moieties
Yuma Matsumoto, Ayumu Karimata, Shuichi Suzuki, Masatoshi Kozaki, Yohei Muramatsu,
Akinori Konnno, Keiji Okada
Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan,
Graduate School of Engineering, Shizuoka University, Johoku, Naka-ku, Hamamatsu,
432-8561, Japan
We have recently reported that a spin-controlled
charge-separated molecular system using a triad platinumcomplex linked to triarylamine and naphthaleneidime
derivatives [1,2]. The charge-separated state of the triad
system was efficiently generated by selective excitation of
the platinum complex moiety. Here we newly designed andsynthesized photoelectric conversion dyads 1–5 consistingof platinum complex as a photosensitizer and triarylamine
moieties as electron donors linked by ethtynylene spacers
with different distance (Figure 1). We have carried out
photocurrent measurements with a dye-sensitized solar cell.
The effects of the donors and spacers on the dyads will bereported.

Figure 1. Molecular structure ofphotoelectric conversion dyads

References[1] Suzuki, S.; Sugimura, R.; Kozaki, M.; Keyaki, K.; Nozaki, K.; Ikeda, N.; Akiyama, K.;
Okada, K. J. Am. Chem. Soc. 2009, 131, 10374–10375.
[2] Suzuki, S.; Matsumoto, Y.; Tsubamoto, M.; Sugimura, R.; Kozaki, M.; Kimoto, K.;
Iwamura, M.; Nozaki, K.; Senju, N.; Uragami, C.; Hashimoto, H.; Muramatsu, Y.; Konno, A.;
Okada, K. Phys. Chem. Chem. Phys. 2013, 15, 8088–8094.

̶ 52 ̶Studies on inhibition mechanism of herbicides
to Photosystem II electron-transfer
Ayako Tanaka1, Satoshi Suzuri1, Toshio Asada2, Keisuke Kawakami3,
Yasufumi Umena3,5, Jian-Ren Shen4, Ikuko Miyahara1,3, Nobuo Kamiya3,1
1Graduate School of Science, Osaka City University; 2Depart of Chemistry, Osaka

Prefecture University; 3The OCU Advanced Research Institute for Natural
Science and Technology (OCARINA), Osaka City University; 4Graduate School of
Natural Science and Technology/Faculty of Science, Okayama University.; 5Japan
Science and Technology Agency (JST), Precursory Research for Embryonic Scienceand Technology
Photosystem II (PSII) is embedded in thylakoid membranes as a dimer withmolecular weight of 700 kDa. PSII catalyzes the water-splitting andoxygen-evolving reaction. It consists of 20 subunits and many cofactors. The
oxygen-evolving center, Mn4CaO5 cluster, is located in the D1 subunit. After light
excitation and charge separation in a reaction center chlorophyll dimer (P680),
an electron is transferred to plastoquinone QA via pheophytin, then toplastoquinone QB. QB is reduced to plastoquinol, resulting in its release from thebinding site. Water molecules are oxidized by the Mn4CaO5 cluster and theextracted electron is transferred to P680+. To understand the electron transfer
mechanism, the redox potential of each component is a key factor. Herbicides
bind to the QB site and block the electron transfer from QA. Although the
herbicide activities are well known, their inhibition mechanisms are not clear yet.
The herbicides have been classified into several types; phenolic-, triazine-, uracil-,and urea-types. Representative compounds for the four types of herbicides are
bromoxynil, terbutryn, bromacil, and DCMU, respectively (see Figure 1).
Recently, we solved four crystal structures of PSII complexes with the herbicides
at resolutions of 1.9 -2.3 Å, and revealed their binding modes at the QB site.

