PREFACE

It gives us immense pleasure to invite you to the 3rd International Conference of
OCU-Advanced Research Institute for Natural Science and Technology (OCARINA) to be held
during March 7-９, 2011 at Osaka City Media Center and Library.
This annual conference follows the very successful first and second meetings held at
Cultural Exchange Center in OCU (2009) and at Awaji Yumebutai in Hyogo Pref. (2010). The
institute was initially planned by Late-vice president, Professor Kakuno with his enthusiastic
desire for the future of Osaka City University. His basic design for the institute was nothing
different from nowadays OCARINA. Without his initiation, it is impossible to find OCARINA
at this time as it is. He passed away in Dec. 2009 just before OCARINA became real institute.
Therefore the conference is dedicated to Late Prof. Dr. Kakuno for his great idea.
The conference will cover recent advances and new findings in OCARINA especially for the
Photosynthetic research and the Urban environmental topics.
This conference also intends to find “The Novel Prize” class idea for the new project fromwide ranges of the research now progressing in OCU. This session will be open for people who
intend to appeal a proposal/idea for the next project of OCARINA. In the fiscal year of 2013,OCARINA will have spaces for the next projects, thus this is a good opportunity to collectideas and two candidates will propose their plans for this.
Our institute always intends to develop the idea of equal opportunity for men and women
to work together in our place. Thus one of the sessions will be dedicate to this idea.
OCARINA will intend to collaborate with Urban Plaza and related Social Science
researchers to develop the outstanding idea for our future. We need to think our lives like anancient poem “Manyo-shu” (萬葉集) that deals daily life, peace, war and especially LOVE. We
need to remember the fact that every subject for university is just for us human beings.
Without the collaboration, our university becomes a simple aggregation of Faculties. It isquite possible to have intimate relationship between faculties to produce fruitful result from
OCU. This symposium also has a session for this purpose.

The OCU Advanced Research Institute for Natural Science and Technology (OCARINA)
Director

Prof. Dr. Isamu Kinoshita

The 3rd International Conference of the OCU Advanced Research Institutefor Natural Science and Technology (OCARINA)------------ KAKUNO Memorial-------------Date : 7~9th March, 2011
Venue: 10th Floor, Osaka City Univ. Media Center

Programme
Monday, 7th March, 201109:15~
09:30~09:40

Opening Remarks

09:40~09:50

Message from Dr. Yoshiki Nishizawa, President of Osaka City University

09:50~10:20

Annual Report from Group A
by Nobuo Kamiya(OCARINA/Osaka City University)

10:20~10:50

Annual Report from Group B
by Harue Masuda(Graduate of Science, Osaka City University)

10:50~11:00

Break

11:00~11:30

Annual Report from Group C
by Hideki Sakai(Faculty of Human Life Science, Osaka City University)

11:30~11:50

Misaki Nakai (Kansai University, JPN)

11:50~12:10

Yuriko Matsumura (Seikei University, JPN)

12:10~14:10

Poster sessions & Lunch Break

14:20~14:50

Toshio Asada (Osaka Prefecture University, JPN)

14:50~15:20

Masako Kato (Hokkaido University, JPN)

15:20~15:50

Ritsuko Fujii (OCARINA, Osaka City University, JPN)

16:50~16:10

Break

16:10~16:40

OCARINA new proposal 1
by Tetsuro Shinada (Graduate school of Science, Osaka City University)

16:40~17:10

OCARINA new proposal 2
by Makoto Miyata (Graduate school of Science, Osaka City University)

Tuesday, 8th March, 2011
09:00~09:30

Plenary Talk - Richard J. Cogdell (University of Glasgow, UK)

09:30~10:10

Kazi Matin Ahmed (University of Dhaka, Bangladesh)

10:10~10:50

Guoji Ding (Shanghai University, China)

10:50~11:05

Break

11:05~11:45"Manyo-shu"(萬葉集) - by Masahiro Murata(Graduate school of Literature and Human Science, Osaka City University)

11:45~12:25

Mitsuo Toda (Shizuoka University, JPN)

12:30~14:10

Poster sessions & Lunch Break

14:20~15:00

Satoshi Matsuda (Shizuoka University, JPN)

15:00~15:30

Sarah Henry (University of Glasgow, UK)

15:30~16:00

Tom Moore (Arizona State University, USA)

16:00~16:10

Break

16:10~16:40

Ana Moore (Arizona State University, USA)

16:40~17:10

Hideki Hashimoto (OCARINA, Osaka City University, JPN)

17:10~17:40

Dario Polli (Politecnico di Milano, Italy)

18:00~

Conference Party

Wednesday, 9th March, 2011
KAKUNO Memorial Ceremony
10:00~10:10

10 10~10:40

10:40~11:10

11 10~11:40

11:40~11:50

OCARINA annual report

A group

Photosynthesis

B group

Urban environment and disaster prevention

C group

Urban functionality

Structure of Mn4CaO5 Cluster of Photosystem II;
The heart of Oxygen-Evolving Photosynthesis
Nobuo Kamiya, The OCU Advanced Research Institute for Natural
Science and Technology (OCARINA), Osaka City University, Osaka
558-8585, Japan. E-mail: nkamiya@sci.osaka-cu.ac.jp
Under the flag of “Artificial Leaf”, Professors Hashimoto and Kamiya, and otherresearchers are organized in the Group-A of OCARINA. A total report covering all
valuable results achieved in 2010 F.Y. by all members of the Group-A is out of my ability,and hereafter, I will present only results according to the title of this abstract, which will
be published soon [1]. Photosystem II (PSII) performs light-induced electron transfer
and water-splitting reactions, which lead to the formation of molecular oxygen essential
for almost all of the life on the earth. PSII from thermophilic cyanobacteria consists 17
membrane-spanning subunits, 3 hydrophilic, peripheral subunits, and many cofactors
with a total molecular mass of 350 kDa for a monomer. The X-ray crystal structures of
PSII have been reported at 3.8-2.9 Å resolution for PSII isolated from Thermosynechococcus elongatus or T. vulcanus, which provided the arrangement of protein
subunits and most of the cofactors involved in the electron transfer reactions. However,the detailed structure of the Mn4Ca-clulster, the catalytic center of light-induced oxygen
evolution, has not been resolved due to the limited resolution and radiation damage
induced during the X-ray experiments. We have improved the resolution and diffraction
quality of PSII crystals significantly, and succeeded in solving the crystal structure of
PSII from T. vulcanus at 1.9 Å resolution [1]. In order to reduce the X-ray radiation
damage to the Mn4Ca-cluster, we employed a slide-oscillation method to collect a
low-dose X-ray diffraction data set at BL44XU, SPring-8, using large PSII crystals. In the
crystal structure obtained at 1.9 Å resolution, the electron density distributions for each of
the 5 metal ions in the Mn4Ca-cluster were clearly separated, allowing us to locate theindividual metal atoms and all of the ligands to the metal cluster unambiguously. Five
oxygen atoms forming the oxo-bridges between the metal ions were identified bydifference Fourier map, and four water molecules were found to be associated with themetal cluster, some of which may serve as substrates in the oxygen-evolving reaction.
Two chloride-binding sites were identified in the anomalous D-Fourier map calculatedwith a data set of 1.75 Å wavelength, which were located in the same position as in Br or
I substituted PSII reported previously. In addition, more than three thousands of watermolecules were found in the structure of PSII dimmer in a crystallographic asymmetricunit. Some of the water molecules form hydrogen-bond networks linking the catalytic site
and the bulk phase. We will discuss the detailed structure of PSII at the atomic resolution.
[1] Umena, U., Kawakami, K., Shen. J.-R., Kamiya, N., nature (2011), in press.

