2010 OCU Interna.onal Symposiumon the Founda.on of Environmental Research
8‐9 March, 2010
Awaji Yumebutai Interna0onal Conference Center

Supported by
JST‐CREST
Human Fron0er Science Program
MEXT
SPACC‐CSJ
Specially Dis0nguished Research Project in Osaka City University
The Integrate Advanced Research Ins0tute of Osaka City University

Preface

Hideki Hashimoto (Project Leader)
CREST-JST and Graduate School of Science, Osaka City University

Shortage of energy and water resources (= food production) and the global warming
are the grave crises that the human beings on this planet are currently facing. These
crises are generated during the course of the development of cities. And now they areseriously affect the life of the people, who are living in the modern cities. In this sense,
the global crises can be regarded as a symbolic matter of civic problems. They cannot
be simply ignored by us, who are living in one of the major ordinance-designed cities“Osaka”. Therefore it is a challenging subject to find out possible ways to suggest
powerful measures to cope well with these problems.
There are three scientific faculties (Faculties of Science, Engineering, and Human
Life Science) at the Sugimoto campus in Osaka City University. These faculties areaccounted to be the treasure troves of Osaka city in the scientific field. Since the issue
of global crisis extends over the whole planet, it is required to assimilate the knowledge
accumulated by the scientists in these three independent faculties to correctly deal withthe urgent issue of the global crises. This is an exact reason why we have launched a
new research institute whose members are carefully selected from the above threefaculties. The new research institute is named as “The Integrated Advanced ResearchInstitute of Osaka City University”. The first approved research project in this instituteis the one that challenges the regeneration of the urban environment, and it tries totackle the problems of biological systems and the sound and innovative use andcirculation of energy and groundwater. The project is constituted with three strategic
research subjects and is guided by three research teams as listed below.
Subject of Team A:
Subject of Team B:
Subject of Team C:

Development and Industrial Application of the Next Generation
Energy Resources
Utilization of Groundwater for the Preservation of Civil
Environment and for the Prevention against Geo-hazard
Space and Time Evolution of the Environment and Biological
Systems in the Urban Area

These subjects cover the broad area of scientific research ranging from microscopic
space to macroscopic prediction. In order to effectively use the outcome of the project it
is very important to facilitate the mutual communication among the three researchgroups. Without mutual understandings it is impossible to meet the problems of theurban environment and the global issues. Furthermore, the outcomes of the project
should be informed toward all over the world.
This international Symposium is held on the subject of environmental research.
Eminent active researchers at home and abroad in the relevant research fields are invitedias keynote speakers of this symposium. I hope that, through an animated discussion, we
can share common realization toward the resolution of worldwide affair. Finally, I
strongly wish that this symposium becomes small but great first step for the dispatch ofintelligence under the slogan of “Saving the World Starting from Osaka”.

Hideki Hashimoto (Project Leader)
CREST-JST and Graduate School of Science, Osaka City University

Invited Speakers
Richard J. Cogdell (University of Glasgow, UK)
Thomas A. Moore (Arizona State University, USA)
Ana L. Moore (Arizona State University, USA)
Bruno Robert (Institute of Biology and Technology of Saclay, FRA)
Leroy Cronin (University of Glasgow, UK)
Timothy J. Storr (Simon Fraser University, CAN)
Lawrence R. Sita (University of Maryland, USA)L. James Wright (University of Auckland, NZ)
Osamu Ishitani (Tokyo Institute of Technology, JPN)
Tsutomu Miyasaka (Toin University of Yokohama, JPN)

ii

Programme
8th March, 2010
13:30~14:00

Opening Remarks
Hideki Hashimoto
Osaka City University (JPN)

14:00~15:00

Plenary Lecture
Richard J. Cogdell……………………………………………1
University of Glasgow (UK)
“What can we learn from photosynthesis about
how to use solar energy to produce fuels? ”

15:00~16:00

Bruno Robert…………………………………………………2
Institute of Biology and Technology of Saclay (FRA)“Bioenergetic Studies in the Parisian Area”

16:00~16:15

Interval

16:15~17:15

Thomas A. Moore……………………………………………3
Arizona State University (USA)“Combining Technology with Biology
for Efficient Energy Production and Use”

17:15~18:15

Osamu Ishitani………………………………………………4
Tokyo Institute of Technology (JPN)“Artificial photosynthetic systems
for reduction of NADP model compounds and CO2”

18:15~19:45

Banquet19:45~21:45

Poster Sessions, Mixeriii

9th March, 2010
09:00~10:00

Timothy J. Storr……………………………………………5
Simon Fraser University (CAN)“Correlation of Electronic Structure and Reactivity- The Case of Oxidized Metal Salens”

10:00~11:00

Tsutomu Miyasaka…………………………………………6Toin University of Yokohama (JPN)“Photoelectrochemical Simulation of Energy Conversion in the
Photosynthetic Primary Processes and Design for Film-type
High-efficiency Dye-sensitized Solar Cells”

11:00~11:10

Interval

11:10~12:10

Ana L.Moore…………………………………………………7
Arizona State University (USA)“Design of photoelectrochemical cells
for the splitting of water and fuel production”

12:10~12:50

Nobuo Kamiya………………………………………………8
Osaka City University (JPN)“Structure around Oxygen-Evolving Mn4OxCa-Cluster of
Photosystem

II

Complexfrom

Thermosynechococcus

vulcanus”
12:50~13:50

Lunch

13:50~14:50

Leroy Cronin…………………………………………………9
University of Glasgow (UK)
“Manganese-Polyoxometalate Architectures:
Towards Water Oxidation Catalysts Inspired by Photosystem II”

14:50~15:50

L. James Wright……………………………………………10
University of Auckland (NZ)
“Green Oxidation Catalysts”
iv

15:50~16:00
16:00~17:00

17:00~17:10

Interval
Lawrence R. Sita……………………………………………11
University of Maryland (USA)“New Platforms for Probing Early Transition Metal Trends for
Bimetallic Dinitrogen Activation and N≡N Bond Cleavage”
Closing Remarks

Conference Venue: Awaji Yumebutai International Conference Center
http://www.yumebutai.org/english/index.html

v

.
.