Figure 1. Chemical structure of herbicides

Based on the crystal structures, we estimated the redox potentials of herbicides
using a quantum mechanical and molecular mechanical (QM/MM) calculations.
̶ 53 ̶

The values for herbicides were higher than that of QA in the native PSII. And, we
obtained inhibition constants of herbicides by measuring oxygen-evolving
activities of PSII in solution. The inhibition constants were correlated with thenumber of hydrogen bonds between the herbicides and the surrounding aminoacids. If the binding free energies are calculated, the inhibitory capacity forherbicides of different types can be determined. To calculate the binding freeenergy by the MM-PBSA method, the calculation condition is underconsideration.

̶ 54 ̶

Synthetic Study of Kainoids by an Intramolecular Cyclization
Azusa Yamada and Tetsuro Shinada
Graduate School of Science, Osaka City University
3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan
Kainoids, such as kainic acid (1), domoic acid, and acromelic acids, are unusual
amino acids that are characterized by the presence of a pyrrolidine core with three contiguouschiral centers. These are known to be agonists of ionotropic glutamate receptors. Kainoids
have attracted much attention as a synthetic target in view of pharmacological activity as wellas these structural feature. In this presentation, we will report a novel synthetic approach toform the pyrrolidine ring by an intramolecular cyclization and the synthesis toward
dihydrokainic acid (2).

CO2H

CO2H

R1

4

N
H

CO2H

R

CO2H

N
H

I

2

R1

OBn

CO2Me
N
Boc

N
CO2Me
Boc

Dihydrokainic acid (2)Kainic acid (1)OBnintramolecularcyclization
R2

We initiated the synthesis of Z-iodo dehydroamino acid 3[1]. N-Alkylation of 3 gave
the cyclization precursers 4a and 4b. Metathesis reaction of 4a with monosubstituted olefingave 5 with different substituents at C4 position. The radical cyclization of 4b gave 6 in 61%
yeild. The synthesis of 2 from 6 is also described.
R1
I
BocHN

OBn
CO2Me

2

R

t-BuOKI

R2

CH2Cl2

OBn

N
CO2Me
Boc

R3

R3
Grubbs 2nd

I

CH2Cl2

toluene, - 20 °C, 61%

5: R3 = Ph, CO2Et

OBn

Bu3SnH
Et3B

CO2Me
N
Boc
6

CO2H
N
H

CO2H

Dihydrokainic acid (2)[1] The 93rd Annual Meeting of the Chemical Society of Japan, 4D1-44 (2013).

̶ 55 ̶

OBn

N
CO2Me
Boc

4a: R1 = R2 = H
4b: R1 = R2 = Me

3

4b

R1

Br

Measuring The Raman Spectra of Shiphonaous green alga, Codium
intricatum, Cultivated at Two Kinds of Light Condition
Chiasa Uragami1, 2, Denise Galzerano3, Andrew Gall3, Yusuke Shigematsu1,
Maïwen Meisterhans3, Naohiro Oka4, Masahiko Iha4, Ritsuko Fujii1, 5, 6,
Bruno Robert3・Hideki Hashimoto1, 5
1Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka
558-8585, Japan
2
Research Fellow of Japan Society for the Promotion of Science, 4-1-8 Honcho Kawaguchi,
Saitama 332-0012, Japan
3
Institute of Biology and Technology of Saclay, CEA (Commissariat à l'Energie Atomique),URA 2096 CNRS (Centre National de la Recherche Scientifique), 91191 Gif sur Yvette, France
4
South Product Co. Ltd., 12-75 Suzaki, Uruma-shi, Okinawa 904-2234, Japan
5
The Osaka City University Advanced Research Institute for Natural Science and Technology(OCARINA), 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan
6
JST-PRESTO, 4-1-8 Honcho Kawaguchi, Saitama 332-0012, Japan
Abstract：Some deep-sea type green algae, so-called siphonous green algae, show an olive drab
color and utilize blue-green light for photosynthesis. The siphonous green alga, Codium (C.)
intricatum was isolated from Okinawa prefecture, Japan, and a unialgal culture in filamentous
form was acquired [1]. The major light-harvesting antenna is analogous to the higher plant type
trimeric LHCII, but contains an unusual carbonyl carotenoid siphonaxanthin. The culture
conditions were optimized to achieve a high content of siphonaxanthin in intact lyophilized
filamentous bodies. Interestingly, the carotenoid composition was different when cultured
under high irradiance: all-trans neoxanthin was accumulated in addition to the normal 9'-cisform [2] in whole cell extract. Resonance Raman spectra of intact filamentous bodies, cultured
under high- and low-light conditions, confirmed that the accumulation of all-trans neoxanthin
under high irradiance conditions. A plausible function of the presence of all-trans neoxanthin
will be discussed in relation to the regulation against high light stress.
References:[1] N. Oka, T. Kusumoto, T. Taira, M. Iha, Y. Shigematsu, R. Fujii, H. Hashimoto,
Carotenoid Science 2012, 17, 19[2] S. Takaichi and M. Mimuro, Plant & Cell Physiol. 1998, 39, 968