Groundwater and its potential and risk as a water resource in Osaka Basin–for planning the integrated management system

Harue MASUDA1, Muneki MITAMURA1, Akihiko OHSHIMA2,
Yoshinori KANJO2, and Sadakazu NISHIKAWA3
1: Graduate School of Science, Osaka City University, 2: Graduate School of Engineering,Osaka City University, 3: Graduate School of Human Life Sciences, Osaka City University
Abstract:
Groundwater is excellent fresh water resource, however, it would cause natural disasters if
not properly controlled to use. Thus, we should understand the hydrological cycle of thewhole basin to construct the management plan of water resources. Osaka basin is one of thelargest Quaternary sedimentary basins, in which rich groundwater is hosted. We havefigured out the whole groundwater system, summarized potential problems and thosesolutions in the Osaka basin to propose ideal management plan of local water resources.
Groundwater in the Osaka basin is categorized according to the depth of aquifers andscale of water cycle; 1) the shallow aquifer including unconfined and uppermost confinedgroundwater, which is in a few to 100 m depths beneath the center of the Osaka Plain. 2)
Deep aquifers including the groundwater between 100 and 600 m depths, where unconfinedmarine clay layers are intercalated in fresh water sandy aquifer sediments. 3) Deepest aquifers
below 600 m depth to 1500 m depth at the maximum. The shallowest aquifers are recharged
by local meteoric water, and have excess hydropressure due to less withdrawal and cutting
groundwater flow by underground constructions such as subways and buildings, potentiallycausing liquefaction when earthquake occurs. Thus, the groundwater must be properly used
to decrease the hydropressure. Groundwater in 100 to 500 m depths is recharged in thesurrounding terraces of the plain at the center of the basin, and flowing rate is slow.
Withdrawal of the groundwater from this depth interval, especially <300 m deoth, isincreasing to use by many hospitals, industries, buildings, etc., instead of the public supplied
water to save the cost. Since intercalated marine clay layers of this depth interval have notbeen consolidated enough at present, subsidence would be a serious problem to cause unequal
settling of buildings, storm surge, etc. Groundwaters below 600 m depth to the basement
rocks are mostly used for hot spas in Osaka. Such deepest groundwaters are principally
fossil water, and it will be depleted due to excessive use. The groundwaters below 100 m
depth in the Osaka basin must be used under proper management for highly public purposes
to prohibit hydrogeological disasters and give priority to the public interests.

Two Next-Generation Retroreflective Materials:
A Countermeasure to Urban Heat Islands
Hideki Sakai
Faculty of Human Life Science, Osaka City University
Abstract:
Making a building reflective reduces the amount of solar heat it absorbs. These "coolroof" products have been widely used to mitigate the urban heat island effects. In
closely-packed building areas, however, heat reflected by one building may be absorbed by
the other (Fig.1, Left). To prevent this opposite effect of high-reflective materials,
retroreflective materials come into use (Fig.1, Right). In retroreflection the incident light isreturned back in the direction of the source (i.e., the sun), with a very small spread in the lightaround this particular direction[1].

Figure 1 High reflective (Left) and retroreflective (Right) materials
Technically, computer-controlled mirrors can also reflect sunlight upward and preventthe opposite effect in much the same way as retroreflective materials. However, mechanicalmoving parts are complicated and need constant maintenance. Thus, it is a distant idea that wecover wide areas of the building exterior with movable mirrors. In contrast, retroreflective
materials have no moving parts, thus, no breakdown; they require little maintenance. This is agreat advantage for building materials.
Retroreflective materials are usually used as the road markings and signs to enhancenight-time visibility [1]. Thus, they were already carefully evaluated with respect to visibility.
From the viewpoint of heat transfer, however, their characteristics were unknown. Therefore,
in the first stage of the study, we showed experimentally that retroreflective materials reduce
the reflected heat of the sun[1]. In Fig.2, when a high reflective paint was used as a sample, its
surface temperature (T1) was kept low under infrared light irradiation (E); however, the road(T2) and the neighboring wall (T3) temperatures were increased by reflected light. When aretroreflective material was used as a sample, not only its surface temperature (T1) but also
the road (T2) and the neighboring wall (T3) temperatures were kept low. Therefore, they canbe used as the building materials to reduce urban heat island effect.

Figure 2 Experimental setup (miniature model)
RSpe: specular reflectance, RDif: diffuse reflectance, RRet: retroreflectanceIn the next stage, we have evaluated the solar retroreflectances of several retroreflective
materials, which cannot be measured directly by a spectrophotometer. The procedures were as
follows: First, the reflectance without retroreflection was measured by using aspectrophotometer with the integrating sphere. Then, the total reflectance was deduced fromthe amount of temperature rise by solar irradiation. Finally, the retroreflective component wascalculated by subtracting the former from the latter. The measured retroreflectances are 20 to30 percent for the prism-array type, about 20 percent for the capsule-lens type, and about 10
percent for the bead-embedded type.
Our study is now in the third stage. We are proposing two new-type retroreflective
materials: high-spec directional retroreflective ones and low-cost, simplified ones.
References:[1] CIE Publ.180. Road Transport Lighting For Developing Countries. Vienna: CIE Central
Bureau, 2007
[2] H. Sakai, K.Emura, N.Igawa, H.Iyota, Reduction of Reflected Heat of the Sun byRetroreflective Materials, Proc. the Second International Conference on Countermeasures
to Urban Heat Islands (SICCUHI), CD-ROM 211450, pp.1-6, 2009

Equal Opportunity
for All Researchers
related to OCARINA project

Active Female Researchers
related to Photo ScienceSyntheses of Sugar Linked Indium Porphyrin As a Dual
Drug and their Photodynamic Activities
Misaki Nakaia, Tomohiro Maedaa, Shigenobu Yanob, Shiho Sakumac,
Eriko Otakec, Akira Maedac, Akimichi Moritac, Yasuo NakabayashiaaMaterials and Bioengineering, Kansai University, 3-3-35,Yamate cho,
Suita city, OSAKA, 564-8680, bInnovative Collaboration Center, Kyoto University, cGraduate
School of Medical Sciences and Medical School, Nagoya City University,
Abstract: The development of photosensitizers for photodynamic therapy (PDT) is a very
important for cancer treatment. Therefore, sugar-linked porphyrins and fullerene derivatives
were synthesized and investigated for phototoxic properties. When diagnostic metals such as
111
In, 67Ga, 99mTc, and Gd are complexed to these porphyrin derivatives, the resulting
compounds are expected to be bifunctional, exhibiting diagnostic imaging and the PDT
effects. Therefore, towards our aim of developing a dual function drug, the sugar linked freebaseporphyrin
5-{4-(2-O-tetraacetlyE-D-gluconopynanosyl)ethoxy}-10,15,20triphenylporphyrin (1), Indium porphyrinderivative (2), and Zinc porphyrin derivative(5) were synthesized. The deacetylated sugar
linked free base (3) and Indium porphyrins(4) were also synthesized from 1 and 2 (Fig.
1).

