Microsoft Word - .docTime Dec. 13th (Thursday)
15:30-19:00 Registration and Check-in at the Lakeshore hotel for all speakers
Reception Hosts Professor Yu-Tai Tao, Sue-Lein Wang and Chien-Tien Chen
19:40-21:40 Reception at the Lakeshore hotel
2
Time Dec. 14th (Friday) 08:00-08:40 Registration 08:45-09:00 Opening Remarks
Chair person
10:00-10:20 Coffee Break Chair person Chia-Chun Chen (OFET-A) Chien-Tien Chen
(Cat-B)
10:20-11:00 IL-01: John E. Anthony (USA) IL-02: Shu Kobayashi (Tokyo, Japan)
11:00-11:20 IL-03: Jye-Shane Yang (NTU) IL-04: Bor-Cherng Hong (NCCU) 11:20-11:40 IL-05: Chen-Sheng Yeh (NCKU) IL-06: Ming-Chang P. Yeh (NTNU)
11:40-12:20 IL-07: Hwan Kyu Kim (S. Korea) IL-08: Hiroaki Sasai (Osaka, Japan)
12:20-14:00 Lunch
Chair person
Wen-Feng Liaw (NTHU) (Cat-D)
15:00-15:20 IL-13: Hsiu-Fu Hsu (TKU) IL-14: Yun-Ming Wang (KMU) 15:20-15:40 Coffee Break
Chair person
15:40-16:20 IL-15: Y. Yamamoto (Tohoku, Japan) IL-16: Julie Kovacs (USA)
16:20-17:00 IL-17: Shie-Ming Peng (NTU) IL-18: Kuo-Chu Hwang (NTHU)
17:00-17:20 Coffee Break Chair person
Sue-Lein Wang (NTHU) (OE)
3
Time Dec. 15th (Saturday)
10:00-10:20 Coffee Break Chair person
Chi-Huay wong (President of AS) (OLED-E)
10:20-11:20 KL-03: Alan Heeger (Nobel Laureate, (USA)
Chair person
Yun Chi (NTHU) (OE-C)
Leung, Man-Kit (NTU) (OE-C)
11:20-12:00 IL-19: Sang Ook Kang (S. Korea) IL20: Leonard V. Interrante (USA)
12:00-12:20 IL-21: Hong-Ping Lin (NCKU) IL22: Jiann-Tsuen Lin (AS) 12:20-12:30 Group photos for all ICCT chairpersons and speakers
12:30-14:00 Lunch and Poster
14:00-14:40 IL-23: M. G. Finn (USA) IL-24: Carsten Bolm (Germany)
14:40-15:00 IL-25: Kuang-Lieh Lu (AS) IL-26: Chu-Chieh Lin (NCHU)
15:00-15:20 IL-27: Chun-Hsien Chen (NTU) IL-28: Chien-Tien Chen (NTNU) 15:20-15:40 Coffee Break
Chair person
15:40-16:20 IL-29: Alex K.-Y. Jen (USA) IL-30: Li Deng (USA)
16:20-17:00 IL-31: Kuei-Hsien Chen (NTU) IL-32: Takeo Kawabata (Kyoto, Japan)
17:00-17:20 Coffee Break Chair person
I-Jy Chang (NTNU) (Cat-D)
19:00-21:00 Dinner (Hotel Royal Hsinchu)
4
Time Dec. 16th (Sunday) Chair person
Yu-Tai Tao (AS) (Nano-B1)
Kwang-Hwa Lii (NCU) (Nano-B2)
10:20-11:00 IL-33: Wai-Yeung Wong (Hong Kong) IL-34: Gion Calzaferri (Switzerland)
11:00-11:20 IL-35: Chin-Ti Chen (AS) IL-36: Chun-Guey Wu (NCU)
11:20-11:40 IL-37: Ken-Tsung Wong (NTU) IL-38: Chao-Ping Hsu (AS)
11:40-12:20 IL-39: Soo Young Park (S. Korea) IL-40: Hicham Fenniri (Canada)
12:20-14:00 Lunch and Poster Chair person
Chung-Yuan Mou (NTU) (OLED-E)
Wei-Hsiu Hung (NTNU) (Nano-B2)
14:00-14:40 IL-41: Carlo A. Bignozzi (Italy) IL-42: Guillermo Bazan (USA)
14:40-15:20 IL-43: Kung-Hwa Wei (NCTU) IL-44: Pi-Tai Chou (NTU)
15:20-15:40 Coffee Break Chair person
Yuan-Pern Lee (NCTU) (OE-C)
Chun-Hung Lin (AS) (Nano-B2)
16:20-16:40 IL-47: Eric Wei-Guang Diau (NCTU) IL-48: Chun-Cheng Lin (NTHU) 16:40-17:00 IL-49: Juen-Kai Wang (NTU) IL-50: Jim-Min Fang (NTU)
17:00-17:10 Coffee Break
17:10-17:20 Closing Remarks
Annual Chinese Chemical Society & ICCT 2007 Joint Conference Time
Dec. 14thFriday
08:45- 09:00
Auditorium Oepning Remarks By President Wen-Tsuen Chen (National Tsing Hua University)
09:00- 10:00
Auditorium OE-CC Chain-Shu Hsu (National Chiao Tung University) Ben L. Feringa Holland Moving at the Nanoscale: Molecular Switches and Motors
10:00- 10:20
Coffee Break
10:20- 11:00
11:00- 11:20
() Jye-Shane Yang (National Taiwan University) The Meta vs Para Conjugation Effects on the Electronic Properties of π-Conjugated Systems
11:20- 11:40
11:40- 12:20
OFET-A () Chia-Chun Chen (National Taiwan Normal University
Hwan Kyu Kim (S. Korea) Lanthanide(III)-Cored Dendrimer Complexes: New Design Criteria and Unusual Photophysical Investigations
10:20- 11:00
11:00- 11:20
11:20- 11:40
() Ming-Chang P. Yeh (National Taiwan Normal University) Intramolecular Addition of Conjugated Dienes to Alkynes Catalyzed by Platinum and Gold
11:40- 12:20
International Conference Hall Cat-B B () Chien-Tien Chen (National Taiwan Normal University)
Hiroaki Sasai (Japan) Novel Enantioselective Reactions Promoted by Pd(II)-SPRIX Catalyst
12:20- 14:00
2-3 Food CourtShui Mu Student Center2-3F,Feng Yun Building
Lunch
14:00- 14:40
14:40- 15:00
() Hong-Cheu Lin (National Chiao Tung University) Applications of Supramolecular Structures in LC and Light- Emitting Materials
15:00- 15:20
Zyxel Auditorium
OFET-A and LC - A () Ru-Shi Liu (National Taiwan University)
() Hsiu-Fu Hsu (Tamkang University) Maneuver of Long-Range Molecular Order by Liquid Crystal Engineering
14:00- 14:40
14:40- 15:00
() Chen-Hsiung Hung (Academia Sinica) Chemistry of Nitrogen Oxides Probed by N-Confused Porphyrin Iron Complex
15:00- 15:20
International Conference Hall Cat-D -D () Wen-Feng Liaw (National Tsing Hua University) ()
Yun-Ming Wang (Kaohsiung Medical University) The novel bio-activated and targeted contrast agents for MRI