̶ 56 ̶

X-ray crystal structure analysis of hydroxylamine-treated photosystem II
Takeda Yuri1, Kawakami Keisuke2,3, Umena Yasufumi2,4, Kamiya Nobuo2,1
1
Graduate school of Science, Osaka City University, Osaka, Japan, 2The OCU Advanced
Research Institute for Natural Science & Technology (OCARINA), 3JST-CREST, 4JST-PREST
Abstract:
Photosynthetic oxygen evolution of photosystem II (PSII) embedded in thylakoid
membranes of higher plants and cyanobacteria is the catalysis on the Mn4CaO5-cluster
performing water-splitting reaction. Overall structure of PSII was reported at a resolution of
1.9 Å in 2011 (PDBcode: 3ARC), and the detailed structure of Mn4CaO5-cluster was
identified including precise arrangement of amino acid residues ligated to the cluster [1].
This study aims to understand the assembly process of the Mn4CaO5-cluster in order toobtain useful information for the synthesis of artificial catalysts mimicking the
Mn4CaO5-cluster. Because of difficulties to trap the process in vivo, we are going to reveal areverse of assembly, that is, the dissociation process of the Mn4CaO5-cluster. A strong
reducing agent, hydroxylamine, decreases the oxygen-evolving activity of PSII from spinach.
It is caused by the reduction of manganese atoms and their dissociations from the
Mn4CaO5-cluster [2]. We searched a suitable concentration of hydroxylamine to inactivate theoxygen-evolving activity of PSII from thermophilic cyanobacteria in solution. PSII wascompletely inactivated at hydroxylamine concentration of 1 mM, at room temperature, andafter incubation for 15 hours. Native-PSII crystal was soaked at the above condition, and
X-ray diffraction intensities were measured at SPring-8. The crystal structure ofhydroxylamine-treated PSII was analyzed at a resolution of 2.0 Å. Electron density
distributions showed the dissociation of the Mn4CaO5-cluster and large conformationalchanges of the surrounding amino acid residues (Figure 1). Three manganese atoms
completely disappeared, and one manganese atom remained at two alternative positions withoccupancy values of 0.5. Additionally, an atom was coordinated with D1-Gln165, D1-Asp170,
and D1-Ala344, which may be a calcium atom. In conclusion, we succeeded in disrupting the
Mn4CaO5-cluster by the hydroxylamine treatment and resolving the structure at a highresolution.

̶ 57 ̶

Figure 1: The structural differences between hydroxylamine-treated PSII and 3ARC. Aminoacid residues of hydroxylamine-treated PSII and 3ARC were colored in green and light blue,
respectively. Manganese: purple, calcium: green, oxygen: red.
[1] Y.Umena, K.Kawakami, Shen.JR, and N.Kamiya, Nature 2011, 473, 55-60[2] R.D.Guiles, Vittal K. Yachandra, Ann E. McDermott, James L. Cole, S. L. Dexheimer, R.
D. Britt, Kenneth Sauer, and Melvin P. Klein, Biochemistry 1990, 29, 486-496