Fig.1 structures of sugar linked porphyrins

The photocytotoxic efficiency for Colo679 was investigated with 1, 2, 3, 4 and 5 after 24 hof incubation and irradiation with a light dose of 16 J/cm2 (Table 1). Laserphrin was used as astandard. The PDT effect of 4 was most efficient of all compounds. Compared with 2, Indium
porphyrin 4 was higher photocytotoxitiy. The metalation of porphyrin was effective forincreasing PDT activity. It is due to the deference of singlet oxygen production activity. The
photocytotoxicity of 4 is higher than that of compound 3. It indicated that the sugar moiety
was also effective for PDT
Table 1. IC50 values against Colo679
activity.
The
confocal(b) IC50 / PM(a) IC50 / PMcompound(a) / (b)microscopic images of Colo679 exposed to compound 1
and 2, suggested that uptakeof 1 is greater than 2. The
deference of IC50 between 3
and 4 was results in theamount of uptaken in the cell.

in dark condition

with light irradiation

H2TPPOAcGlc (1)

160

> 47

< 3.4

[InTPPOAcGlc ]NO3 (2)

0.90

0.35

2.6

H2TPPGlc (3)1.5[InTPPGlc ]NO3 (4)

4.6

10

0.50
-2

1.2

10

3.0
-2

3.8

ZnTPPOAcGlc (5)

81

27

3.0

Laserphyrin

31

14

2.2

Preparation of gold nanoparticles using
thermo-responsive copolymers having a fluorescentquinoxaline derivative
Yuriko Matsumura1, Takayuki Onodera1, Takanori Nishioka2, andKeisuke Kurita1
1

Department of Materials and Life Science, Faculty of Science and Technology, Seikei
University, 3-3-1 Kichijoji-kitamachi, Musashino-shi, Tokyo 180-8633, Japan
2
Division of Molecular Materials Science, Graduate School of Science, Osaka City University,
3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan
Abstract: It is well known that localized surface plasmon (LSP) generated in gold
nanoparticles upon visible light irradiation produces a strong electric field in the near field of
the gold nanoparticles. This phenomenon can be used for modifications of both absorption
and emission processes of the molecular fluorescence. When the distance between gold
nanoparticles and a fluorophore is more than several tens of nanometers, there is nointeraction between them. On the other hand, when it is less than 10 nm, fluorescence canbe enhanced by LSP. However, quenching occurs when they are located too close to eachother. We have been focusing our attention on the switchable strong photon-molecule
coupling field based on the interaction between gold nanoparticles and fluorophores labeled
CH3
CH3
with a thermo-responsive polymer. In this study,
CH2 CH CH2 C
CH2 C
gold nanoparticles were prepared by using
HN
HN O
O O
O
thermo-responsivepoly(N-n-propylacrylamide)
N
Et2N
N N
(PNNPAM) having a pyrazole-fused quinoxalineNN
X/Y = NNPAM/DMAEMA(DEDPQx) as a fluorophore and N,N-dimethylaminoethylmethacrylate(DMAEMA) as a stabilizer
Fig. 1. Structure of poly(DEDPQxof gold nanoparticles (Fig. 1).
The SPR
co-NNPAM-co-DMAEMA)(X/Y).
absorption band at 522 nm gradually appeared
when poly(DEDPQx-co-NNPAM-co-DMAEMA)(70/30) was used in the molar ratio of tertiaryamino groups (DMAEMA) to HAuCl4 of 8 underpH 8 (Fig. 2). Gold nanoparticles obtained werestable in water at least for a month at room
temperature and their diameters were 7.1
0.8
nm.
These results suggest that the gold
nanoparticles formed by autoreduction oftetrachloroauric acid were stabilized by the
copolymer having tertiary amino groups. The
fluorescence property of the copolymer with gold
nanoparticles upon heating is also discussed.

Fig. 2. Time-dependent UV-vis absorption
spectra of the poly(DEDPQx-coNNPAM-co-DMAEMA)(70/30)coated gold nanoparticles (DMAEMA /Au = 8) synthesized at pH 8.

Computational Approach for Enzymatic Reaction
using QM/MM Method
Toshio Asada
Depart of Chemistry, Osaka Prefecture University, Gakuen-cho,Naka-ku, Sakai-city 599-8531, Japan
Chemical reactions in a large molecular assembly usually proceed on the free energy
surface. In recent computation approaches, the combined quantum mechanical and molecularmechanical (QM/MM) calculation [1] can provide reliable physical properties for a given
structure. However, it is still difficult to predict reaction paths and free energy barriers,
because acceptable conformational entropies can only be evaluated from long time simulationsuch as Monte Carlo or molecular dynamics (MD) simulations.
To obtain reaction paths on the free energy surface, our Amber-Gaussian interface [2]can be applied to employ both the free energy gradient (FEG) and the nudged elastic band
(NEB) methods. Using FEG-NEB method, the reaction path can be optimized as a series ofchain of conformations on the free energy surface automatically. It is applied to theisomerization reaction of the simple glycine molecule in an aqueous solution and the
enzymatic reaction in the trypsin-BPTI complex.
For the glycine molecule, the zwitter ion form (ZW) is known to be more stable than
the neutral form (NF) in an aqueous solution, while NF is stable in the gas phase. The
calculated free energy barrier of 16.4 kcal/mol is reasonably agreement with the experimental
one as shown in Fig.1. The calculated results for the acylation reaction in trypsin-BPTI will
also be discussed (see Fig.2)
Free Energy,kcal/mol

20

TS 16.4

18(exp 14.6) 16

product

1412TS2Intermediate

10

ZW

8

BPTI-sideserineTS1 reactant

Trypsin-side

6

NF 4.1

4(exp. 7.3)

2
0

-1.5

-1

-0.5

0

0.5

1

1.5

ZW
NF
intrinsic reaction coordinate2

Fig.1 Calculated free energy curves by FEG-NEB method

Fig.2 Optimized acylation reaction path intrypsin-BPTI complex

References:[1] Asada,T.; Koseki,S.; Nagaoka, M. Phys.Chem.Chem.Phys. 2011, 13, 1590-1596.
[2] Okamoto,T.; Yamada,K.; Koyano,Y.; Asada,T.; Koga,N.; Nagaoka,M. J.Comp.Chem.,
2011, 32, 932-942.