What can we learn from photosynthesis about
how to use solar energy to produce fuels?
Richard J. Cogdell1*, Leroy Cronin2 and Hideki Hashimoto3,
Departments of 1Molecular and Cellular Biology, and 2Chemistry,
University of Glasgow, Glasgow, UK and 3‘CREST/JST’, Departmentof Physics, Graduate School of Science, Osaka City University, 3-3138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan
Corresponding author*, e-mail: R.Cogdell@bio.gla.ac.uk
Currently in the developed world we obtain about 70% of our energy requirements byburning fossil fuels such as oil, coal and gas. Due to the fact that supplies of both oil andgas are fast running out and because of worries about climate change and its links to risesin the concentration of atmospheric carbon dioxide mankind urgently needs to startdeveloping new sustainable ways to produce fuels. If these fuels cannot be ‘zero carbon’then they should be as ‘carbon neutral’ as possible.
There is one major chemical process on the planet that does use solar energy to power tosynthesis of fuel and this is photosynthesis. So is it possible to learn from photosynthesis
to devise novel strategies to use solar energy to make fuels, especially those that can beused for transportation?
Although, at present we do not have all the detailed information that is needed in order toproduce such systems it is possible from a consideration of the essence of photosynthesis
to start a long the path towards succeeding in this aim. Photosynthesis can be divided into
four key partial reactions [1]. These are light-harvesting (light-concentration), using thisconcentrated light-energy to separate charge across a membrane, accumulation of positive
charges on one side of this membrane in order to extract electrons from water (water
splitting) and accumulation of the negative charges on the other side of this membrane inorder to do catalysis to produce a fuel (e.g. the conversion of carbon dioxide tocarbohydrate)
Jim Barber from Imperial College in London has championed the idea of an artificial leaf.
This is an elegant concept that really clearly illustrates the idea of using the photosynthetic
blueprint in order to design ways of using solar energy to produce fuels. We will consider
in this presentation each of the four key partial reactions of photosynthesis, outlined above,in order to assess where current research is along path to producing fuels from solar
energy. We will describe both our current approaches and where we think the majorbottlenecks are.
[1]
ESF report on “Harnessing solar energy for the production of clean fuels”.
http://ssnmr.leidenuniv.nl/files/ssnmr/CleanSolarFuels.pdf

1Bioenergetic Studies in the Parisian Area
Bruno RobertInstitute of Biology and Technology of Saclay
CEA Saclay 91191 Gif/Yvette France

In the area south-west Paris is currently built the largest research campus in France. Studies
concerning climate, energy and environment constitute an important aspect of this operation.
The different facets of this project, whether these concern fundamental or applied research
will be detailed, as well as their insertion in largest European initiatives.
Research in bioenergetics performed at the Institute of Biology and Technology of Saclay
constitutes the 'bio' branch of this project. They mainly concern(i)the design of new, bioinspired, photocatalysts, able to perform reactions involving
more than one electron, with the final aim to photodissociate water.

(ii)

design of mutant hydrogenase proteins, (more) resistant to the presence of hydrogen(iii)

the characterisation of the cascade of events following stress in oxygenic organisms,
which ultimately result in the quenching of the incoming solar energy : these reactions
occur whether these organisms are submitted to light-, drought- or cold-stress, andconstitute a serious limitation to biomass production. We have recently characterised
the proteins involved in this quenching process, as well as the molecular mechanisms
which allow an efficient trapping of the excess excitation energy [1-3]. Recent
advances in this field will be described, in plants, diatoms and cyanobacteria.