15:20- 15:40
15:40- 16:20
Y. Yamamoto (Japan) Top 5 Program (WPI) in Japan and Evaluation of Research Accomplishments.
16:20- 17:00
Zyxel Auditorium OE-C C () I-Jy Chang (National Taiwan Normal University)
() Shie-Ming Peng (National Taiwan University) Molecular Metal Wires and Molecular Switches
15:40- 16:20
Julie Kovacs (USA) Understanding How the Thiolate Contributes to the Function of the Non-Heme Iron Enzyme Superoxide Reductase
16:20- 17:00
International Conference Hall Cat-D -D () Chien-Chung Cheng (National Chiayi University)
() Kuo-Chu Hwang (National Tsing Hua University) Cooperative Catalysis in the Catalytic Subunits of Xanthine Oxidase
17:00- 17:20
17:20- 18:20
Auditorium OE () Sue-Lein Wang (National Tsing Hua University) Gérard Férey (France) Hybrid Porous solids: A New World
18:20- 21:00
7

09:00- 10:00
Chinese Chemical Society Member Meeting And Poster Session 10:00- 10:20
Coffee Break
Chi-Huey Wong (President of Academia Sinica) Alan Heeger ( )
(Nobel Laureate, USA; Department of Physics, Department of Materials, University of California at Santa Barbara, California)
Low Cost Plastic Solar Cells: Progress & Prospects
11:20- 12:00
Sang Ook Kang (S. Korea) Enhanced Charge Carrier Mobility Derived from Cyclization of a Silene Unit on Silole Derivatives: Syntheses, Photophysical Properties and Device Fabrication of Spiro- Siloles
12:00- 12:20
Hong-Ping Lin (National Cheng Kung University) Synthesis and Applications of Mesoporous Carbon
11:20- 12:00
Leonard V. Interrante (USA) Polycarbosilanes as Ceramic Precursors and Low-k Dielectric Materials
12:00- 12:20
Man-Kit Leung (National Taiwan University)
()
Jiann-Tsuen Lin (Academia Sinica) Materials Capable of Ambipolar Transport for OLEDs
12:20- 12:30
Group photos for all ICCT chairpersons and speakers
12:30- 14:00
Lunch and Poster 14:00-
14:40-
15:00
15:00-

Ming- Chang Yeh
8
15:20 Measurements of Single Molecular Conductance by STM Break Junction
14:00-
14:40
Ring-Opening Polymerization of Lactides and Related Cyclic Esters Initiated by Metal Alkoxides
15:00-
15:20

()
Jwu-Ting Chen
Chien-Tien Chen (National Taiwan Normal University)
Directed Evolution of Chiral Vanadyl(V) Complexes into C4- Symmetric Pentanuclear Clusters by Exclusive Recognition of Potassium Vanadate from Aqueous Solution: New Aspects in Asymmetric Catalysis
15:20- 15:40
16:20- 17:00
Chin-Ti Chen (Academia Sinica)
Label-free Dual Sensing of DNA Molecules Using DNA
Nanowires
15:40-
16:20
Alkaloids
16:20-
17:00

Shiuh-Tzung Liu
17:00- 17:20
I-Jy Chang (National Taiwan Normal University) John H. Dawson (USA) Mechanistic Studies of Oxidative Halophenol Dehalogenation by Heme-Containing Peroxidases
19:00- 21:00
9

Time
Yu-Tai Tao (Academia Sinica)
Eiichi Nakamura (Japan) Imaging of Single Organic Molecules in Motion
10:00- 10:20

Coffee Break
10:20- 11:00
11:00- 11:20
()
11:20- 11:40
()
11:40- 12:20
()
Soo Young Park (S.Korea) Luminescent Molecular Materials: Enhanced Emission, Excited-state Prototropy, Inter-ligand Energy Transfer, and Luminescence Switching
10:20- 11::00
Gion Calzaferri (Switzerland) Mimicking the antenna system of green plants
11:00- 11:20
()
11:20- 11:40
()
Chao-Ping Hsu (Academia Sinica) Electronic coupling in ground and excited state molecules
11:40- 12:20
()
Hicham Fenniri (Canada) Thermoreversible Supramolecular Homochirality from an Achiral Pool
12:20- 14:00
2-3 Food CourtShui Mu Student Center2-3F,Feng Yun Building
Lunch and Poster
International Conference Hall OLED-E - E
Carlo A. Bignozzi (Italy) Dye Engineering and Electron Mediators for Dye Sensitized Solar Cells
10
() Kung-Hwa Wei (National Chiao Tung University) Nanopatricles Enhanced Polymer Light Emitting Diode
14:00- 14:40
14:40- 15:20
CB2
() Pi-Tai Chou (National Taiwan University) En Route to the Molecules/Nanomaterials of Highly Efficient Emission
15:20- 15:40
16:20- 16:40
() Eric Wei-Guang Diau (National Chiao Tung University) Fabrication and Characterization of Dye/TiO2 Nanostructural
Thin Films for DSSC Applications
16:40- 17:00
() Yuan-Pern Lee (National Chiao Tung University)
() Juen-Kai Wang (National Taiwan University) Some Progresses of Our Studies in Surface-Enhanced Raman
Scattering
16:20- 16:40
() Chun-Cheng Lin (National Tsing Hua University) Application of Functionalized Nanoparticle in Protein Isolation, Detection and Targeting
16:40- 17:00
International Conference Hall NANO-B2 -B2 () Chun-Hung Lin (Academia Sinica)
() Jim-Min Fang (National Taiwan University) Conjugation of Carbohydrate Molecules for Glycobiology: Carbohydrate Modified Quantum Dots and Direct Amide Bond Linkage
17:00- 17:10
Closing Remarks
Keynote Lecturers
Prof. Ben L. Feringa Distinguished Jacobus van ‘t Hoff Professor of Molecular Sciences
Stratingh Institute for Chemistry, University of Groningen; Groningen, The Netherlands " Moving at the Nanoscale: Molecular Switches and Motors"
Prof. Gérard Férey
Prof. Alan Heeger
Physics Department, University of California, Santa Barbara, CA, USA “Low Cost Plastic Solar Cells: Progress & Prospects”
Prof. John H. Dawson
Carolina Distinguished Professor, Director of Graduate Studies in Chemistry Department of Chemistry and Biochemistry Information
University of South Carolina, Columbia, SC, USA “Mechanistic Studies of Oxidative Halophenol Dehalogenation by Heme-Containing
Peroxidases”
Prof. Eiichi Nakamura Department of Chemistry, School of Science, The University of Tokyo, Japan
“Imaging of Single Organic Molecules in Motion”
12
Invited Lecturers OFET-A
Prof. John E. Anthony Department of Chemistry, University of Kentucky, USA
“Small-molecule design for organic electronics”
Prof. Hwan Kyu Kim Center for Smart Light-Harvesting Materials, & Department of Polymer Science & Engineering
Hannam Universit, Daejon 306-791, Korea “Lanthanide(III)-Cored Dendrimer Complexes: New Design Criteria and Unusual
Photophysical Investigations”
Prof. Yoshiro Yamashita Tokyo Institute of Technology; Department of Electronic Chemistry Interdisciplinary Graduate School of Science and Engineering, Japan
“Molecular design of organic semiconductors for high-performance n-type field-effect transistors”
Professor Y. Yamamoto Department of Chemistry, Graduate School of Science, Tohoku University
Editor of Tetrahedron Letters (Elsevier) “Imaging of Single Organic Molecules in Motion”
Jye-Shane Yang Dept. of Chemistry, National Taiwan University
“The Meta vs Para Conjugation Effects on the Electronic Properties of π−Conjugated Systems”