̶ 58 ̶

Construction of Carotenoid Molecularly-Oriented Film:
A Model System of Photosynthetic Antenna
Syohei Kita1, Ritsuko Fujii 2, 3, 4, Hideki Hashimoto1, 41Depertment of Physics, Graduate School of Science, Osaka City University, 3-3-138
Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan
2
Depertment of Chemistry, Graduate School of Science, Osaka City University, 3-3-138
Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan
3
JST-PRESTO, 4-1-8 Honcho Kawaguchi, Saitama 332-0012
4
The Osaka City University Advanced Research Institute for Natural Science and Technology(OCARINA), 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan
Abstract: Carotenoid is a pigment molecule that absorbs light energy and transfers it tonearby chlorophylls in photosynthetic antenna. The efficiency of the energy transfer depends
mainly on the intermolecular distance and the molecular orientation. The aim of this researchis to construct a carotenoid film where the intermolecular distance and molecular orientationof carotenoids are controlled to correlate the efficiency of the energy transfer as a function ofthese parameters. In this work, we prepared a barium stearate Langmuir-Blodgett film
containing all-trans-�-carotene [1] or fucoxanthin with a lipid to substrate ratio of 10 / 1 (v/v)(Figure 1, 2), and evaluated the accuracy of adsorption of LB films by optical absorption
spectroscopies and atomic force microscope. We also determined the molecular orientation of
carotenoids by polarized optical absorption spectroscopies [1].
References: [1] Hashimoto, H.; Kiyohara, D.; Kamo, Y.; Komuta, H.; Mori, Y. Jpn. J. Appl.
Phys. 2008, 35, 281.

carotenoid
LB film

mixed LB film

Figure 1. Schematic image of mixed LB film

̶ 59 ̶

Figure 2. Structure of carotenoids

The Back and Forth of Energy Flow in Purple Bacterial Photosynthetic
Antennas
D. Kosumi1, S. Maruta2, R. Fujii1,3, M. Sugisaki2, S. Takaichi4, R.J. Cogdell5, H. Hashimoto1,2
1
Osaka City University Advanced Research Institute for Natural Science and Technology(OCARINA), 2Department of Physics, Graduate School of Science, Osaka City University,
3
JST/PRESTO, 4Department of Biology, Nippon Medical School, 5Glasgow Biomedical
Research Centre, University of Glasgow
Abstract: Carotenoids (Cars) are naturally-occurring photosynthetic pigments that play thetwo important roles of light-harvesting (LH) and photo-protection in photosynthesis of plants,
algae, and bacteria [1]. Cars absorb sunlight in the blue-green regions of the spectrum andefficiently transfer it to nearby bacteriochlorophyll a (Bchl a) in purple bacterial LH
complexes (LH1 and LH2 shown Fig. 1(a)). The ultrafast spectroscopic measurements on
LH1 and LH2 proposed that the singlet-singlet excitation energy transfer (EET) from Car to
Bchl a involves two pathways of S2→Qx and S1→Qy. The overall efficiency of Car→Bchl a
EET has been reported to be 30~100% depending strongly on number of conjugated double
bonds n of the Cars involved [1]. Recently, we reported a new EET pathway of Bchl a
Qx→Car S1 in LH1 from Rhoddospirillum (Rsp.) rubrum S1 involving the Car, spirilloxanthin(Spx) with n=13 [2]. The reverse EET pathway of Bchl a Qx→Car S1 in LH2 has been also
confirmed by broadband two-dimensional electronic spectroscopy [3]. In this study, themutual EET dynamics between Car and Bchl a in LH2 complexes containing Car withdifferent n (Fig. 1(A)) were investigated by femtosecond pump-probe spectroscopy upon
excitation either into S2 of Car or Qx of Bchl a (Fig. 1(B)). The results demonstrated that thereverse Bchl a Qx→Car S1EET depends strongly on n.
(B)

(A)

900 800 700

Wavelength (nm)
600
500

400

(C)

OCH3

S2 (11Bu+)

Rba. shaeroides 2.4.1
spheroidene n=10

Qx

Qy

Qx
S2

S1 (21Ag‐)
Qy

Absorbance

C6H11O6

B850

Rps. acidophila 10050
rhodopin glucoside n=11

B800
B850

Qx exc.
S2 exc.