References[1] Pascal AA, Liu ZF, Broess K, van Oort, B, van Amerongen H, Wang C, Horton P, Robert
B, Chang W and Ruban A (2005) Nature 436 (7047): 134-137. (128)[2] Ruban AV, Berera R, Ilioaia C, van Stokkum IHM, Kennis JTM, Pascal AA, vanAmerongen H, Robert B, Horton P, van Grondelle R (2007) Nature, 450, (7169), 575-579.
(71)[3] Wilson A, Punginelli C, Gall A, Bonetti C, Alexandre M, Routaboul JM, Kerfeld CA, van
Grondelle R, Robert B, Kennis JT, Kirilovsky D. (2008) Proc Natl Acad Sci U S A.
105:12075-80 (8)2Combining Technology with Biology for Efficient Energy Production andUseThomas A. Moore*, Ana L. Moore and Devens Gust
Center for Bioenergy and Photosynthesis, Department of Chemistry andBiochemistry, Arizona State University, Tempe, AZ, USA 85287-1604*Corresponding author, e-mail: tmoore@asu.edu
The anthropocene era is characterized by an increasing imbalance in many Earth systems1.
Although our understanding of the coupling between the climate system and human activity is
incomplete, there is little doubt that the climate system is linked to CO2 emissions from fossil fuelproduction and use. Conservation and increases in energy transformation efficiency can play key
roles in reducing emissions. Progress in these efforts is increasingly urgent as the first world
responds to the challenge of convergence of Earth’s developmentally diverse peoples tosustainability. Biological energy transduction processes address the issue of efficiency byoffering examples of elegant machinery, composed of earth-abundant materials, that operates
efficiently and essentially isothermally. Moreover, biological systems exhibit repair, selfassembly and replication – features that so far remain elusive to human-engineering of devices.
Biological mainstream processes that might be advantageously incorporated into emerging
energy technologies include catalysts for O2/H2O, H+/H2, CO2/CH2O redox reactions, reactions
involving making/breaking carbon-carbon bonds, the redox chemistry of nitrogen, and manyothers. Focusing on solar energy conversion, photosynthesis inspires us to imagine technologies
that would convert solar energy to fuel at rates commensurate with human use. Aspects ofphotosynthetic machinery that are important to future solar technologies include energy transfer,
photoinduced electron transfer at molecular heterojunctions, catalysis, protective mechanisms,
and control networks. In addition to the design, synthesis and assembly of constructs that carryout such processes, artificial photosynthesis can define the design parameters to be used in thenascent field of synthetic biology to make vast, much needed improvements in the energy yield ofphotosynthesis2,3. Several bio-inspired constructs for solar energy conversion have beenassembled and will be presented. In one, a photobiofuel cell uses artificial reaction centers,
visible light and two enzymes to reform biological substrates such as ethanol into hydrogen4. Thissystem interfaces redox chemistry with electromotive force at two junctions, and demonstrates
two methods for coupling biological redox catalysts with emf. In a second system, solar-driven
water oxidation using an IrO2 catalyst and an external boost of about 0.2 V allows the electrons to
combine with protons, producing hydrogen at the cathode5. We have developed energy andelectron transfer-based models for incorporation of control features into artificial systems6,7.
REFERENCES[1] Rockstrom, J., et al., Nature, 2009, 461, 472.
[2] Hambourger, M., et al., Chem. Soc. Rev., 2009, 38, 25.
[3] Gust, D., et al., MRS Bulletin, 2008, 33, 383.
[4] Hambourger, M., et al., J. Am. Chem. Soc., 2008, 130, 2015.
[5] Youngblood, W. J., et al., J. Am. Chem. Soc., 2009, 131, 926–927.
[6] Straight, S. D., et al., Nature Nano, 2008, 3, 280.
[7] Berera, R., et al., Proc. Nat. Acad. Sci., 2006, 103, 5343.

3

Artificial photosynthetic systems for reduction ofNADP model compounds and CO2
Osamu Ishitani
Department of Chemistry, Tokyo Institute of Technology,
Meguro-ku, O-okayama, Tokyo 152-8551, Japan

Both problems of the global warming and shortage of the fossil fuels have brought
about great interest in artificial photosynthesis. In photosynthesis of green plants,
electrons captured from water using solar energy are stored into the coenzyme NADP.
The product NADPH is used for reduction of CO2 as a reductant in the Calvin cycle.
Therefore, development of both photocatalysts for reduction of NADP and CO2, which
require two-electron (hydride) reduction, should be important targets in the field of theartificial photosynthesis.
I report our recent results about architectural investigation of such photocatalysts.
We have developed highly efficient photocatalytic systems using the rhenium(I)complex(es) as either photocatalyst or catalyst for CO2 reduction.1
I will focus on thefollowing systems in my talk.
(1) Development of the most efficient photocatalystic system with two different Re(I)complexes (ΦCO = 59 %).1a(2) Architecture of supramolecular metal complexes with both Ru(II) and Re(I)complexes as photosensitizer and catalyst, respectively.2
Ordinary photocatalysts, which initiate intermolecular electron transfer, is useless for
reduction of NADP model compounds to the corresponding 1,4-duhydroforms becauseof rapid coupling reactions of the one-electron reduced radicals of the models.
(3) We have developed a novel type of photocatalytic systems which can drive only
hydride reduction of an NADP model compound with high selectivity andefficiency.3
References
1 (a) J. Am. Chem. Soc., 2008, 130, 2023-2031. (b) J. Am. Chem. Soc., 2005, 127, 15544-15555.
(c) Res. Chem. Intermediat. 2007, 33, 37-48. (d) J. Photochem. Photobiol. A: Chem., 1996,
96, 171-174. (e) Organometallics, 1997, 16, 5724-5729. (f) J. Chem. Soc., Dalton Trans.,
1997, 1019-1023.
2 (a) Inorg. Chem., 2005, 44, 2326-2336. (b) Photochem. Photobiol. Sci., 2007, 6, 454-461. (c)J. Photochem. Photobiol., A: Chem. in press.
3 (a) Inorganic Chemistry 2009, 48, 10138. (b) Chem. Eur. J. 2005, 11, 4219.
(c)Organometallics 2001, 20, 3361. (d) J. Chem. Soc., Chem. Commun. 1994, 367.

4

Correlation of Electronic Structure and Reactivity- The Case of Oxidized
Metal Salens
Tim Storr1* , Yuichi Shimazaki2 , Erik C. Wasinger3 , and T. Daniel P. Stack4
1