Vapor-induced Multichromic Luminescence ofPlatinum(II) Complexes with Dicarboxybipyridine
Masako Kato
Department of Chemistry, Faculty of Science, Hokkaido University,
Sapporo 060-0810, Japan
Luminescent metal complexes exhibiting vapor-induced
chromic behavior (i.e. vapochromism) have recently drawn
much attention as promising chemical sensing materials. In thiscontext, we have developed various luminescent metal
complexes with sensing functionalities [1]. Herein, our recent
progress regarding vapochromic behavior of platinum(II)complexes bearing carboxy groups which can act as a goodFig. 1.
supramolecular synthon (Fig. 1) is introduced.
+
The platinum(II) complex, [Pt(CN)2(H2dcbpy)] (H2dcbpy = A = H : [Pt(CN)2(H2dcbpy)]
A = Na+: Na2[Pt(CN)2(dcbpy)]
4,4’-dicarboxy-2,2’-bipyridine) was found to
exhibit diverse color changes in the solid state
under different atmospheres of organic vapors[2]. The complex can form a porous
three-dimensional network structure by thehydrogen bonds and Pt···Pt interactions. It
exhibits red luminescence originated from the3
MMLCT state as is well known for theplatinum(II) complexes with short Pt···Pt
distances. When the dried sample of thecomplex is exposed to various organic vapors,
the luminescence spectrum shifts more than
200 nm in the visible region depending on thekind of vapors. The color changes are
attributed to the changes in the Pt···Ptinteractions. On the basis of the powder X-ray
Fig. 2. Luminescence spectral changes and thediffraction (PXRD), it was clarified that thetwo-step
structuraltransformationofcolor changes in the complex occur by[Pt(CN)2(H2dcbpy)] induced by DMF vapor.
two-step structural transformation (Fig. 2). It
is noteworthy that the three-dimensional structure is reconstructed spontaneously from theamorphous solid in the atmosphere of particular vapors. The details of the interesting
phenomena of these complexes as well as other related systems will be discussed [3].
[1] Kato, M. Bull. Chem. Soc. Jpn. 2007, 80, 287; Kato, M. et al., Chem. Lett. 2008, 37, 16;
Kobayashi, A. et al., Chem. Lett. 2009, 38, 998; Dalton Trans., 2010, 39, 3400; J. Am.
Chem. Soc., 2010, 132, 15286.
[2] Kato, M.; Kishi, S. et al., Chem. Lett., 2005, 34, 1368.
[3] Kobayashi, A.; Yonemura, T.; Kato, M. Eur. J. Inorg. Chem., 2010, 2465.

Pigments and Function of the Oceanic Photosynthetic
Antenna from Japanese Brown Alga, “Okinawa Mozuku”
Ritsuko Fujii1,2, Mamiko Kita2,3, Naoki Senju3, Daisuke Kosumi2,3,
Matsumi Doe1, Masahiko Iha4, Tadashi Mizoguchi5and Hideki Hashimoto 1,2,3
1

The OCU Advanced Research Institute for Natural Science and Technology (OCARINA),CREST/JST and 3 Dept. of Physics, Graduate School of Science, Osaka City University,
3-3-138, Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan; 4 South Product Co. Ltd., 12-75
Suzaki, Uruma-shi, Okinawa 904-2234, Japan; 5 Dept. of Bioscience and Biotechnology,
Faculty of Science and Engineering, Ritsumeikan University, Kusatsu, Shiga 525-8577, Japan
2

Oceanic photosynthetic organisms contribute almost one quarter of global primary production[1]. In adapting to the fluctuated light conditions of their habitat, they are evolving a varietyof light-harvesting antennae. They widely possess the membrane-intrinsic antenna contains aunique porphyrin type chlorophyll (Chl), Chl c in addition to the general Chl a [2]. The
aminoacid sequences of the Chl a/c type antennae are similar to that of the well-known
peripheral Chl a/b type antenna in higher plants, LHCII, although the X-ray structure was notclarified yet [2]. One of the major Chl a/c type antennae is “fucoxanthin-Chl a/c protein”(FCP) found mainly in brown algae and diatoms. In the FCP, both fucoxanthin and Chl ccollect the light energy and transfer it to Chl a, followed by the energy transfer to theoxygenic reaction centers (both photosystems I and II) where charge separation occurs. To
elucidate the mechanisms of the energy transduction, excited-state properties of the pigments
should be investigated. The study on the excited-state properties of Chl c left behind [2].
Cladosiphon okamuranus, “Okinawa Mozuku” in Japanese, is an original strain of a brown
alga in Okinawa, Japan. Super large-scale culture of the strain has been established in the“discoid germiling” form. The discoid germiling is a beneficial source of photosynthetic
apparatus because it is a micron-size without tough lipids and polysaccharides. Therefore byusing this strain, we are targeted to clarify the structure and function of the FCP. We havealready established the purification of the “Mozuku FCP”. Subunit analyses and amino acidsequencings by using TOF-MS/MS spectrometry are on going to determine the proteomics of
the “Mozuku FCP”. In this presentation, we focused on our recent progress on the pigmentsbound to the “Mozuku FCP”. Pigment composition and temperature tolerance of thepigment-binding were determined. Large scale purification of Chl c was established. Binding
properties of the pigments in the FCP were discussed based on a FCP-model structure.
References: [1] Jeffrey, S. W. et al. (Eds.), “Phytoplankton Pigments in Oceanography”,
UNESCO, Madrid, 2nd Ed., 2005 [2] Macpherson, A. N. and Hiller, R., In: Green, B. R.,
Parson, W. W. (Eds.) “Light-Harvesting Antennas in Phosotynshesis”, Kluwer Academic
Publishers, Netherlands, 2003

Proposals for
the OCARINA projectAdvance Molecular Science Research ProgramTetsuro Shinada
Graduate School of Science, Osaka City University
Abstract:
The molecular science research covering fundamental research areas of organic, inorganic,
analytical, and physical chemistries has been contributed to human prosperity because
chemical reactions and transformations are the key to the innovation of useful materials andunderstanding biological processes in the levels of molecular structures.
Herein, “Advanced Molecular Science Research Program” toward contribution to prosperityof Osaka City is proposed. The experts of chemical and biological researches in OCU arecollected into “the agora of molecular science” a field of the collective intelligence. Their idea
and knowledge are exchanged to encourage the progress of the research proposals to create
various advanced materials for human health, energy accumulation and transformations,electronics device, molecular sensor devices, and green chemistry.
The outline and details of this proposal will be presented on behalf of the project members.