OH

Qy exc.

Ros. goensis
3,4 didehydrorhopine n=12

B800

2
car

3
Photon Energy (eV)S0 (11Ag‐)
carotenoid

bacteriochlorophyll

Fig.1. (A) Steady-state absorption spectra of LH2 complexes. Insets show the chemical structures of carotenoids contained in antennacomplexes. (B) Energy diagrams of carotenoid and bacteriochlorophyll a. (C) The crystal structure of LH2 from Rps. acidophila 10050.

Refferences[1]
T. Polivka, V. Sundstrom, Chem. Rev. 104 (2004) 2021.
[2]
D. Kosumi, S. Maruta, T. Horibe, R. Fujii, M. Sugisaki, R.J. Cogdell, H. Hashimoto, Angew.
Chem., Int. Ed. 50 (2011) 1097.
[3]
E.E. Ostroumov, R.M. Mulvaney, R.J. Cogdell, G.D. Scholes, Science 340 (2013) 52.

̶ 60 ̶

Femtosecond time-resolved spectroscopy on Carotenoid-Chlorophyll
artificial light-harvesting antenna
Tomoya Nishiguchi1, Daisuke Kosumi2, Yutaka Amao2, Hideki Hashimoto2
1
Department of Physics, School of Science, Osaka City University
2
The Osaka City University Advanced Research Institute for Natural Science and Technology(OCARINA)
Carotenoids (Cars) bound to light harvesting complexes carry out the two crucial tasks oflight-harvesting and photoprotection in photosynthetic system. Cars absorb light in theblue-green region and transfer the energy to nearby Chlorophyll (Chl) molecules. The energy
is consequently transferred to reaction centers (RC). In this study, we constructed the artificial
antenna complex based on the Cars Crocetin (Cro) electrostatically immobilized onto thesurface or into the inside of cationic surfactant micelles including Chl a [1] and clarified
excitation energy transfer (EET) processes from Cro to Chl a by femtosecond time-resolved
spectroscopy.
Fig. 1(A) represents that the photo-induced absorption spectra of Cro and Cro–Chl acomplex, taken at 5.0 ps after excitation into the optically allowed S2 state. The transientabsorption due to the lower-lying S1 state appears at 510 nm in the spectra. Then, an
appearance of the Chl a bleaching demonstrates an energy transfer from Cro to Chl a. Fig.
1(B) shows the kinetic traces of the S1 transient absorption. On the basis of the analysis of the
kinetic traces, the EET efficiency from Cro to Chl a was estimated to be more than 80%.
(B)
1

Cro S1 transient absorption

Cro-Chl a 5 ps
Cro 5 ps
Cro-Chl a St. Abs.

0
Chl a bleachingO
HO-1Cro bleaching
HO 400OH
O

Crocetin

500
600
Wavelength [nm]Normalized Abosrobance Change

Normalized Absorbance/Absorbance Change(A)1

Cro 512nm
Cro-Chl a 512nm

0.5

0
0

700

115 ps
21 ps

100

200

300

40

Delay Time [ps]Fig. 1. (A) Photo-induced absorbance change spectra of Cro and Cro–Chl a. (B) Kinetic traces of thetransient absorption of Cro and Cro–Chl a