Chen-Sheng Yeh Department of Chemistry, National Cheng-Kung University “Bio-nanomaterials show in vitro and in vivo potential”
OFET-A and LC
Lin, Hong-Cheu Dept. of Materials Science and Engineering, National Chiao Tung University
13
Cat-B
Prof. Shu Kobayashi Department of Chemistry, School of Science, The University of Tokyo, Japan
“Novel Catalysts for Green Sustainable Chemistry”
Prof. Hiroaki Sasai The Institute of Scientific and Industrial Research (ISIR), Osaka University, Japan
“Novel Enantioselective Reactions Promoted by Pd(II)-SPRIX Catalyst”
Prof. M. G. Finn Department of Chemistry and the Skaggs Institute for Chemical Biology
The Scripps Research Institute, CA, 92037, USA “Playing with Fire: the Mechanism of Copper-Catalyzed Azide-Alkyne Cycloaddition”
Prof. Carsten Bolm
Prof. Li Deng
Chemistry Department, Brandeis University, MS 015, 415 South Street, Waltham, MA 02454, USA
“Cooprative Hydrogen-Bonding Catalysis With Cinchona Alkaloids”
Prof. Takeo Kawabata Institute for Chemical Research, Kyoto University; Uji, Kyoto, Japan
“Fine Molecular Transformation by Nucleophilic Catalysis”
Bor-Cherng Hong
Hsiu-Fu Hsu Department of Chemistry, Tamg-Kang University
“Maneuver of Long-Range Molecular Order by Liquid Crystal Engineering”
14
Ming-Chang P. Yeh
Gold”
Cat-D
“Molecdular Design of Organometalloenzymes”
Prof. Julia Kovacs Department of Chemistry, University of Washington, USA
“Understanding How the Thiolate Contributes to the Function of the Non-Heme Iron Enzyme Superoxide Reductase”
Chen-Hsiung Hung
Institute of Chemistry, Academia Sinica “Chemistry of Nitrogen Oxides Probed by N-Confused Porphyrin Iron Complex”
Professor Yun-Ming Wang
Dept. of Medicinal and Applied Chemistry, National Kao-Hsiung Medical University “The Novel Bioactivated and Targeted Contrast Agents for MRI”
Kuo-Chu Hwang
Catalysis
Alkoxides”
15
Department of Chemistry, National Taiwan Normal University “Directed Evolution of Chiral Vanadyl(V) Complexes into C4-Symmetric Pentanuclear Clusters by Exclusive Recognition of Potassium Vanadate from Aqueous Solution: New
Aspects in Asymmetric Catalysis”
Prof. Sang Ook Kang
Department of Advanced Materials, Korea University, Chungnam, South Korea “Enhanced Charge Carrier Mobility Derived from Cyclization of a Silene Unit on Silole
Derivatives: Syntheses, Photophysical Properties and Device Fabrication of Spiro-Siloles”
Prof. Leonard V. Interrante
Prof. Thuc-Quyen Nguyen
Center for Polymers and Organic Solids, Department of Chemistry and Biochemistry University of California, Santa Barbara, CA 93106-9510, USA
“Charge Injection Mechanism in Polymer Light-Emitting Diodes using Conjugated Polyelectrolytes as Electron Transporting Layers”
Shie-Ming Peng
Dept. Of Chemistry, National Taiwan University “Molecular Metal Wires and Molecular Switches”
Jiann-Tsuen Lin
Institute of Chemistry, Academia Sinica “Materials Capable of Ambipolar Transport for OLEDs”
Eric Wei-Guang Diau
Institute of Molecular Science, National Chiao Tung University “Fabrication and Characterization of Dye/TiO2 Nanostructural Thin Films for DSSC
Applications”
Center for Condensed Matter Sciences, National Taiwan University “Some Progresses of Our Studies in Surface-Enhanced Raman Scattering”
Nano-B1
Department of Chemistry, University of Washington, 302F Roberts Hall, Seattle, USA “Molecular Design, Self-Assembly, and Interface Engineering for Molecular and Organic
Electronics”
Institute of Atomic and Molecular Science, Academia Sinica “Label-free Dual Sensing of DNA Molecules Using DNA Nanowires”
OE-C and Nano-B1
Hong-Ping Lin
Kuang-Lieh Lu
Institute of Chemistry, Academia Sinica “Design, Self-Assembly and Sensing Device of Re-Based Metallacycles”
Chun-Hsien Chen
Nano-B2
Prof. Gion Galazferri Department of Chemistry and Biochemistry, Freiestrasse 3, University of Bern, CH-3012 Bern,
Switzerland “Mimicking the antenna system of green plants”
Prof. Hicham Fenniri National Institute for Nanotechnology, The University of Alberta, AB, CANADA
17
Prof. Guillermo Carlos Bazan Departments of Chemistry and Biochemistry, and Materials, University of California Santa
Barbara, CA 93106-9510, USA “New Conjugated Polyelectrolyte Materials for Biosensor Design and Device Fabrication”
Prof. Soledad Penades Laboratory of Glyconanotechnology, Biofunctional Nanomaterials, CIC biomaGUNE, Spain
“Glyconanotechnology: A strategy for the preparation of multifunctional nanoparticles with application in Biomedicine and Material Science”
Chun-Guey Wu Department of Chemistry, National Central University
“Molecular Design of Ruthenium Complexes for High Performance DSSC Cells”
Chao-Ping Hsu Institute of Chemistry, Academia Sinica
“Electronic coupling in ground and excited state molecules”
Pi-Tai Chou
Department of Chemistry, National Taiwan University “En Route to the Molecules/Nanomaterials of Highly Efficient Emission”
Chun-Cheng Lin
Jim-Min Fang Department of Chemistry, National Taiwan University
“Conjugation of Carbohydrate Molecules for Glycobiology: Carbohydrate Modified Quantum Dots and Direct Amide Bond Linkage”
OLED-E
Department of Chemistry and Centre for Advanced Luminescence Materials, Hong Kong Baptist University; Waterloo Road, Hong Kong, P.R. China
“Heavy Metal Electrophosphors Derived from Multifunctional Chromophores”
Prof. Soo Young Park School of Materials Science and Engineering; Seoul National University
Director; Organic Nano-Photonics Lab, Seoul National University, South Korea “Luminescent Molecular Materials: Enhanced Emission, Excited-state Prototropy, Inter-
ligand Energy Transfer, and Luminescence Switching”
Prof. Carlo A. Bignozzi Dipartimento di Chimica Università di Ferrara, Via L. Borsari 46, 44100 Ferrara, Italy
“Dye Engineering and Electron Mediators for Dye Sensitized Solar Cells”
Chin-Ti Chen Institute of Chemistry, Academia Sinica
“Development of Solid-State Non-Fluorescence Quenching Red Fluorophores for Organic Light-Emitting Diodes”
Ken-Tsung Wong Department of Chemistry, National Taiwan University
“Large Band-gap Organic Conjugated Materials for Highly Efficient Electrophosphorescence Devices”
Kung-Hwa Wei
Department of Materials Science and Engineering, National Chiao Tung University “Nanopatricles Enhanced Polymer Light Emitting Diode”
19
Ben L. Feringa Department of Organic Chemistry, Stratingh Institute, University of Groningen, Nijenborgh 4, 9747 AG Groningen.