Project outline

A novel biomotility, Mycoplasma gliding
Makoto Miyata
Department of Biology, Graduate School of Science, Osaka City University
Sumiyoshi-ku, Osaka 558-8585 Japan
Mycoplasma, a group of pathogenic bacteria is thecause of “walking pneumonie”, which is very epidemic
this year in Japan. They form a membrane protrusion
at a cell pole as presented in the figure, bind to animalcells with the protrusion, and glide. Although thegliding is fast and smooth, the mechanism is not related
at all to the known bacterial motility systems such as
flagella or pili, or conventional motor proteins including
myosin. The gliding motility is essential for their pathogenicity, but the mechanism had notbeen studied, before we started our study.
We have studied mainly on the fastest species, Mycoplasma mobile, which glides with 4
micron per s, i.e. 7 times of cell length on glass, focusing on the following subjects: (i)Gliding machinery including supporting structure, (ii) Component proteins of machinery, (iii)
Measurements of force and steps, (iv) Direct energy source and its coupling to cycle, and (v)binding target as the rail. Based on these observations, we proposed a working model.
“The gliding machinery is composed of four huge proteins at the base of membrane
protrusion and supported by a cytoskeletal architecture from the cell inside. Many flexible
legs about 50 nm long are sticking out from the machinery. The movements generated by
ATP hydrolysis cell inside transmits to “leg” protein through “gear” protein, resulting in therepeated catching, pulling, and releasing of the sialic acids fixed on the surface by the legs.”[1] Uenoyama, A.; Miyata, M. Proceedings of the National Academy of Sciences of the UnitedStates of America 2005, 102, 12754.
[2] Hiratsuka, Y.; Miyata, M.; Tada, T.; Uyeda, T. Q. Proceedings of the National Academy of
Sciences of the United States of America 2006, 103, 13618.
[3] Nakane, D.; Miyata, M. Proceedings of the National Academy of Sciences of the UnitedStates of America 2007, 104, 19518.
[4] Miyata, M. Trends in Microbiology 2008, 16, 6.
[5] Miyata, M. Annual Review of Microbiology 2010, 64, 519.

Invited Lectures

An Overview of the Human Frontiers of Science Program:
Report on the Grant
Richard Cogdell
Microbial Photosynthesis Lab, Glasgow Biomedical Research Centre,
120 University Place, University of Glasgow, G12 8TA,UK

Abstract:
One of the grand challenges facing mankind is to develop ways to convert solar energy into
dense portable fuels. There is one global scale biological/chemical process that does this,namely photosynthesis. The essence of photosynthesis can be broken down into four key steps.

Our research program is focussed on steps one and two. We are trying to determine the design
flexibility in organising light harvesting modules and reaction analogues onto surfaces toefficiently harvest solar energy and use it to separate charge. This requires two challenging
problems to be overcome. Firstly to be able to order these modules on a surface with nanoscaleprecision and secondly to be able to image and measure light harvesting processes on the same
nanoscale. Both these aims are very challenging.
Our approaches to solving these problems will be described. Then in the following talks
each of the groups involved in this program will give progress reports.

Groundwater Development Constraints in Urban and Rural
Bangladesh: Options for Sustainable Management
Kazi Matin Ahmed
Department of Geology, University of Dhaka, Dhaka 1000, Bangladesh

Abstract:
Bangladesh depends heavily on groundwater for all uses in urban and rural areas. Potablewater supply in urban and rural areas mostly provided by groundwater abstracted fromshallow and deep aquifers. Municipal water supplies exists around 100 urban centers whereas
rural water supply is mainly through more than 10 million domestic hand tube wells. Apartfrom shallow hand tube wells there are thousands of deep hand tube wells, mostly in the
coastal region.
Irrigation is the main consumer of groundwater which uses more than 90% of the abstracted
water. Irrigation water is provided by thousands of shallow tube wells fitted with centrifugal
pumps and few thousand of deep tube wells fitted with turbine pumps. Of the current irrigatedareas more than 70% comes from groundwater sources.
Groundwater has been the backbone of providing access to safe water and providing security
for a national with a population of more than 150 millions. However, there have been recent
problems both in terms of quantity and quality of groundwater. High abstractions for
irrigation cause domestic wells to dry up and results into water shortage in certain areas
during dry season. Also high abstractions in urban areas like Dhaka cause water level todecline and dewatering parts of the aquifer. Wells have to drilled into deeper and deeper levels
to provide water supply to the megacity dwellers.
Most severe problems related to groundwater development in Bangladesh are related to water
quality. Arsenic occurs over a vast part of the country at shallow aquifers exposing over 22
million people to arsenic at allowable limit. Apart from arsenic Manganese is also wide
spread in the country. Chloride is a quality constraint in coastal areas and certain pockets
inland.
Though the country is heavily dependent on groundwater there is no groundwater
management in place. As a result of unregulated use, groundwater is becoming an endangered
resource. A proper management strategy is needed to protect the vital natural resources of thecountry.

EXCESS SLUDGE REDUCTION BY COMBINEDPROCESS OF PHYSICAL PRETREATMENT AND
MICROFAUNA OF PREDATION ACTIVITY
Guoji Ding, Fei Yu, Li Mu, Yanjing Yu, Haihua Shen, Huiqing Qiu
Shanghai University, Shanghai, China, gjding@shu.edu.cn
Excess sludge treatment is a big challenging problem in wastewater treatment plants
due to economic and environmental factors. Excess sludge reduction by predatory activityof microfauna may be an ecological method with low energy consumption. The ingestion
efficiency of sludge by microfauna is restricted by the size of sludge, which can be
improved by physico-chemical treatment. Based on study of various physico-chemical
methods, effects of sludge crushing were investigated. The result indicated that on thepremise of low energy consumption, ozone oxidation or microwave radiation had little
effects on sludge size to satisfy the requirement of predation by Aeolosoma hemprichii.
While ultrasonic treatment or mechanical shearing could efficiently reduce the particle size
and improve the percentage of sludge which can be ingest by A. hemprichii. Comparedwith other physico-chemical treatments, mechanical shearing was more suitable for the
new technology, since it just required simple equipments and was easy to implement. In
addition, some of biologically active substances were studied for promoting the growth of
A. hemprichii in a reactor of biological wastewater treatment. It is clear that honey residue
and rice bran had a significant role on promoting the growth of A. hemprichii. The
population density can be doubled and population growth increased by 10.2% with theaddition of honey residue and rice bran.
Acknowledgement:
Authors sincerely thank the National Hi-Tech Research and Development Program ofChina (No. 2007AA06Z347), the Key Special Program on the S&T for the Pollution
Control and Treatment of Water Bodies (No. 2008ZX07421-004), and the Shanghai
Leading Academic Discipline (No. S30109).
References:[1] Low, E.W., Chase, H.A., 1999, Reducing production of excess biomass during
wastewater treatment [J]. Water Research, 33(5):1119-1132[2] Song, B.Y., Chen, X.F., 2009, Effect of Aeolosoma hemprichii on excess activatedsludge reduction [J]. Journal of Hazardous Materials, 162(1):300-304[3] Zhang, G., He, J., Zhang P, et a1., 2009, Ultrasonic reduction of excess sludge from
activated sludge system II: Urban sewage treatment. Hazard. Mater, 164:1105-1109

Keywords: excess sludge reduction, particle size, physico-chemical treatment, microfauna,predation

The Works of Sights in Manyoh-shu,
The Anthology of Ancient Japanese Poems
Masahiro Murata

Department of Literature, Osaka City University

(

)
(

)

Environment of Lake SANARU: A small urban watershed
Mitsuo TODA
Faculty of Engineering, Shizuoka University
3-5-1 johoku, Hamamatsu, Shizuoka, 432-8561 JAPAN
Abstract:
introduction
Lake Sanaru known as a small eutrophic lake islocated in Hamamatsu city. Population of the city is over
800,000 and population density of watershed is 2800/km2.
One of the main pollution loading is human waste becauseof high population density, though the sewerage is build up
to over 90%. In addition, nonpoint source pollution(synthetic fertilizer, natural loading from precipitation

Fig.1 Location of lake SANARU

and ecosystem) especially inorganic nitrogen is serious.
It had been the most polluted lake by COD-Mn from2001 to 2006 in Japan. Profiles of the lake are shown in
Table 1.