Department of Chemistry, Simon Fraser University, Burnaby, BC, V5A-1S6, Canada
College of Science, Ibaraki University, Bunkyo, Mito 310-8512, Japan3
Department of Chemistry and Biochemistry, California State University, Chico, CA, 95929, USA
4
Department of Chemistry, Stanford University, Stanford, CA, 94305, USA
2*Corresponding author, e-mail: tim_storr@sfu.ca
The interplay of redox-active transition metal ions and pro-radical ligands in metalloenzyme sites is
an area of considerable research interest. Galactose oxidase (GOase), a mononuclear copper
enzyme with a Cu(II)-phenoxyl radical active oxidant, is the archetypical example. The simplicityof the single copper active site of the enzyme galactose oxidase[1], which functions by catalyzing
the oxidation of primary alcohols to aldehydes while reducing dioxygen to hydrogen peroxide, has
inspired efforts to develop small molecule mimics capable of mild and selective alcohol oxidation.
To this end, we have investigated the chemistry of a series of simple oxidized bis-phenoxide metal
complexes, which demonstrate that ostensibly small variations of the ligand structure affect thelocus of oxidation. Oxidation of the neutral bis-phenoxide complexes with a variety of one electronoxidants leads to highly coloured oxidized metal complexes in solution; the nature and stability ofthese species has been found to depend on the solvent and counterion present.[2,3] Integration of
information from near infrared spectroscopy, magnetic susceptibility, electrochemistry, resonanceRaman spectroscopy, x-ray crystallography and x-ray absorption spectroscopy provide criticalinsights into the nature of the localization/delocalization of the oxidation locus. An intriguing
example is the one-electron oxidized form of [Cu(II)Sal] (Sal = (rac)- N,N’-bis(3,5-di-tertbutylsalicylidene)cyclohexane-1,2-diamine) that is a Cu(III) species in the solid state, yet exists in aspin equilibrium in solution between the ligand-radical-Cu(II) species and Cu(III) forms,
demonstrating the near isoenergetic nature of these two electronic descriptions. In addition, we haveinvestigated a series of group 10 metal complexes (Ni, Pd, Pt), probing the effect of the metal ion
bridge on the degree of electronic communication between the two redox-active phenolate
ligands.[4] An account of our most recent work with asymmetric ligands, thereby limiting ligand
radical delocalization, will also be described.
[1] Ito, N.; Phillips, S. E. V.; Stevens, C.; Ogel, Z. B.; McPherson, M. J.; Keen, J. N.; Yadav, K. D.
S.; Knowles, P. F. Nature 1991, 350, 87.
[2] Shimazaki, Y.; Tani, F.; Fukui, K.; Naruta, Y.; Yamauchi, O. J. Am. Chem. Soc. 2003, 125,
10512.
[3] Storr, T.; Wasinger, E. C.; Pratt, R. C.; Stack, T. D. P. Angew. Chem. Int. Ed. 2007, 46, 5198.
[4] Shimazaki, Y.; Stack, T. D. P.; Storr, T. Inorg. Chem. 2009, 48, 8383.

5Photoelectrochemical Simulation of Energy Conversion in the
Photosynthetic Primary Processes and Design for Film-type
High-efficiency Dye-sensitized Solar Cells
Tsutomu Miyasaka* and Masashi Ikegami
Graduate School of Engineering, Toin University of Yokohama, 1614 Kurogane-cho,
Aoba, Yokohama, Kanagawa 225-8502, Japan.
*Corresponding author, e-mail: miyasaka@cc.toin.ac.jp
Dye-sensitized solar cell (DSSC) uses environmentally benign materials and low-cost
printing processes. In DSSC, Ru bipyridyl complex dyes, which had been also
employed by M. Calvin’s group to mimic the photosynthetic water splitting reaction, arenow capable of yielding high efficiency in solar energy conversion up to 12%, which
well competes with amorphous Si solar cells. We have been focusing on developing
film-type DSSCs using plastic substrates to realize a leaf-like flexible cell. The
conversion efficiency of 5-7% has been achieved using organic dye sensitizers andmesoporous TiO2 as semiconductor [1]. Fig. 1 shows a plastic DSSC which allows
transmission of red light to activate plant photosynthesis while absorbing green light for
power generation. Many natural dyes also function as good sensitizers to TiO2 and ZnO.
As a metal-free chlorophyll derivative, chlorin-e6, is useful for designing a DSSC
(green color) of 4.4% conversion efficiency, which exhibits an action spectrum ofphotocurrent similar to that of natural photosynthesis (Fig. 2)[2]. Environmentallybenign photovoltaic cells are constructed based on our low-temperature electrodefabrication techniques. Proof-of-concept experiments, including manufacture oflarge-area modules and durability tests, are in progress.
60

4
3

50

1: Chl-e6 alone in water
2: Chl-e6 alone in methanol
3: Chl-e6 & CA in methanol
4: Chl-e6 & DCA in methanol
5: Chl-e6 & CDCA in methanol[ Chl-e6]=0.2 mM[coabsorbent]=60 mM

IPCE %

5

40
30
2

20
10
0
350

1

400

450

500

550

600

650

700

750

800

Wavelength / nm

Fig. 1 Full-plastic DSSC module with a series DC
connection for a high voltage output of 7.2V

Fig. 2 Action spectra of chlorin-e6 sensitized
DSSC. The dye absorption on TiO2 was done withvarious concentrations of co-absorbers (cholic acid,CA). Electrode substrate was FTO-coated glass.

[1] T. Miyasaka, M. Ikegami, Y. Kijitori, J. Electrochem. Soc., 154, A455 (2007).
[2] M. Ikegami, M. Ozeki, Y. Kijitori, T. Miyasaka, Electrochemistry, 76, 140 (2008).