E-mail feringa@chem.rug.nl
In our body a fascinating collection of ingenious molecular motors make it possible that our cells divide, that we can use our muscles and that the consumption of ATP can be used to generate force and mobility. A billion times larger than these nanoscale protein motors in Nature are the plethora of macrocopic motors that power the cars and machinery in daily life. Artificial molecular motors stand out among the most challenging goals of nanoscience and these systems will provide the engines for future nanomachines. Inspired by Natural we design molecular systems in which the control of molecular dynamics is coupled to specific functions. Toward the bottom up construction of photo- and electro-active systems the focus is on photo- or electro-chemical switching and control of motion. In this lecture molecular switches for data storage, molecular
electronics and nanomechanical devices are presented. We developed the first light-driven unidirectional molecular motor and although primitive in nature it can be seen as a milestone at the dawn of the nanotechnology era. Pertinent questions that we currently address are “how to accelerate a molecular motor”? and “how to construct a nanoscale “windmill park” powered by light’? The design of a new generation motors will be presented in which the speed of rotation has been increased over a million fold. Furthermore the motion of a large collection of motors on a surface is presented as well as its application in smart materials. Besides rotary motion induced by light we present unique molecular motors that run on a chemical fuel.
[1]. Browne, B.L. Feringa, “Synthetic Molecular Machines at Work-Automotive Mechanics in Nanoland”, Nature –
Nanotechnology, 2006, 1, 25-35.
[2]. Pollard, M. Klok, D. Pijper, B.L. Feringa, RateAcceleration of Light-driven Rotary Motors, Adv. Func. Mater.
Feature article,2007, 17, 718-72.
[3]. Feringa “The Art of Building Small: From Molecular Switches to Molecular Motors”, J. Org. Chem.,Perspective,
2007, 72, 6635-6652.
Ben L. Feringa, University of Groningen (BS 1973; MS 1975; Ph.D. 1978, Prof. Hans Wynberg),
Research Chemist, Royal Dutch Shell, Shell Laboratories, Amsterdam.(1978-1982) Lecturer
Amsterdam (Hogere Analistenschool). (1979-1982) Research Chemist, Shell Biosciences
Laboratories, Sittingbourne, UK (1982-1983) Chairman Department Organic and Molecular
Inorganic Chemistry (1991 - 1995) Appointed Distinguished Jacobus H. van ´t Hoff Professor in
Molecular Sciences (2003-)
Gérard Férey*
Institut Lavoisier (UMR CNRS 8180), University of Versailles. 78035. Versailles (France); ferey@chimie.uvsq.fr
This lecture will present an overview of the new
field of hybrid porous solids (1). After a comparison
with other types of porous solids, their similarities
and their differences, a review of the the different
ways of their hydrothermal synthesis will be
presented. Their structures are governed by the two
concepts of augmented nets an scale chemistry
which allow the search of porous structures with
giant pores. From the proof that the secondary
building units (SBU) which describe the structures
really exist in the hydrothermal solution before the
precipitation of the final solid, it was possible to
create the computer simulation of the different ways
of connection of the SBU and therefore the
prediction of the different possible structures which
can exist.
lead to the discovery of the first crystallized
mesoporous hybrid solids MIL-100 and MIL-101
(Mil stands for Materials of Institut Lavoisier) with
unprecedented properties related to the current
societal problems concerning energy, sustainable
development and health.
hybrids will be evoked. All the current applications
of these solids will be presented at the end of the
talk. They concern the fields of adsorption and
storage of strategic gases (H2, CO2, CH4…), liquids,
molecular species, but also those of drug delivery
and the use of these hybrids as nanoreactors and
nanomoulds in the domain of nanosciences.
(1) Férey, G.; Chem. Soc. Rev. 2008, ASAP in press. (2) ) Férey, G. et al.; Acc. Chem. Res.. 2005, 38, 317 (3) Férey,
G.et al Angew. Chem Int Ed. 2004, 43, 6296 (4) Férey, G.et al Science 2005, 309, 2040.
Gérard Férey, b 1941 in Bréhal (France). Caen Univ. (MS 1965), Univ. of Le Mans (Ph.D.
1977, Prof. R. De Pape), Associate Prof. (1968), Professor (1981-). Director of Institut
Lavoisier (Versailles Univ. (1996-), Member of the French Academy of Sciences (2003-),
Alexander von Humboldt Fellow, FRSC. Research field: Synthesis, structures, mechanisms
of formation, structure prediction and properties of micro- and mesoporous solids, either
purely inorganic or hybrids.
Alan J. Heeger
University of California at Santa Barbara, California
I will summarize recent progress in the quest for a technology for low cost plastic solar cells. Recent results include 5-6% efficiency from single cells and 6.5% efficiency from Tandem Cells. New polymers are now available with absorption spectra that are
better matched to the solar spectrum. Prospects for large scale printing (roll-to-roll) will be summarized as well as opportunities to increase the efficiency to values in the 10 - 15% range.
Alan J. Heeger, b. 1936 in Sioux City, Iowa. University of Nebraska (B.S. with High
Distinction 1957), University of California at Berkeley (Ph.D. 1961), University of
Pennsylvania Assistant Professor (1962 – 64), Associate Professor (1964-67), Professor
(1967 – 82), Director, Lab. for Research on the Structure of Matter (1978 – 81), Acting
Vice-Provost for Research (1981 – 82), University of California at Santa Barbara Professor
of Physics (1982 - ), Director, Institute for Polymers and Organic Solids (1982 – 99),
Professor of Materials (1985 - ), Nobel Prize in Chemistry (2000)
22
John H. Dawson
Department of Chemistry and Biochemistry, and the School of Medicine; University of South Carolina;
dawson@sc.edu
processes and pose both environmental risks and
health hazards. Curiously, marine worms in coastal
sediments also produce noxious halophenols,
apparently to deter predators. To survive in the
presence of such poisons, the marine worm Amphitrite
ornata uses a catalytically-active globin
dehaloperoxidase to oxidatively dehalogenate
mechanisms for this reaction have been proposed: a
direct two-electron oxygen atom transfer and a
mechanism involving two successive one-electron
steps via a phenoxy radical. We have also shown
that the most versatile heme-containing peroxidase,
Caldariomyces fumago chloroperoxidase (CCPO) -
oxygen transport protein myoglobin both catalyze
halophenol dehalogenation. With all three enzymes,
the mechanism has been probed using para-
halophenols, and the product distribution is consistent
with involvement of a phenoxy radical intermediate.