The lake has two rivers and there branches inTable 1 Profile of lake SANARU
Lake size

2.2 km×0.6 km×2 m

upstream and connects to Pacific Ocean via Lake

Lake volume

2.4×106 m3

Hamanako. To decrease the pollution, Shizuoka

Lake area

1.2 km2

University established the team “amenity SANARUKO

Watershed area

up:18.3 km2, down:40.0 km2

project”. This work is one of the outputs of the project.

Population

1.6×105 km2

The presentation consists of two topics based on the

Population density

2822 km-2

stable isotope analysis. One is for hydrology, and

COD-Mn (average)~ 9 ppm

another is for food web of the lake.

Hydraulic residence time

~ 46 days

Salinity (anerage)

5‰

Tidal flow

~ 1×106 m3day-1

In 2009, COD-Mn decreased to 7.6 ppm andthpollution rank was 10 . It is the result of the steadycontrol measures. In addition, we believe understandingof mass balance and mass transfer must be important for restoration of the environment in next step.
Hydrology of lake Sanaru
We collected the water samples from lake, rivers, ground waters and precipitations. After filtration,salinity and stable isotopes ratio (δD and δ18O) were measured. Mixing ratio of seawater and freshwater
was calculated by salinity. Mixing ratio of seawater varied in the range of 3 % - 26 %. On the other hand,δ18O value of ground water (-7 ‰) and running water (-10.2 ‰) vary in only narrow range. (Fig.2)
the proportion of freshwater from different sources is able to calculate usingδ18O value.

So,

In some case,18

calculation is difficult because of fluctuation inδ O of precipitation. So we collected the samples ofprecipitation at 30 min intervals during period of hard rainfall. This time, we will estimate the proportion
usingδ18O value.

Fig.2 Distribution of G18O value in the watershed
Food web of lake Sanaru
The lake connects to the Pacific Ocean via lake Hamanako. Therefore the water is brackish andnormal salinity of the lake is around 5‰. There are over 50 fishes includes freshwater, seawater andamphidromous spices. Eutrophic water and flat shallow structure (average depth 2m, max. 2.5 m ) enable
the high production of organic matter by phytoplankton. Almost all days of the year, water is muddy andtransparency is under than 30 cm. In order to find any key to the settlement of the environmental problem,
we were interested in food web and mass balance of lake Sanaru. We collected many fishes, other animals
and SS. In Fig.3, G15N and G13C value of each samples were shown. Fig.4 represents the outline of theunexpected simple food web consist of only three trophic levels.

G15N

G13C
Fig.3 Food web analysis of lake SANARU

Fig.4 Three trophic levels of lake SANARU

What is the Most Environmentally Friendly
Utilization of Biomass?
Satoshi MATSUDA
Department of Materials Science and Chemical Engineering, Shizuoka
University,
3-5-1 Johoku, Naka-ku, Hamamatsu, 432-8561 Japan
Abstract:
Recently the liquid fuel production from crops and other biomass resources (‘biofuel’)
has attracted much attention in the world as the prevention of global warming is becoming anurgent issue, because the biofuel is perceived to be ‘carbon neutral’ and useful as acountermeasure against global warming. In fact, the production of biofuel has been put into
practical use not only in the US, EU, Brazil and other countries but also in Japan. As for its
impact on the environment, however, evaluations still vary including those on the influence of
biofuel on the global economy, for example the food price crisis that might have been causedby competition with food. In the previous study [1], the author pointed out that ‘bio-ethanol’
from crops is never ‘carbon neutral’, which means the production and use of the fuel does notlead to a net increase in atmospheric CO2 concentration, nor is useful as a countermeasureagainst global warming.
Since the shortage of food crops affected by the expansion of biofuel production becamea critical issue, the ‘second-generation’ of biofuel made from non-food biomass has attracted
much attention all over the world. In particular, the following statement in the Hokkaido
Toyako G8 summit held in Nov. 2008 accelerated this trend which made ‘use of biofuels withfood security and accelerated the development and commercialization of sustainablesecond-generation biofuels from non-food plant materials and inedible biomass’ (in ‘G8
Leaders Statement on Global Food Security’ [2] ).
The target biomass has a wide variety of kinds; cellulosic materials such as woody
biomass and paddy straw, algae and some kinds of oil producing plants, which are considered
as sustainable. Research on the kinds of the target biomass is in progress. Among them
‘Jatropha’ has emerged as one of the best candidates for future biodiesel production [3],partially because the production of bio-ethanol from cellulosic materials has encounteredmany difficulties in practice. For example in Indonesia, there is a national program forbiofuels development in which 20% of diesel consumption will be supplied with biodiesel
utilization mainly by Jatropha oil(equiv. 10.22 million kL) by the year 2016 to 2025. But a
positive result of an assessment on the validity of Jatropha production was not obtained fromresearch by the author, in which a feasibility study was tried as quantitatively as possibleusing the data obtained from a field survey in Indonesia conducted by the author in January
and March of 2009 [4].

The situation regarding the utilization of biomass is rather complicated: There aremany problems in the liquid biofuel production pointed out from various points of view, andthe author has considered the liquid biofuel to be not environmentally friendly. The
estimation of the real amount of utilizable biomass resources is also a very difficult task.
However, the fact remains true that biomass should be utilized effectively as one of the mostvaluable renewable resources in our society which should be sustainable and independent of
petroleum, because biomass is the main source of food, timber, paper and also fuel. In thispresentation, the real and effective estimation of biomass use was discussed, concrete
examples of the quantitative evaluation of biomass utilization were exhibited, and a concrete
plan for increasing the production of domestic forest biomass was proposed, because thelargest biomass resource in Japan is undoubtedly forest biomass whereas domestic forestry
has been following a course of decline.
The emphasized points in this presentation are as follows:
1) In order to quantitatively estimate the contribution of biofuel to the reduction of CO2
emission, a new index of CO2 emission reduction as well as its calculation method should be
proposed.
2) The validity of biomass utilization should be assessed from the standpoint of bothresources (=the amount and distribution of really utilizable biomass resources and acomparison of the amount with their demand, and also environmental impacts) andtechnology with the utilization system (=how to utilize the biomass resources).
3) The priority of biomass use should be as follows according to its economical value: humanfood > animal feed > industrial material > fuel (energy), thus the cascade type of the biomass
utilization system should be sought.
4) Automobiles should be driven with electricity rather than an internal combustion engine
using bio-ethanol or bio-diesel because the former is highly efficient in energy utilization.
5) If the purpose is to obtain electricity from solar energy, solar cell is a much better option
than the power generation with biomass combustion due to the difference in conversion
efficiency.
6) The absolute amount of really utilizable biomass in the energy equivalent value comparedwith fossil fuel is rather small; only a small percent of the world's primary energy can besupplied with biomass, meaning that biomass should be only used as one of the local energy
sources.