6

DESIGN OF PHOTOELECTROCHEMICAL CELLS FOR THE
SPLITTING OF WATER AND FUEL PRODUCTION
Gary F. Moore,1 Michael Hambourger,1 Smitha Pillai,1 Jesse Bergkamp,1John Tomlin,1 Benjamin Sherman,1 Ernesto Mariño-Ochoa,2 Marcelo
Videa,2 Devens Gust,1 Thomas A. Moore1 and Ana L. Moore11Center for Bioenergy and Photosynthesis, Department of Chemistry andBiochemistry, Arizona State University, Tempe, AZ, USA 85287-1604; 2Department ofChemistry, Tecnológico de Monterrey, Campus Monterrey, Monterrey, N.L., México 64849
The long-term objective of our research is the design of bioinspired schemes that couple
solar energy conversion to the oxidation of water and the subsequent use of the reducing
equivalents to synthesize energy-rich compounds, such as hydrogen or fuels based on
reduced carbon. In order to establish the design principles for a tandem, two junction (orthreshold) photocell, we are assembling Grätzel-type photoelectrodes that model
photosystems I and II (PSI and PSII). The photoanode model of PSII will contain a mimic ofthe 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 abenzimidazole-phenol pair (BiP) that mimics the TyrZ-His190 pair in PSII. Electrochemical
studies show that the phenoxyl radical/phenol couple of the model system is chemicallyreversible with a midpoint potential of 1.24 V vs. NHE and is therefore thermodynamicallycapable 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 theporphyrin (BiPPF10•+-TiO2•–) or the phenol (BiP•+-PF10-TiO2•–). EPR provides a clear
spectroscopic picture of these processes.1
The photoelectrode model of PSI will be sensitized by low potential naphthalocyanines orphthalocyanines, 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 to effectively drive the reduction of protons tohydrogen at a cathode. The semiconductor will be electrically wired to a cathode suitable forhydrogen production: either a metal electrode (Pt or Ni) or a hydrogenase-modified carbon
electrode. Cyclic voltammetric studies of Clostridium acetobutylicum [FeFe]-hydrogenase(HydA) films on carbon electrodes demonstrate cathodic proton reduction and anodichydrogen oxidation. The high surface area carbon felt/hydrogenase electrode shows
promising properties as the cathode of the photoelectrode mimic of PSI.2
This arrangement of two photosystems operating in tandem has the potential of being much
more efficient than natural photosynthesis because the artificial PSI and PSII, in contrast to
their natural counterparts, do not compete for the same region of the solar spectrum.
1. Moore, G. F. et al. J. Am. Chem. Soc. 2008, 130, 10466–10467.
2. Hambourger M. et al. J. Am. Chem. Soc. 2008, 130, 2015–202

7Structure around Oxygen-Evolving Mn4OxCa-Clusterof Photosystem II Complex from Thermosynechococcus
vulcanus
Nobuo Kamiya, Graduate School of Science, Osaka City University,
Osaka 558-8585, Japan. E-mail: nkamiya@sci.osaka-cu.ac.jp
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 thelife on the earth. The components of PSII from cyanobacteria include 17
membrane-spanning subunits, 3 hydrophilic, peripheral subunits, and over 90 cofactors
such as chlorophylls, Mn, Ca, Cl, Fe, plastoquinones, carotenoids, and lipids, which giverise to a total molecular mass of 350 kDa for a monomer. The structure of PSII has beenreported at 3.8-2.9 Å resolution by X-ray crystallographic analyses of PSII isolated fromtwo thermophilic cyanobacteria, Thermosynechococcus elongatus and T. vulcanus. In
the structural model of PSII from T. elongates most recently reported by Zouni andSaenger’s group in Berlin [1], the locations of all 20 subunits and 96 cofactors wereidentified. One of the cofactors is a chloride anion (Cl-), known to be essential foroxygen evolution of PSII and closely associated with the Mn4OxCa-cluster. The anion
locates in one of the channels proposed for the transport of protons. However, thestructure of Mn4OxCa-cluster itself is still unclear because the resolution of 2.9 Å isinsufficient to resolve the positions of Mn, Ca, and oxygen atoms independently, andbecause the cluster is highly sensitive to X-ray radiations so that the intact cluster
structure is easily destroyed as shown by the technique of Extended X-ray Absorption
Fine Structure. In order to overcome the X-ray damage problem of PSII crystals, adamage reducing protocol was adopted at the SPring-8 beamlines for the diffraction
intensity measurements using relatively large PSII crystals. Discussions will be given
from this point of view. Another point of our presentation will be on the number ofCl--binding site. We substituted Cl- with Br- or I- in the crystals of PSII from T.
vulcanus, and analyzed the crystal structures [2]. The results clearly showed that there
exist two anion-binding sites in one monomer of PSII, instead of one site as reported by
the Berlin group.
The two sites were located in positions surrounding the
Mn4OxCa-cluster at equal distances to the metal cluster. Possible function of the second
binding site will be discussed.
[1] Guskov, A., Kern, J., Gabdulkhakov, A., Broser, M., Zouni, A., Saenger, W., Nat.
Struct. Mol. Biol. 16(3) 334 (2009).
[2] Kawakami, K., Umena, U., Kamiya, N., Shen. J.-R., PNAS, 106, 8567 (2009).