References[1] Amao, Y.; Maki, Y.; Fuchino, Y. J. Phys. Chem. C 2009, 113,16811

̶ 61 ̶

Syntheses and structures of Trinuclear Mo-S Complexes with Schiff Base
Ligands
Keisuke KAWAMOTO
Grasuate School of Science, Osaka City University, Osaka, Japankeisuke@sci.osaka-cu.ac.jp
Abstract: Two novel complexes, [Mo3S4(LXMe)3]+ (LXMe, HOPhC=N-(n-Pr)-XMe; X = S
or Se) have been synthesized (Chart 1). The X-ray analysis of [Mo3S4(LSMe)3]PF6 revealed
that every sulfur atom in LSMes coordinates trans to µ3-S of the Mo3S4 core. The bonds
between the molybdenum center and sulfur atom of LSMe generate three centers of chirality
at the coordinated sulfur atoms, respectively.
In the cyclic voltammetry, both complexes exhibit two reversible one electron reduction
waves at ca.-1.2 V and ca.-1.9 V (vs. Fc+/Fc) assigned to Mo(IV IV IV)/Mo(III IV IV) andMo(III IV IV)/Mo(III III IV), respectively. In addition, the catalytic current for the proton
reduction in the presence of CH3COOH is observed near the onset of the second reduction
peak of the original complexes.
The structural properties of [Mo3S4(LXMe)3]+ (X = S or Se) have been estimated by using
NMR measurements. VT-1H NMR spectra of [Mo3S4(LSMe)3]+ revealed that the following
features: 1) the protons of propyl chain were observed as six signals because of diastereotopic
nature of the propyl chain. This result indicates that the bonds between Mo and X atom
maintain in solution. 2) the methyl protons show a dynamic behavior of steric inversion of X
atoms.
In this OCARINA annual meeting, we hope to discuss the structural properties of[Mo3S4(LXMe)3]+ in solution.

Chart 1. Structure of [Mo3S4(LXMe)3]+ (X = S or Se)

O
N
X

S
Mo
O

X N
Mo
S
S

S
Mo

O
X

N

̶ 62 ̶Long-Range Photoinduced Electron Transfer Dynamics in Rigid Media
Akitaka Ito†,‡ and Thomas J. Meyer††
The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599, United States.
‡
Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan.
Poly(ethyleneglycol)dimethacrylate films and monoliths undergo thermal or
photochemical polymerization to give optically transparent materials with features
conformable to the nanoscale. We have shown that the emission energies from Metal-toLigand Charge Transfer (MLCT) excited states of a series of polypyridyl Ru(II) and Os(II)complexes, including [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine), increase upon film formation bypolymerization of PEG-DMA550, whose structure is shown in Scheme. The semi-rigid film
environment leads to higher-energy excited states by “rigid medium effect” increasing
emission energy, leading to enhanced emission quantum yields and longer excited-state
lifetimes. The latter are consistent with qualitative and quantitative predictions of the energy
gap law for nonradiative excited-state decay [1,2].
In semi-rigid PEG-DMA550 films with added reductive quenchers, electron transfer
quenching of the MLCT excited state(s) of [Ru(bpy)3]2+ occurs by both rapid, fixed-site, andslow, diffusional, quenching processes. Stern-Volmer analysis of diffusional quenchingreveals diffusion-controlled quenching both in the fluid and film with the latter greatly
inhibited by the high viscosity of the medium. The data for fixed-site quenching are consistent
with electron tunneling with the expected
2+
N
exponential distance dependence. Based on thisNN
Ru
analysis long-range electron transfer occurs with aNNO
distance attenuation factor β of ~0.47 Å–1 (PTZNOO
9and DMAOMe) with a notable decrease, β = 0.16
O
–1
PEG-DMA550[Ru(bpy)3] 2+
Å , when the quencher is incorporated into the
PEG backbone (PEG-TMBD). Fixed-site electronNtransfer quenching varies with driving force. BackH
Nelectron transfer is complex, as expected for a
R 2N
NR2
S
OMe
distribution of fixed sites, and varies with power
PEG-TMBDPTZDMAOMe(R = -(CH2CH2O) 3-H)
law kinetics [3].
References[1] Knight, T. E.; Goldstein, A. P.; Brennaman, M. K.; Cardolaccia, T.; Pandya, A.;
DeSimone, J. M.; Meyer, T. J. J. Phys. Chem. B 2011, 115, 64.
[2] Ito, A.; Knight, T. E.; Stewart, D. J.; Brennaman, M. K.; Meyer, T. J. in preparation.
[3] Ito, A.; Fang, Z.; Brennaman, M. K.; Meyer, T. J. Phys. Chem. Chem. Phys. 2014, 16,4880.
̶ 63 ̶