Furthermore, since CCPO forms relatively stable
high-valent Compound I and II intermediates
(respectively two and one electron oxidized relative to
the ferric state), it provides an ideal system with
which to use rapid-scan stopped-flow techniques to
differentiate between the two mechanisms. Parallel
studies with A. ornata dehaloperoxidase and
myoglobin have also been pursued. Finally, as
Manderville has recently shown that phenoxy radicals
and quinones bind irreversibly and covalently to DNA
[1], the ability of myoglobin to oxidatively
dehalogenate halophenols may explain their
carcinogenicity.
[1] Dai, J.; Sloat, A.L.; Wright, M.W.; Manderville, R.A. Role of phenoxyl radicals in DNA adduction by
chlorophenol xenobiotics following peroxidase activation. Chem. Res. Toxicol. 2005; 18, 771-779.
John H. Dawson, b 1950 in Englewood, NJ, USA; Columbia Univ. (BA
1972), Stanford Univ. (PhD 1976, Profs. C. Djerassi & B.S. Hudson),
California Inst. of Technology (NIH Postdoctoral. 1976-78, Prof. H.B. Gray)
Assistant/Associate Professor (1978-85), Carolina Distinguished Professor
(1986-) Research field: Bio-inorganic, bio-physical, and bio-organic
chemistry; spectroscopy and mechanisms of action of dioxygen- and
peroxide-activating heme iron enzymes and model systems; cytochrome
P450; magnetic circular dichroism spectroscopy.
23
Eiichi Nakamura Department of Chemistry and Nakamura Functional Carbon Cluster Project, ERATO, Japan Science and
Technology, Agency, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo, 133-0033 Japan
nakamura@chem.s.u-tokyo.ac.jp
Chemists are "molecular architects". They enjoy building molecular architectures, and feel happy about learning whether or not they behave as expected. However, the molecules are too small and too fast moving to see directly their dynamic behavior. Therefore, the concept of molecules has remained very hard to understand even for chemistry students, not to mention, lay people. How many of us would really understand the molecular mechanism of the action of a pill for curing your headache? For sometime, we ponder the possibility of taking a look at molecules by a high-resolution transmission electron microscope, and succeeded very recently in obtaining time- resolved, near atomic resolution images of organic molecules in action (see below). The talk will be describe such molecular images that have
just become available as well as some discussions of implications of the new finding. Reference: Imaging Single Molecules in Motion, M. Koshino, T. Tanaka, N. Solin, K. Suenaga, H. Isobe, and E. Nakamura, Science, 316, 853 (2007); Imaging of Aromatic Amide in Motion, N. Solin, M. Koshino, T. Tanaka, Shinya Takenaga, H. Kataura, H. Isobe, and E. Nakamura, Chem. Lett., 36, 1208-1209 (2007).
Reference: Imaging Single Molecules in Motion, M. Koshino, T. Tanaka, N. Solin, K. Suenaga, H. Isobe, and E. Nakamura, Science, 316, 853 (2007); Imaging of Aromatic Amide in Motion, N. Solin, M. Koshino, T. Tanaka, Shinya Takenaga, H. Kataura, H. Isobe, and E. Nakamura, Chem. Lett., 36, 1208-1209 (2007).
Eiichi Nakamura born 1951 in Tokyo, Japan. Tokyo Institute of
Technology (B 1973, Prof. Teruaki Mukaiyama; PhD 1978, Prof. Isao Kuwajima),
Postdoc. Columbia Univ. (Prof. G. Stork, 1978-1980), Assis. Prof. Tokyo Institute of
Technology (1980-1984), Assoc. Prof. Tokyo Institute of Technology (1984-1993),
Prof. Tokyo Institute of Technology (1993-1995), Prof. Univ. of Tokyo (1995-
present). Senior Program Officer in Chemistry, JSPS (2003-2007), ERATO program
research director, JST (2004-2010). Research filed: organic synthesis, physical
organic chemistry, nano-science.
John E. Anthony*
To fulfill the promise of low-cost large-area
electronics (displays, solar cells and solid-state
lighting), materials for organic electronic applications
must be easily prepared, stable, and amenable to
solution deposition methods. The latter requirement
typically thwarts most efforts to develop new
materials - approaches to solubilize large aromatic
chromophores typically do so by disrupting the strong
intermolecular interactions necessary for electronic
device performance. Our group has taken a holistic
approach to improving both solubility and stability
while simultaneously engineering the solid state
organization of linear aromatic compounds to induce
strong π-stacking interactions. Separating the "waxy"
solubilizing substituent from the rigid aromatic core
by a flexible alkyne spacer allows the aromatic
moieties to interact strongly, while the solubilizing
substituents segregate into domains of insulating
hydrocarbon. The ethyne substituent also increases
the oxidation potential of the aromatic chromophore,
significantly enhancing material stability. This
approach to chromophore functionalization has
yielded high-performance materials for thin film
transistors, light emitting diodes and flexible solar
cells. Furthermore, the stabilization afforded by
properly selected substituents has allowed us to
explore heretofore poorly studied materials such as
hexacene and heptacene. This talk will focus on
materials optimization for a variety of electronic
applications, including functionality that converts
normally p-type acenes to n-type semiconductors, and
will explore the complex relationship between
functionalization, crystal packing, thin-film
performance.
John E. Anthony, b 1967 in Los Angeles, California. Reed College (BA 1989), Univ. of
California at Los Angeles (Ph.D. 1994, Prof. F. Diederich), Univ. of California at Los
Angeles (Postdoc. 1994 - 1996, Prof. Y. Rubin), University of Kentucky Assistant Prof.
(1996 - 2002), Associate Professor (2002-2006), Gill Professor of Chemistry (2006 - ).
Research field: Aromatic chemistry, organic electronics, flexible displays and photovoltaics.
25
Shu _ Kobayashi
Department of Chemistry, School of Science, The University of Tokyo; Hongo, Bunkyo-ku, Tokyo 113-
0033, Japan; shu_kobayashi@chem.s.u-tokyo.ac.jp
chemistry. From this aspect, our group has focused
on the use of water as a reaction media in catalysis as
well as the use of immobilized catalysts in organic
synthesis. We have recently developed novel
polymer incarcerated gold nano-cluster catalysts (PI-
Au catalysts) by microencapsulation of gold nano-
cluster and cross-linking using a co-polymer based on
polystyrene.1 Transmission electron microscopy
gold clusters whose size was nano order. This
catalyst could be used in aerobic oxidation of various
alcohols to aldehydes and ketones under atmospheric
conditions at room temperature. The oxidation
reactions using PI-Au catalysts are excellent in terms
of atom economy and energy efficiency because the
reactions proceed without extra heating and only
molecular oxygen is consumed and water is generated
as the sole co-product. Also in the oxidation of sec-
phenethyl alcohol at 160 degree, turnover number
frequency exceeded 20,000 /h.
calcium which promote the catalytic asymmetric 1,4-
addition reactions and [3+2] cycloaddition reactions
of α-amino acid derivatives with α,β-unsaturated
carbonyl compounds will also be discussed.2
.
[1] Miyamura, H.; Matsubara, R.: Miyazaki, Y.; Kobayashi, S. Angew. Chem. Int. Ed. 2007, 46, 4151;
Miyamura, H.; Matsubara, R.: Kobayashi, S. submitted. [2] S. Saito, T. Tsubogo, S. Kobayashi, J. Am.
Chem. Soc. 2007, 129, 5364.