8

Manganese-Polyoxometalate Architectures: Towards Water Oxidation
Catalysts Inspired by Photosystem II
Leroy Cronin1*, Richard J. Cogdell2
1
WestCHEM, Dept. of Chemistry, and 2Glasgow Biomedical Research Centre,
Institute of Biomedical and Life Sciences,
University of Glasgow, Glasgow, Scotland 8QQ,Corresponding Author Email: L.Cronin@chem.gla.ac.uk; Web: http://www.croninlab.com
Photo conversion of water provides a route leading to reducing equivalents of NADPH byphotosynthetic organisms and this is an extremely efficient process in which molecular oxygen is
generated as a by-product. The first stages of the process take place in the WOC (water-oxidisingcomplex) present in photosystem II. At the heart of this complex is an inorganic cofactor; acubane comprising three manganese centres and a calcium centre connected by oxo, or oxoderived bridges. It is at this site where the oxidation of water is thought to occur via four proton
coupled electron transfer events in this redox-active cubane. Although a number of catalytically
active coordination model compounds have been synthesised, their absolute activity, stability,
and turn over can be limited due to the stability of the organic groups associated with the cluster.
Here we present an approach to substitute the organic directing ligands by a more robust
polyoxometalate clusters.1 Polyoxometalates aremolecular metal oxides based upon a variety ofmetals (either W, Mo, V, Nb) and representinteresting candidates not only to their stability,
but also due to their tunable redox potentials andability to take part in multiple electron transfer
processes. In our recent work we have shown thatmanganese substituted POMs display a fantastic
variety of architectures, and one very important
cluster recently revealed by us, has both interesting
electrochemical and magnetic properties,2 see
Figure 1.
Figure 1. The POM-Mn cluster: {[XW9O34]2[MnIII4MnII2O4(H2O)4]}12-. Colour scheme: purple
polyhedra: WO6; orange spheres: Mn; green spheres: X (Si or Ge), red spheres: oxygen.
In this talk I will explain the background behind molecular metal oxide clusters(Polyoxometalates), their architecture,3 and their physical properties and postulate some new
directions that could allow the assembly and fabrication of new catalyst-devices that could
oxidise water.
References
1. D–L. Long, E. Burkholder, L. Cronin, Chem. Soc. Rev., 2007, 36, 105;
2. C. Ritchie, A. Ferguson, H. Nojiri, H. N. Miras, Y.-F. Song, D.-L. Long, E. Burkholder, M.
Murrie, P. Kögerler, E. K. Brechin, and L. Cronin, Angew. Chem. Int. Ed., 2008, 47, 5609.
3.H. N. Miras, G. J. T. Cooper, D.-L. Long, , H. Bögge. A. Müller, C. Streb, L. Cronin, Science
2010, 327, 72.

9Green Oxidation Catalysts
Terry J. Collins,3 Colin P. Horwitz,3 Laura G. Raymond,1 Hayden J.
Smith,1 Trevor R. Stuthridge,2 and L. James Wright1*
1

Dpt of Chemistry, University of Auckland, Auckland, New Zealand.
Forest Research Limited, Private Bag 3020, Rotorua, New Zealand.
3
Carnegie Mellon University, 4400 Fifth Av, Pittsburgh, PA 15213, USA.
2*

Corresponding author, e-mail: lj.wright@auckland.ac.nz

Oxidation chemistry plays a central role in many large industrial processes. In situations
where chlorine-based oxidants are used in conjunction with organic compounds the formationof potentially harmful organo-chlorine compounds is often an inevitable side reaction.
Inexpensive, alternative oxidants that do not pose this problem include oxygen and hydrogen
peroxide, and accordingly these are often referred to as “green oxidants”. However, reactions
under mild conditions with these reagents are usually very slow and indiscriminate. There is
therefore an important need to develop suitable catalysts that will improve the efficiency andeffectiveness of these oxidants. Prof. Collins and his group have developed a class of ironcomplexes known as TAMLs® that catalyse oxidations with hydrogen peroxide [1]. These
catalysts are water soluble and are highly
O H2O
effective at very low concentrations. In
Ocollaboration with Prof. Collins we have studied®
NN
the possibility of using the TAML /hydrogenFeperoxide oxidation system to replace the use ofNN
chlorine-based bleaches in the pulp and paperO
industry and also as a remediation treatment forO
waste-water streams [2]. An important aspect ofIron TAML® complex
the tetra-amido macrocyclic ligands that are at
the heart of the TAML® catalysts is that they are amenable to chemical modification. In
collaboration with Prof. Collins we have explored a number of these modifications and haverecently developed a new type of TAML® complex that has quite different but
complimentary properties to the original class of TAMLs®. In this lecture the use of
TAML®/hydrogen peroxide as a green oxidation system will be discussed and our new
developments in the synthesis and study of modified TAMLs® will be presented.
[1] T. J. Collins, Acc. Chem. Res. 2002, 35, 782-790[2] T. J. Collins, J. A. Hall, L. D. Vuocolo, N. L. Fattaleh, I. Suckling, C. P. Horwitz, S. W.
Gordon-Wylie, R. W. Allison, T. J. Fullerton, L. J. Wright. “The activation of hydrogen
peroxide for selective, efficient wood pulp bleaching in “Green Chemistry: Challenging
Perspectives” P. Tundo, ed., Oxford University Press, Oxford, pp 79-105, 2000.

10

New Platforms for Probing Early Transition Metal Trends for
Bimetallic Dinitrogen Activation and N≡N Bond Cleavage
Masakazu Hirotsu, Philip P. Fontaine, Brendan Yonke andLawrence R. Sita*
Department of Chemistry and Biochemistry
University of Maryland, College Park, MD 20742*Corresponding author, email: lsita@umd.edu
At the heart of potential solutions to many existing and future problems associated withexpansion of the global population by an estimated 3 to 4 billion additional people over the
next 50 yrs are scientific breakthroughs that must be made in the near term to increase the‘clean technology’ quotient of many industrial chemical processes that can simultaneously
reduce energy and environmental requirements and consequences. In this respect, the current
energy and environmental costs for existing nitrogen-based fertilizer production employing
the Haber-Bosch (HB) process, which converts dinitrogen to ammonia through directhydrogenation over iron-based catalysts at high temperature and pressure, are quite high,even if presently unavoidable.
Toward the goal of developing more energy-efficient processes involving transition metalmediated N2 activation, N≡N cleavage, and N-atom functionalization processes, we initiateda program to systematically investigate the roles played by formal metal oxidation state anddn electron count across several different ligand-centered iso-structural (LCIS) series ofbimetallic [LnM]2(μ-N2) complexes for the group 4 - 6 metals in which the mode of N2
coordination and extent of activation might vary, but for which the steric and electronic
features of the ligand sphere remain invariant [1,2] This talk will focus on recent results
obtained to date for two new families of supporting transition metal ligand environments,
monocyclopentadienyl, amidinate (X = Me) (CpAm) and monocyclopentadienyl, guanidinate(X = NMe2) (CpGu), that appear to be ideally suited for achieving this goal.
R
R
R' R
N
N
M
N
or
R' N M N
R' N M
φ N X
N
N
R'
R'
R'
X
X
M = Ti, Zr, Hf, Ta, Mo, and W
X = Me or NMe2