Excited-State Dynamics of Pentacene Derivatives
Having Stable Radical Substituents
Akihiro Shimizu, Noriaki Kishida, Akitaka Ito, Yusuke Kawanaka,
Daisuke Kosumi, Hideki Hashimoto and Yoshio Teki
Osaka City University, Osaka, Japan; teki@sci.osaka-cu.ac.jp
Pentacene has been paid attention in the past decades owing to its characteristics as ap-type semiconductor material. However, it is chemically unstable under light irradiation in
the presence of oxygen. Therefore, stabilization of pentacene is of importance, with notable
examples by introducing substituents such as triisopropylsilylethynyl group into active 6- and13-positions of pentacene [1]. We recently reported that pentacene–radical hybrids, whose
structures are shown in Scheme 1, were quite stable owing to the presence of radical substituents [2]. In this study, the excited-state dynamics of the pentacene–radical derivatives(Pn-Ph-R; -R

-NN and -OV) were evaluated in detail.
Transient absorption measurements for the Pn-Ph-R in dichloromethane at room
temperature were carried out. Immediately after photoexcitation at 587 nm, the derivatives
showed the absorption band assigned to excited singlet state of the pentacene moiety (1Pn*) at
a450 nm. The 1Pn* signal decayed very quickly with anaverage lifetime of a10 ps, and new structured absorption
band assigned to excited triplet state of the pentacene
moiety (3Pn*) appeared at a510 nm with the sametimescale. Since the rate constants are extremely large
compared with those of the corresponding precursors, theresults are indicative of ultrafast 3Pn* formation byintroducing radical substituents. The 3Pn* species of the
Pn-Ph-R also decayed quickly with the lifetime of a500
ps. Schematic illustration of the excited-state dynamics
of the Pn-Ph-R is shown in Scheme 1. The ultrafast 3Pn*formation followed by thermal deactivation to theelectronic ground state is expected to arise from“spin-allowed” 1Pn*o3Pn* reaction by introducing
radical substituents and to cause remarkable protection
Scheme 1. Chemical structures andfrom photodegradation of the pentacene moiety [3].
excited-state dynamics of Pn-Ph-R.
[1] Anthony, J. E. Angew. Chem. Int. Ed. 2008, 47, 452.
[2] Kawanaka, Y.; Shimizu, A.; Shinada, T.; Tanaka, R.; Teki, Y. Angew. Chem. Int. Ed.
2013, 52, 6643.
[3] Ito, A.; Shimizu, A.; Kishida, N.; Kawanaka, Y.; Kosumi, D.; Hashimoto, H.; Teki, Y.
submitted for publication.