Shu _
Kobayashi, b 1959 in Tokyo, Japan. The University of Tokyo (BS 1983; Ph.D.
1988, Prof. T. Mukaiyama). Assistant Prof. (1987), Lecturer (1991), Associate
Professor (1992) in Science University of Tokyo, Professor (1998) in Pharmaceutical
Sciences in The University of Tokyo, Professor (2007) in Department of Chemistry,
School of Science in The University of Tokyo (2007). Research filed: green
sustainable chemistry, synthetic organic chemistry, and drug discovery, etc.
26
The Meta vs Para Conjugation Effects on the Electronic Properties of π-Conjugated Systems
Jye-Shane Yang
jsyang@ntu.edu.tw
photoluminescence, energy migration, electron
electronic coupling (delocalization) between the
subunits. It is well known that electronic coupling
through a meta-phenylene (m-Ph) bridge is inherently
weaker than through a para-phenylene (p-Ph) one.
However, recent studies have shown that their
difference becomes smaller on going from the ground
to the excited state, and the meta conjugation effect
could be further enhanced by structural modifications
on the Ph bridge (e.g., replaced by pyridyl or phenol
groups) or the subunits (e.g., presence of electron-
donating amino or alkoxy groups). In this talk, the
meta and para conjugation effects on the electronic
properties of π-conjugated systems will be presented
for several systems such as aminostilbenes [1,2], the
amino analogs of the green fluorescence protein
(GFP) chromophore [3], isotruxene vs truxene-derived
star-shaped systems [4].
R3R3
R3
R1R2R1R2
R1
R2
isotruxene derivatives [1] J.-S. Yang, K.-L. Liau, C.-Y. Li,. M.-Y. Chen, J. Am. Chem.Soc. 2007, 129, in press. [2] J.-S. Yang, K.-L. Liau, C.-M. Wang, C.-Y. Hwang, J. Am. Chem. Soc. 2004, 126, 12325-12335. [3] J.-S. Yang, G.-C. Huang, G.-H. Lee, S.-M. Peng, submitted. [4] J.-S. Yang, Y.-R. Lee, J.-L. Yan, M.-C. Lu, Org. Lett. 2006, 8, 5813-5816.
Jye-Shane Yang (), born in 1966, National Taiwan University (B.S. 1988;
M.S. 1990), Northwestern University, USA (Ph.D. 1997, Prof. F. D. Lewis), MIT
(postdoct. 1998, Prof. T. M. Swager), Assistant Prof. (1998) and Associate Prof.
(2002) of National Central University, Associated Prof. (2005) and Prof. (2007)
of National Taiwan University. Research interests: physical organic chemistry,
design and synthesis of fluoroionophores, photoinduced charge-transfer behavior
of donor-acceptor molecules, and synthesis and optoelectronic properties of
conjugated molecular systems.
Bor-Cherng Hong,* Ming-Fun Wu, Hsing-Chang Tseng, Guo-Fong Huang, Cheng-Feng
Su and Ju-Hsiou Liao
chebch@ccu.edu.tw
were achieved, catalyzed by L-proline and trialkyl
amines and providing the formal [4 + 2]
cycloaddition adducts. Additionally, in some examples
in the catalysis with diarylpyrrolinol silyl ethers, the
reactions afforded the [4 + 2] adducts with high
enantioselectivity (>99.5% ee). The structure of the
adduct, obtained from the reaction of 3-methylbut-2-
enal and (E)-3-(2-nitrophenyl)acryaldehyde, was
configurations of some [4 + 2] cycloadducts were
investigated, and the methodology was applied in the
synthesis of (+)-palitantin.
(+)-Palitantin
R2 = CH2G
(1) Hong, B.-C.; Wu, M.-F.; Tseng, H.-C.; Liao, J.-H. Organic Letters, 2006, 8, 2217. (2) Hong, B.-C.;
Nimje, R. Y.; Yang, C.-Y. Tetrahedron Lett. 2007, 48, 1121. (3) Hong, B.-C.; Tseng, H.-C.; Chen, S.-H.
Tetrahedron 2007, 63, 2840-2850. (4) Hong, B.-C. et. al. J. Org. Chem. 2007, 0000.
Bor-Cherng Hong, b 1962 in Changhua, Taiwan. Tunghai Univ. (BS 1984); National
Taiwan University (MS 1986), Univ. of Chicago (Ph.D. 1992, Prof. J. D. Winkler),
Harvard University (Postdoc. 1994, Prof. E. J. Corey) Associate Prof. (1994),
Professor (1999-).
synthetic methodologies, and medicinal chemistry.
28
Chen-Sheng Yeh,* I-Fang Li, Wen-Shuo Kuo, and Chia-Hao Su Department of Chemistry, National Cheng Kung University, Tainan, Taiwan; csyeh@mail.ncku.edu.tw
Functional nanoscale materials are promising new
paradigms in pharmacotherapy and provide many
applications in the areas of gene therapy, drug delivery,
imaging, and novel drug discovery techniques. The
aim of nanodiagnostics is to identify disease at its
earliest stage, particularly at the molecular level.
Nanomaterial-based systems have set a unique
platform for cellular tracking, targeted diagnostic
studies, and image-monitored therapy. The variety
strategies have been demonstrated to fabricate
functional nanomaterials. For example, the
Gd2O(CO3)2·H2O colloidal particles have been
prepared by a reflux of the mixture containing
GdCl3·6H2O and urea solution. The biocompatible
amorphous Gd2O(CO3)2·H2O spheres were
demonstrated showing T1-enhancing and T2-lowering
effects, which provide an alternative choice for an
MRI contrast agent. In the other case, the infectious
E. coli bacteria have been successfully transformed
into a biocompatible therapeutic platform. When the E.
coli bacteria were incubated with HAuCl4 precursors
without addition of reducing agent, Au nanoshell was
generated and covered onto the bacteria surface.
Interestingly, the bacteria coating with Au
nanomaterials remained alive and showed no toxicity. The living gold nanoshell-coated bacteria
(bacteria@Au) served as the photothermal therapeutic
agents and were conjugated with anti-EGFR
antibodies to destroy cancerous cells with a NIR laser.
Chen-Sheng Yeh, b 1961, Tamkang Univ. (BS 1984), National Tsing Hua
Univ. (MS 1986), Univ. of Georgia (Ph.D. 1993, Prof. M. Duncan),
Purdue Univ. (Postdoc. 1994, Prof. B. Freiser) Associate Prof. (1995),
Professor (2001-). Research filed:
2. MRI Applications of Nano-related Materials.
3. Bio-system Applications of Nano-related Materials.
29
NR
( )n ( )n
R = H or alkyl
Intramolecular Addition of Conjugated Dienes to Alkynes Catalyzed by Platinum and Gold
Ming-Chang Yeh,* Whei-Fen Bai, J-Lin Lin, Li-Lin Liu, Yu-Shiang Liu and Tern-Chi Lin
Department of Chemistry, National Taiwan Normal University; Taipei, Taiwan; cheyeh@scc.ntnu.edu.tw
Platinumdichloride-catalyzed hydroxy- or
derivatives, whereas hydroxy- or alkoxycyclization of
cycloheptadienynes produce azulenol derivatives.
stereocontrol of three contiguous stereogenic centers
of the fused bicyclic skeletons. The transient reactive
intermediate can be trapped intramolecularly by a
hydroxyl group to afford an
oxatricyclo[5.4.0.04,8]undecane ring skeleton with
extreme diastereoselctivity.
generated via AuCl(PPh3) catalyzed intramolecular
addition of cyclic 1,3-dienes to a tethered alkyne.