[1]
[2]

R'

X
N
N
M
R'

N
R

M. Hirotsu, P. P. Fontaine, P. Y. Zavalij, L. R. Sita, J. Am. Chem. Soc. 2007, 129,
12690-12692.
M. Hirotsu, P. P. Fontaine, A. Epshteyn, P. Y. Zavalij, L. R. Sita, J. Am. Chem. Soc.
2007, 129, 9284-9285.

11

.
.

Titles of Poster Presentations
Studies on Spin-controlled Electron Transfer System Based on
Platinum Complex as Triplet Photosensitizer

1

Shuichi Suzuki1, Ryoji Sugimura1, Masatoshi Kozaki1, Kazutoshi
Keyaki2, Koichi Nozaki2, Noriaki Ikeda3, Kimio Akiyama4 and Keiji
Okada1
1. Graduate School of Science, Osaka City University
2. University of Toyama
3. Kyoto Institute of Technology
4. Tohoku University

Unprecedented Reactions of Fe and Ni Complexes Supportedby Tris(2-pyridylthio)methyl Ligand

2

Naoto Kuwamura1, Ryo Kato1, Ken'ichi Kitano1, Masakazu Hirotsu1,
Takanori Nishioka1, Hideki Hashimoto2 and Isamu Kinoshita1
1. Department of Material Science, Graduate School of Science,
Osaka City University
2. CREST-JST and Graduate School of Science, Osaka City
University

Three-photon
Photocycloreversion
andTwo-photon
photocyclodimerization of Anthracene Photodimers andBiplanemer in Solution by Intense Femtosecond Laser Pulses
Tomoyuki Yatsuhashi1,2, Yuki Nakahagi1, Hideki Okamoto3 and Nobuaki
Nakashima1
1. Department of Chemistry, Graduate School of Science, Osaka
City University
2. PRESTO, Japan Science and Technology Agency
3. Department of Chemistry, Graduate School of Natural Scienceand Technology, Okayama University

3

Stepwise Synthesis of Multinuclear Dinitrogen Complexes
Using Bridging Thiolato Ligands

4

Ryoichi Takada, Masakazu Hirotsu, Takanori Nishioka and Isamu
Kinoshita
Department of Material Science, Graduate School of Science, Osaka
City University

Squaric Acid as a New Tool for Peptide Chemistry5

Tetsuro Shinada, Toshikazu Ishida, Yuuichi Kiniwa and Yasufumi
OhfuneGraduate School of Science, Osaka City University

Structure Determination of A New Juvenile Hormone from A
Heteropteran Insect

6

Kanako Kaihara, Tetsuro Shinada, Yasufumi Ohfune, Hideharu Numata,and Toyomi Kotaki
Graduate School of Science, Osaka City University

Studies on Efficient Synthesis of Kainoids

7

Kentaro Oe, Tetsuro Shinada and Yasufumi Ohfune
Graduate School of Science, Osaka City University

Total Synthesis of (-)-Funebrine using Au-catalyzed Cyclizationof Allenylsilane

8

Takuya Okada, Kazuhiko Sakaguchi and Yasufumi Ohfune
Graduate School of Science, Osaka City University

Artificial light-harvesting antennas prepared by metal
complexes with synthetic 3-substituted chlorophylls
Yusuke Kinoshita, Youhei Yamamoto and Hitoshi Tamiaki
Department of Bioscience and Biotechnology, Faculty of Science andEngineering, Ritsumeikan University

9Stimulated photon-echo measurements of β-carotene

10

Mitsuru Sugisaki, Daisuke Kosumi, Keisuke Saito and Hideki
Hashimoto
CREST-JST and Graduate School of Science, Osaka City University

Photocarrier Dynamics of The P3HT/PCBM Composite
Photovoltaic Device as Revealed by Bleaching Spectroscopy

11

Katsuichi Kanemoto2, Akihiko Ogata1, Daisuke Kosumi2 and Hideki
Hashimoto2
1. Department of Physics, Osaka City University
2. CREST-JST and Graduate School of Science, Osaka City
University

Femtosecond transient absorption spectroscopic study on apolar carotenoid analogue, 2-(all-trans-retinylidene)
indan-1,3-dione

12

Toshiyuki Kusumoto1, Daisuke Kosumi1, Chiasa Uragami2, Harry A.
Frank3, Robert R. Birge3, Richard J. Cogdell4 and Hideki Hashimoto1
1. CREST-JST and Graduate School of Science, Osaka City
University
2. Department of Physics, Osaka City University
3. Department of Chemistry, University of Connecticut, USA
4. Glasgow Biomedical Research Centre, University of Glasgow, UK

Synthesis and Properties of Cyclic Porphyrin array witholigo-phenylene-ethynylene backbones

13

Masatoshi Kozaki, Atsuhiro Uetomo, Shuichi Suzuki and Keiji Okada
Graduate School of Science, Osaka City University

Synthesis of pyrazole-fused quinoxalines and evaluation of theirspectroscopic properties in the presence of gold nanoparticles
Yuriko Matsumura and Takayuki Onodera
Department of Materials and Life Science, Faculty of Science andTechnology, Seikei University