References:[1] Matsuda, S.; J. Environ. Information Sci. 2009, 37(5), 1.
[2] http://www.mofa.go.jp/policy/economy/summit/2008/doc/doc080709_04_en.html[3] Fairless, D.; Nature 2007, 449, 652.
[4] Matsuda, S. et.al. ; J. Automation, Mobile Robotics & Intelligent Systems 2009, 3(4), 18.

HFSP ‘Team Glasgow’ Progress ReportSarah Henry, Richard Cogdell
Microbial Photosynthesis Lab, Glasgow Biomedical ResearchCentre,120 University Place, University of Glasgow, G12 8TA,UK

Abstract: The work in Glasgow consists of two main themes; (1) to understand energy
transfer within native purple bacterial photosynthetic membranes and (2) to use thisknowledge to help us understand the requirements necessary to obtain directed energy transfer
on surfaces.
Photosynthetic bacteria are able to alter the architecture of their photosynthetic membranes in
response to different light conditions. Many spectroscopic studies have been performed on
individual, purified complexes, whereas in Glasgow we wish to understand energy transfer
within the intact membrane and how the complexes work together. To this end we are able toproduce membranes from a variety of different species and from cells grown under different
environmental conditions [1], which can then be investigated using time resolved
spectroscopy [2]. The second part of the work is to understand all the parameters necessaryfor energy transfer between photosynthetic complexes attached to fixed surfaces.
Photosynthetic complexes with specific tags should allow complexes to be attached in adefined orientation and so facilitate energy transfer along the surface. We have access to astate of the art nanotechnology facility to produce gold patterns on fixed substrates. To
overcome any quenching of the fluorescence from the gold, work is underway to produce
tagged and linkered light harvesting proteins with variable height and orientation.
The understanding of energy transfer within the intact native membrane and the application ofthese principles to energy transfer along fixed surfaces should allow the basic principles to beestablished from which an artificial light-harvesting device can be designed.
References:
1. Gardiner, A. T.; Cogdell, R. J.; Takaichi, S., The Effect of Growth-Conditions on theLight-Harvesting Apparatus in Rhodopseudomonas-Acidophila. Photosynthesis Research
1993, 38, (2), 159-167.
2. Moulisova, V.; Luer, L.; Hoseinkhani, S.; Brotosudarmo, T. H. P.; Collins, A. M.; Lanzani,G.; Blankenship, R. E.; Cogdell, R. J., Low Light Adaptation: Energy Transfer Processes in
Different Types of Light Harvesting Complexes from Rhodopseudomonas palustris.
Biophysical Journal 2009, 97, (11), 3019-3028.

Optimizing Light Absorption and Controlling Energy Flow in Artificial
and Natural Photosynthesis
Thomas A. Moore, Devens Gust and Ana L. Moore
Center for Bioenergy and Photosynthesis, Department of Chemistry andBiochemistry, Arizona State University, Tempe, AZ, USA 85287-1604*Corresponding author, e-mail: tmoore@asu.edu

Even though photosynthesis powers the planet, its global rate of energy flow of ~120 TW iscurrently totally reserved for biosphere service and food and bioenergy production for humanuse. There are no reserves of photosynthetic capacity to provide increasing amounts of
biofuel for growing the human GDP and food for the ever-increasing human population.
Indeed, when such demands are made, the capacity comes at the peril of biosphere service.
Fortunately for us, photosynthesis can be dramatically improved to meet human needs. The
theoretical limit to solar energy conversion efficiency is set by fundamental thermodynamic
principles that apply to the isothermal conversion of light into chemical and/or electricalpotential. While human ingenuity in photovoltaic technology uses these principles to achieve
record efficiencies of solar to electrical power conversion today, photosynthesis, having been
optimized by Darwinian selection to push genes forward, is not optimal for providing thesolar-derived fuel to support human activities. Measured against maximum conversion
efficiency, the less-than-optimal efficiency of photosynthesis starts with a poor match of theabsorption of light by photosynthetic organisms to the solar spectrum. In selected
photosynthetic systems, rational design based on the principles demonstrated in artificial
systems and the techniques of molecular and synthetic biology, can be used to optimize solarto-biofuel conversion efficiencies to meet particular needs. Key biological parts necessary toinitiate this research are found in photosynthetic organisms; I will present our progress on
using fundamental design principles and existing technology to inspire the design of highefficiency artificial and natural photosynthesis. This combination of technology with biology
can be a step towards achieving sustainable energy production based on efficient solar-driven
water oxidation and carbon reduction. Indeed, along these lines, I plan to also bring up workfrom other labs in which new hybrid systems using PV cells to drive geobacteria growth withremarkable faradaic efficiency and energy conversion efficiency have been reported. I will
also present our latest work on the photonic control of energy transfer in multichromophoricmodel antenna systems done in collaboration with the Fleming group based on a pH sensor
and an actinic light intensity sensor. Model systems have also been recently developed incollaboration with the Kennis and van Grondelle groups to define a new exciton-based
coupling mechanism between carotenoid pigments and tetrapyrroles.

Design of Photoelectrochemical Cells for the Splitting of Water andProduction of Fuel
Ana L. Moore*, Thomas A. Moore and Devens Gust
Center for Bioenergy and Photosynthesis, Department of Chemistry andBiochemistry, Arizona State University, Tempe, AZ, 85287-1604, USA*Corresponding author, e-mail: amoore@asu.edu
The design of bioinspired schemes that couple solar energy conversion to the oxidation ofwater and the subsequent use of the reducing equivalents to synthesize energy-richcompounds, such as hydrogen or fuels based on reduced carbon is the main objective of ourpresent research.1 In order to establish the design principles for a tandem, two junction (orthreshold) photochemical cell, we are assembling Grätzel-type photoelectrodes that model
photosystems I and II (PSI and PSII) of plants. The photoanode model of PSII will contain amimic of the donor side (water oxidizing side) of PSII reaction centers. In PSII, tyrosine Z(TyrZ) mediates charge transport between the photo-oxidized primary donor (P680•+) and theoxygen-evolving complex (OEC). The oxidation of TyrZ by P680•+ likely occurs with thetransfer of the phenolic proton to a hydrogen-bonded histidine residue (His190). This
coupling of proton and redox chemistry is thought to poise the TyrZ oxidation potential
between those of P680•+ and the OEC. We have prepared a bioinspired system (BiP-PF10)
consisting of a high oxidation potential porphyrin (PF10, 1.59 V vs. NHE, a model of P680)
that is covalently attached to a benzimidazole-phenol pair (BiP) that mimics the TyrZ-His190
pair in PSII. Electrochemical studies show that the phenoxyl radical/phenol couple of themodel system is chemically reversible with a midpoint potential of 1.24 V vs. NHE and istherefore thermodynamically capable of water oxidation. When the BiP-PF10 construct is
attached to TiO2 nanoparticles and excited with visible light, it undergoes photoinduced
electron transfer. Electrons are injected into the semiconductor and the corresponding holes
are localized on either the porphyrin (BiPPF10•+-TiO2•–) or the phenol (BiP•+-PF10-TiO2•–).
EPR provides a clear spectroscopic picture of these processes.2 The photoelectrode model of
PSI will be sensitized by low potential naphthalocyanines or phthalocyanines, which absorb
light in the near IR region of the spectrum. Upon photoexcitation, these dyes are designed to
inject electrons into semiconductors having sufficiently negative conduction bands toeffectively drive the reduction of protons to hydrogen at a cathode. The semiconductor will
be electrically wired to a cathode suitable for hydrogen production: either a metal electrode(Pt or Ni) or a hydrogenase-modified carbon electrode.3
References:
1. Hambourger M. et al. Chem. Soc. Rev, 2009, 38, 25–35.
2. Moore, G. F. et al. J. Am. Chem. Soc. 2008, 130, 10466–10467.
3. Hambourger M. et al. J. Am. Chem. Soc. 2008, 130, 2015–2022.