The reactive intermediates can be trapped
intramolecularly by an arene to furnished tetra- and
pentacarbocycles in extreme diastereoselective
fashion and excellent yields.
Hexahydrobenzofuran derivatives can be
constructed via palladium-catalyzed intramolecular
diene. While nitrogen nucleophiles failed to produce
hexahydroindols under the same reaction condition.
However, treatment of nitrogen tethered cyclohexa-
1,3-dienes with AuCl(PPh3) and AgOTf in toluene
under nitrogen smoothly produced hexahydroindols in
good yields.
1. Yeh, M. C. P.; Tsao, W. C.; Wang, Y. J.; Pai, H. F. Organometallics 2007, 26, 4271.
2. Yeh, M. C. P.; Tsao, W. C.; Tu, L. S. Organometallics 2005, 24, 5909-5915.
Ming-Chang P. Yeh , b 1954; National Taiwan Normal University (B.S., 1977); Ph.D.,
Princeton University (Ph.D., 1987, Prof. M. F. Semmelhack); Postdoctoral Fellow,
University of Michigan (1987-1989, Prof. P. Knochel); Research Associate, (Academia
Sinica, 1989-1990); Associate Professor, Department of Chemistry, National Taiwan
Normal University (1990-1993); Full Professor (1993-present). Research fields: metal-
catalyzed organic reaction; synthetic methodology, photo-electronic materials.
30
Lanthanide (III)-Cored Dendrimer Compleses: New Design Criteria and Unusual Photophysical Investigations
Bong Kyu Kwak, Kang-Duk Kang, Dong-Hyun Lee, and Hwan Kyu Kim*
Department of Advanced Materials Chemistry, 208 Seochang, Jochiwon, ChungNam 339-700, Korea. E-mail: hkk777@korea.ac.kr
We present that the stable and inert Er(III)-
encapsulated complexes based on anthracene, naphthalene, and Pt(II)-porphyrin ligands bearing a second generation Fréchet aryl-ether dendron (G2) exhibit much stronger near-IR emission bands at 1530 nm (see Figure 1). The emission intensity of the lanthanide complexes, upon photoexcitation of luminescent ligand at the corresponding absorption maximum wavelength, was dramatically enhanced by introducing a second generation Fréchet aryl- ether dendron (G2), as compared with those of their corresponding Er(III)-encapsulated complexes, mainly due to the site-isolation effect.
Surprisingly, our photophysical studies suggest that energy transfer pathway does not influence the lanthanide emission enhancement: Although ET process via the triplet state to Ln3+ ion is considered as main efficient ET pathway in Ln(III) complex, this sensitization process is not strongly dominated on Ln3+ emission, compared with other ET pathways via singlet or charge transfer state. In other words, the ISC process caused by the heavy Ln3+ ion effect in Ln(III) complexes is not dominant process over
the ICT or the radiative relaxation process. Therefore, to enhance of the near IR emission in
luminescent lanthanide complexes, no matter which ET pathway takes place, the key parameters are the type of luminescent lanthanide complexes such as a direct complex or an indirect complex, the coordination number of lanthanide ions with the complexed ligands, the luminescence quantum efficiency of the ligand and the spectral overlap integral (J) value between the emission band of the ligand and the absorption band of lanthanide ion: (1) The direct luminescent Ln(III) complexes have much higher PL efficiency than the indirect luminescent Ln(III) complexes. (2) Highly coordinated lanthanide-cored complexes (at least 8 to 9 coordination number) have much higher PL efficiency than unsaturated 6-coordinated complex. 3) The key factor for strong lanthanide emission is the ET efficiency between the organic ligand and Ln3+ ion, associated with the quantum yield of a ligand and a proper J value. This study can provide the criteria for designing the ligand to achieve efficient Ln3+ emission.
Figure 1. The Chemical structures and photophysical properties of Er(III)-cored complexes based on dendritic
anthracene and Pt-porphyrin ligands. 1. J. B. Oh, M. K. Nah, Y. H. Kim, M. S. Kang, and H. K. Kim, Adv. Funct. Mater.,2007, 17(3), 413. 2. Y. H. Kim, N. S. Baek, and H. K. Kim, ChemPhysChem, 2006, 7, 213. 3. N. S. Baek, M.-K. Nah, S.-G.. Roh, and H. K. Kim, Adv. Funct. Mater., 2006, 16, 1873.
Hwan Kyu Kim, b 1957 in Ulsan, Korea. Univ. of Ulsan (BS 1980), KAIST (MS 1982), Carnegie Mellon Univ. (Ph.D. 1990, Prof. K. Matyjaszewski), Cornell Univ. (Postdoc. 1991-3, Prof. C. K. Ober), ERTI (Senior Researcher 1993-4), Hannam Univ. (Professor 1994-2007), Korea Univ. (Professor 2007-). Research filed: luminescent lanthanide materials, organic optoelectronic materials for LED & NLO and low-loss polymeric waveguide materials, dye-sensitized solar cell, biosensors, and organic/inorganic hybrid materials for photonic applications.
Er Er
5.0x103
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80
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PL In
te ns
ity (a
PL In
te ns
ity (a
PL In
te ns
ity (a
5.0x103
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2.5x104
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80
5.0x103
1.0x104
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PL In
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Hiroaki Sasai
The Institute of Scientific and Industrial Research (ISIR), Osaka University; Ibaraki-shi, Osaka 567-0047,
Japan; sasai@sanken.osaka-u.ac.jp
spiro skeleton such as spiro bis(isoxazoline) ligands
(SPRIXs) [1-3], spiro bis(isoxazole) ligands [4], and
hybrid type spiro
Pd(II)-iPr-SPRIX complex catalyzes Wacker type
cyclization of alkenyl diol in up to 91% ee and tandem
cyclization of dialkenyl alcohols to give bicyclic
products in up to 95% ee. (eq. 1 and 2) [1]. The first
enantioselective aminocarbonylation of alkenyl
found the Pd(II)-iPr-SPRIX complex promotes 5-
Endo-Trig cyclization of β,γ-unsaturated acids and
their corresponding amides (eq. 4 and 5) to afford γ-
butenolides and/or 2-pyrrolinones. It is noteworthy
that the use of other known asymmetric ligands such
as BINAP, bis(oxazolinyl)propane and iPr-boxax do
not promote these reactions.
[1] Arai, M. A.; Kuraishi,M.; Arai, T.; Sasai, H. J. Am. Chem. Soc. 2001, 123, 2907. [2] Takizawa, S.; Yogo,
J.; Tsujihara, T.; Onitsuka, K.; Sasai, H. J. Organometal. Chem. 2007, 692, 495. [3] Wakita, K.;
Bajracharya, G. B.; Arai, M. A.; Takizawa, S.; Suzuki, T.; Sasai, H. Tetrahedron: Asymmetry, 2007, 18,
372. [4] Wakita, K.; Arai, M. A.; Kato, T.; Shinohara, T.; Sasai, H. Heterocycles, 2004, 62, 831-838. [5]
Koranne, P. S.; Tsujihara, T.; Arai, M. A.; Bajracharya, G. B.; Suzuki, T.; Onitsuka, K.; Sasai, H.