̶ 64 ̶

Asymmetry of the Carotenoid Molecules Bound to
Bacterial Light-Harvesting Complexes
Tomoko Horibe1, Ritsuko Fujii2, Daisuke Kosumi2, Keiji Okada1, Mamoru Nango2,
Pu Qian3, C. Neil Hunter3, and Hideki Hashimoto1,2
1) Department of Physics, Graduate School of Science, Osaka City University (OCU),
3-3-138, Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan2) The OCU Advanced Research Institute for Natural Science and Technology (OCARINA),
3-3-138, Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan
3) Department of Molecular Biology and Biotechnology, University of Sheffield,
Firth Court, Western Bank, Sheffield S10 2TN, UK
The physical processes in photosynthetic light-harvesting (LH) have been discussed on theassumption that the carotenoids’ conjugated polyene chain has C2h symmetry [1,2]. However,
the assumption seems to be inaccurate because carotenoid molecules are truly asymmetrically
deformed through pigment-protein interaction in the native photosynthetic light-harvesting
systems. In this study, the asymmetry of the carotenoid molecules bound to LH isdemonstrated by the experiments (1)~(3) using Stark absorption spectroscopy [3].
(1) The polarization angle dependence of Stark absorption spectra of spirilloxanthin (Fig.
1(a)) bound to the LH1 complex from a purple photosynthetic bacterium Rhodospirillum(Rsp.) rubrum was investigated [4]. The large 'P value (static dipole-moment change upon
photoexcitation) and slightly different values of θΔα and θΔμ (the angle of Δα (polarizabilitychange upon photoexcitation) and Δμ with respect to the direction of transition dipole
moment, respectively) were observed for the spirilloxanthin bound to the native LH1. This
result suggests that the molecular structure of all-trans spirilloxanthin is somehow deformed
so as to lose its center of symmetry according to pigment-protein interaction when bound to
the native LH1 complexes.
(2) The reassociation of the LH1 from the purple photosynthetic bacterium Rsp. rubrum
with four carotenoids, spirilloxanthin, anhydrorhodovibrin (Fig. 1(b)), rhodopin (Fig. 1(c)),
and spheroidene (Fig. 1(e)) have been investigated [5]. The absorption maximum of the Qyband of BChl a for the LH1-rhodopin complex was observed at 881nm, 2 nm shorter
wavelength than that from the other LH1-carotenoid complexes. Singlet-singlet
energy-transfer efficiency from carotenoid to bacteriochlorophyll a (BChl a) was found toincrease with a decrease of the number of C=C bonds (N) of the four carotenoids. However,the plot for the LH1rhodopin complex alone slightly deviates from the linear relation. It has
been anticipated that this small anomaly of LH1rhodopin complex could result from theinteraction between the polar OH group of rhodopin and BChl a. In order to obtain further
insight into these observations, we investigated the reassociation of the LH1 with
3,4-dihydroanhydrorhodovibrin (Fig. 1(d)), which is the OH-protected (OMe) variant of̶ 65 ̶

rhodopin [6]. The reassociation complex LH13,4-dihydroanhydrorhodovibrin exhibited anabsorption maximum at 883 nm. Thus, it is clear that the protection of hydroxyl group of
rhodopin prevent the usual behavior of the BChl a Qy absorption band. Replacing the plot of
the singlet-singlet energy-transfer efficiency of LH1rhodopin with that of
LH13,4-dihydroanhydrorhodovibrin resulted in a straight line with a good correlation
coefficient. This result indicates that the physical process in LH1 can be affected not only by
the conjugated chain but also by the end group of carotenoid.
(3) The Stark absorption spectroscopy was applied to the carotenoid, rhodopin, bound to
the B800-820 and B800-850 complexes from Phaeospirillum molischianum DSM120.
According to both classical and semi-quantum mechanical analyses of the observed Stark
absorption spectra, it was clarified that rhodopin bound to the B800-820 LH2 complex
showed substantially lager value (2 [D/f]) of |'P| than that bound to B800-850 LH2 complex.
The origin of this severe difference was discussed based on the modeled structure of the LH2
complexes as well as the results of semi-empirical molecular orbital calculations. It was
concluded that simultaneous rotation around neighboring C=C and C-C bonds is required to
explain the induction of this large deviation of the |'P| value when rhodopin is embedded inprotein environment.
(a)
(b)
(c)
(d)
(e)
Figure 1: Chemical structures of carotenoids, (a) spirilloxanthin (number of conjugated double bond(N) =13), (b) anhydrorhodovibrin (N=12), (c) rhodopin (N=11), (d) 3,4-dihydroanhydrorhodovibrin (N=11), (e) spheroidene (N=10)
[1]
[2]
[3]
[4]
[5]
[6]

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