14

Phototoxicity and Biological Activity of S-glucosylatedFluorochlorin in Ovarian Cancer

15

Yuki Yoshida1, Hiromi Ohi2, Masami Naemura1, Kazuhiro Moriwaki3,
Ryoto Tsujii3, Haruo Akashi3, Takashi Shibahara3, Hiroko Endo4,
Masahiro Inoue4, Akio Toshimitsu1 and Shigenobu Yano2
1. Graduate School of Engineering, Kyoto University
2. Innovative Collaboration Center, Kyoto University
3. Graduate School of Science, Okayama University of Science4. Osaka Medical Center for Cancer and Cardiovascular Diseases

Ultrafast Intramolecular Charge Transfer Dynamics in Polar
Carotenoid

16

Daisuke Kosumi1, Toshiyuki Kusumoto1, Ritsuko Fujii1, Mitsuru
Sugisaki1, Masahiko Iha2 and Hideki Hashimoto1
1. CREST-JST and Graduate School of Science, Osaka City
University
2. South Product Ltd.

Diastereoselective synthesis of "sugar-coated" NHC Ir(III) andRh(III) complexes

17

Teppei Shibata, Takanori Nishioka, and Isamu Kinoshita
Division of Molecular Materials Science, Graduate School of
Science, Osaka City University

Syntheses and photodynamic activities of sugar linked In
porphyrins as a dual drug of diagnostic imaging andphotodynamic therapy
Misaki Nakai1, Tomohiro Maeda1, Shigenobu Yano2, Shiho Sakuma3,
Eiko Ohtake3, Akira Maeda3, Akimichi Morita3 and Yasuo Nakabayashi1
1. Kansai University
2. Kyoto University
3. Nagoya City University

18

Application of Resonance Raman Micsroscopy to in vivo
carotenoid

19

Chiasa Uragami1, Eiji Yamashita2, Andrew Gall3, Bruno Robert3 andHideki Hashimoto4
1. Department of Physics, Osaka City University
2. Fuji Chemical Industry Co. Ltd., Japan
3. CEA-Saclay, France
4. CREST-JST and Graduate School of Science, Osaka City
University

Stark spectroscopy of spirilloxanthin bound to LH1 isolated
from purple photosynthetic bacteria

20

Tomoko Horibe1, Katsunori Nakagawa2, Toshiyuki Kusumoto1,
Ritsuko Fujii1, Richard J. Cogdell3, Mamoru Nango2 and Hideki
Hashimoto1
1. CREST-JST and Graduate School of Science, Osaka City
University
2. CREST-JST and Department of Life Science and Materials,
Nagoya Institute of Technology
3. Glasgow Biomedical Research Centre, University of Glasgow

In situ observation of reconstituted photosynthetic membrane
by using atomic force microscopy

21

Yuko Sugai1, Ritsuko Fujii1, Mamoru Nango2 and Hideki Hashimoto1
1. CREST-JST and Graduate School of Science, Osaka City
University
2. CREST-JST and Department of Life Science and Materials,
Nagoya Institute of Technology

Synthesis and Characterization of Amino Sugar Linked
Cisplatin Type Pt(II) and Pd(II) Complexes
Hiromi Ohi, Akio Toshimitsu and Shigenobu Yano
Innovative Collaboration Center, Kyoto University

22Light-Induced Transmembrane Electron Transfer Catalyzed
byPhospholipid-Linked Zn Chlorophyll Derivatives on ITO
Electrodes

23

Masaharu Kondo1, Yoshito Takeuchi1, Hongmei Li1, Osamu Goto1,
Shingo Ito1, Shuichi Ishigure1, Kotaro Kuzuya1, Mizuki Amano1,
Takehisa Dewa1, Hideki Hashimoto2,3 and Mamoru Nango1,3
1. Graduate School of Engineering, Nagoya Institute of Technology
2. Graduate school of Science, Osaka City University
3. CREST/JST

Reconstitution of the photosynthetic light harvesting model
polypeptides / pigments complexes

24

Shunsuke Sakai1, Katsunori Nakagawa1,4, Ayano Nakashima1, Kouji
Iida2, Hideki Hashimoto3,4, Ritsuko Fujii3, Toshihisa Mizuno1, Toshiki
Tanaka1, Takehisa Dewa1 and Mamoru Nango1,4
1. Graduate School of Engineering, Nagoya Institute of Technology
2. Nagoya Municipal Industrial Research Institute3. Graduate school of Science, Osaka City University
4. CREST/JST

Synthetic Study of 5',6'-Dihydroanhydrorhodovibrin

25

Takeshi Yamada1, Keiji Okada2, Yasufumi Ohfune1, Tetsuro Shinada1
and Hideki Hashimoto2
1. Graduate School of Schience, Osaka City University
2. CREST-JST and Graduate School of Science, Osaka City
University

Pigment Composition and Optical Properties of the Major
Light-Harvesting Complexes from an Edible Brown Alga,“OKINAWA MOZUKU”
Ritsuko Fujii1, Mamiko Kita1, Masahiko Iha2 and Hideki Hashimoto1
1. CREST-JST and Graduate School of Science, Osaka City
University
2. South Product Ltd., OKINAWA, JAPAN26

Construction and observation using AFM of an artificial lipid
bilayer containing photosynthetic membrane proteins
Ayumi Sumino1, Nobuaki Sakaki1, Natsuko Watanabe1, Takehisa
Dewa1,2, Hideki Hashimoto3,4, Alastair T. Gardiner5, Richard J. Cogdell5
and Mamoru Nango1,4
1. Nagoya Institute of Technology
2. JST/PRESTO
3. Osaka City University
4. JST/CREST
5. University of Glasgow

27