Energy-transfer
dynamics
betweencarotenoid
andbacteriochlorophyll in the light-harvesting system of purple
photosynthetic bacteria as visualized by sub-picosecond
pump-and-probe and sub-20 fs four-wave mixing spectroscopies
Hideki Hashimoto1,2,3, Daisuke Kosumi2,3, Satoshi Maruta2,3, Tomoko Horibe2,3,
Ritsuko Fujii1,2, Mitsuru Sugisaki1,2,3, Mamoru Nango2,3 and R.J. Cogdell4
1

The OCU Advanced Research Institute for Natural Science and Technology (OCARINA), 3-3-138 Sugimoto,Sumiyoshi-ku, Osaka 558-8585 Japan
2
CREST/JST, 4-1-8 Hon-cho Kawaguchi, Saitama 332-0012, Japan3
Department of Physics, Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku,
Osaka 558-8585, Japan
4
Glasgow Biomedical Research Centre, University of Glasgow, 126 University Place, Glasgow, G12 8QQ,
Scotland, UK
E-mail: hassy@sci.osaka-cu.ac.jp

In purple bacterial photosynthesis, carotenoids play the crucial roles of light-harvestingand photoprotection. These functions reflect singlet-singlet and triplet-triplet excitationenergy transfer between carotenoid and bacteriochlorophyll [1]. Singlet-singlet excitationenergy transfer from chlorophyll to carotenoid have been discussed in terms of
non-photochemical quenching of the chlorophyll Qy fluorescence (NPQ) that plays a keyrole of dissipation of excess light energy in oxygenic photosynthesis [2,3]. On the other
hand, the photoprotection of purple bacterial photosynthetic organisms from excess lightenergy has been discussed in terms of triplet-triplet excitation energy transfer frombacteriochlorophyll to carotenoid. Here, singlet-singlet energy transfer frombacteriochlorophyll to carotenoid has not been considered to be active in bacterial
photosynthesis even though it is energetically possible, e.g. the excitation energy transferfrom the bacteriochlorophyll Qx excited state to the carotenoid S1 excited state. In thislecture, we report a discovery of this new singlet-singlet excitation energy transfer pathway
in purple bacterial photosynthetic light-harvesting complexes [4].
Another devotion of the present lecture is the development of new aspect for
time-resolved experiments. In order to achieve this objective we have focused our attention
on sub-20 fs four-wave mixing experiments. We have successfully developed the methods
to understand complicated relaxation dynamics of carotenoids free in solution and thosebound to LH2 antenna pigment-protein complexes. The concurrent dynamics of theelectronic excitation and vibronic oscillations of carotenoids have been investigated bymeans of the transient grating spectroscopy. The experimental results have been comparedwith the theoretical calculations that are based on a Brownian oscillator model. The
excitation energy-transfer processes as well as the internal conversion are modeled within
the framework of Liouville space pathways. We demonstrated a general framework to use
the Feynman-diagrammatic approach that can be readily extended for including some
additional electronic states. The results have been reported in five publications of PhysicalReview B [5].
1)
2)
3)
4)

Frank, H.A. and Cogdell, R.J. (1996) Photochem. Photobiol. 63, 257-264.
Ruban, A.V. et al. (2007) Nature 450, 575-578.
Ma, Y.-Z., et al. (2003) PNAS 100, 4377-4382.
Kosumi, D. et al. (2011) Angew. Chem. Int. Ed. 50, 1097-1100; Maruta, S. et al. (2011) Phys.
Status Solidi B 248, 403-407.
5) Sugisaki, M. et al. (2007) Phys. Rev. B 75, 155110 ; Fujiwara, M. et al. (2008) Phys. Rev. B 77,
205118 ; Fujiwara, M. et al. (2008) Phys. Rev. B 78, 161101(R) ; Sugisaki. M. et al. (2009) Phys.
Rev. B 80, 035118 ; Sugisaki, M. et al. (2010) Phys. Rev. B 81, 245112.

Femtosecond Pump-Probe Confocal Microscopy for
the Study of Excited-State Dynamics with High
Temporal and Spatial Resolution
Dario Polli
Dipartimento di Fisica – Politecnico di Milano (Italy)
Piazza L. da Vinci, 32 – 20133 Milano

Femtosecond pump-probe spectroscopy is a powerful technique for investigating excited state
dynamics in molecules, providing access to both radiative and non-radiative deactivation processes. This
technique has the potential to unravel photophysical processes, but in standard implementations it has limited
spatial resolution: the probed sample area has diameter of about 100 micrometers. We have developed an
instrument combining broadband femtosecond pump-probe spectroscopy and confocal microscopy,
delivering simultaneously high temporal and spatial resolution.
Composites are at the heart of polymer applications in photonics and optoelectronics, and are
indispensable in devices ranging from solar cells to all-optical modulators. In such samples, phenomena
occurring at interfaces between two materials are of fundamental importance but are extremely complex andpoorly understood. Blending different semiconducting polymers leads to samples with enhanced or new
properties. Engineering such composites in order to obtain the desired functionalities is one of the major
challenges in polymer technology, but it also raises fundamental questions about the physics and chemistryat the interfaces between different domains. Phenomena occurring at these interfaces often determine device
performances, but are poorly understood due to the variety of possible electronic states (excitons, excimers,
charge transfer states) and processes (energy transfer and charge separation) and to their complicateddynamics.
We have applied our newly developed tool to study the properties of polymer blends by directly
accessing the dynamics at the interfaces between different materials, which are of fundamental importance tounderstand the fate of the excited states and the relaxation paths which dictate the ultimate device
performance. We will report on pump-probe measurements of phase-separated conjugated-polymer thinfilms with ≈150-fs temporal resolution and ≈300-nm spatial resolution. Our results provide new insight into
their complex structure and single out “dynamical” interfaces, i.e. border regions at the phase separated
islands that behave differently in terms of transient absorption and relaxation dynamics.