Tetrahedron: Asymmetry, 2007, 18, 919. [6] Shinohara, T.; Arai, M. A.; Wakita, K.; Arai, T.; Sasai, H.
Tetrahedron Lett., 2003, 44, 711.
Hiroaki Sasai, b 1956 in Tokyo, Japan. Keio Univ. (BS 1980; MS 1982; Ph.D. 1985,
Prof. T. Suami), Sagami Chemical Research Center (Researcher. 1985, Prof. M.
Shibasaki), Hokkaido Univ. Assistant Prof. (1988), Univ. of Tokyo Associate Prof.
(1992), Osaka Univ. Professor (1997-). Research filed: asymmetric catalysis, green
chemistry, and artificial enzyme using dendritic molecule.
N OO N
[Pd(CH3CN)4](BF4)2 (10 mol%) iPr-SPRIX (11 mol%), CO (1 atm)
p-benzoquinone, MeOH
R OH
p-benzoquinone O
p-benzoquinone NTs
Yoshiro Yamashita
yoshiro@echem.titech.ac.jp
Much attention has been focused on organic field
effect transistors (OFET)s from viewpoints of application purposes for electronic devices as well as basic interest in charge transportation. Although a lot of p-type semiconductors are reported, the number of n-type one is still limited and the performances are not satisfactory. We have designed various kinds of heterocyclic compounds for n-type semiconductors. We report here those n-type FETs.
Usual tetrathiafulvalen (TTF) derivatives show p- type semiconductive behavior owing to their electron-donating properties. Even 1a containing electron-accepting quinoxaline rings afforded p- type FETs.1) We have introduced electron- withdrawing groups into the quinoxaline rings to lower the LUMO levels and found that the derivatives 1b,c showed high performance n-type behavior.2) On the other hand, two halogen atoms- containing derivatives 2a,b showed p-type behavior. This finding confirms that the FET polarity can be
determined by the frontier orbital energies. We have also developed n-type semiconductors
based on heterocyclic co-oligomers with trifluoromethylphenyl groups. The electron mobilities in these systems were very high and the highest mobility of 1.83 cm2/Vs was achieved by using a bithiazole unit.3) However, the threshold values of these systems were high (55–78 V). In order to decrease the threshold values, we have carried out optimization of device structures using a thiazolothiazole derivative 3.4) The threshold voltages were decreased to 22 V by using Ta2O5 with a high dielectric constant. Further decrease was accomplished by developing new molecules 4 with high electron affinity. 5) The device based on 4 showed a low threshold value of 3 V. Introduction of Se atoms in 4 was effective to increase the electron affinity. The relationship between the structures and FET characteristics will be discussed here.
N
N
S
SR
2a: R = F 2b: R = Cl
N
SN
S
S
S
F3C
CF3
4 ( X = S, Se)
(1) Naraso, J. Nishida, S. Ando, J. Yamaguchi, K. Itaka, H. Koinuma, H. Tada, S. Tokito, and Y. Yamashita, J. Am. Chem. Soc., 127, 10142 (2005). (2) Naraso, J. Nishida, D. Kumaki, S. Tokito, and Y. Yamashita, J. Am. Chem. Soc., 128, 9598 (2006). (3) S. Ando, R. Murakami, J. Nishida, H. Tada, Y. Inoue, S. Tokito, and Y. Yamashita, J. Am. Chem. Soc., 127, 14996 (2005). (4) D. Kumaki, S. Ando, S. Shimono, Y. Yamashita, T. Umeda, and S. Tokito, Appl. Phys. Lett., 90, 053506 (2007). (5) T. Kono, D. Kumaki, J. Nishida, T. Sakanoue, M. Kakita, H. Tada, S. Tokito, and Y. Yamashita, Chem. Mater., 19 1218 (2007).
Yoshiro Yamashita, b 1950 in Odawara, Japan. Tohoku Univ. (BS 1973; PhD 1978), Assistant
Prof. at Tokushima Univ. (1978) and Tohoku Univ. (1984). Associate Prof. at Inst. of Molecular
Science (1989), Professor at Tokyo Inst. Tech. (2000-). Research filed: Development of novel
organic compounds such as organic semiconductors for transistors and ELs.
33
We have successfully reconstituted apo-
myoglobin with a series of M complexes having
different coordination structures and solved their
crystal structures (Fig 1).1,2 Further, we are able to
regulate the enantioselectivity of thioanisole
sulfoxidation catalyzed by MIII(Schiff- base)•apo-Mbs
by designing the Schiff-base ligands.3 We have also
prepared a zero-valent palladium cluster by chemical
reduction of palladium ions in the apo-ferritin cage
and examined its catalytic reduction activity. The
palladium clusters catalyzes size-selective olefin
hydrogenation4 because substrates must penetrate into
the ferritin cavity through the size restricted channels.
Through the Pd•apo-Feritin study, we have found that
there are Pd ion binding sites in the apo-ferritin to
capture as many as 300 Pd ions. The protein inerior
suface of apo-ferritin contains amino acid residues
such as cysteine, histidine, glutamate, aspartate, and
methionine. These residues could ligate to metal
anions to accommodate them. Thus, we have
examined crystal structures of apo-ferritin containing
various amounts of Pd ions. The crystal structures of
Pd•apo-Fr has been refined to 1.65Å resolution (Fig
2).5 We have further found that different metal inons
utilize different binding sites beaing different
coordination structure. By taking these features,
we have prepared alloy and core-shell types of metal
nano-clusters of Au/Pd in ferritin. The catalytic
activities of these metal-protein composites will be
discussed.
(1) Y. Satake, et al, Organometallics, 26, 4904-4908 (2007). (2) S. Abe, et al., Inorg. Chem. 46, 5137-5139
(2007).(3) T. Ueno et al., J. Am. Chem. Soc., 127, 6556-6562 (2005). (4) T. Ueno et al, Angew. Chem. Int. Ed., 43,
2527-2530 (2004). (5) M. Suzuki et al., in submission.
Yoshihito Watanabe, b 1953 in Japan. Tohoku Univ. (BS 1976), Univ. of Tsukuba (Ph.D. 1982),
Univ. Michigan and Princeton Univ. (Postdoc. 1982-1987), Kyoto Univ. (Associate Prof. 1990-
1994), the Inst. Mol. Sci. (Prof, 1994-2001), Nagoya Univ. (Prof, 2001-) Research filed: molecular
mchanisms of oxygen activation by heme enzymes and molecular design of metalloenzymes.
Fig 1 The crystal structures of Apo-Mb reconstituted with Rh Fig 2 The crystal structures of Pd bound and Cu complexes. ferritin and its detailed structure.
34
Hong-Cheu Lin,* Ling-Yung Wang, Tzung-Chi Liang, Po-Jen Yang, Shen-Chang Wu
Department of Materials Sci. & Eng., National Chiao Tung University; Hsinchu, Taiwan; linhc@cc.nctu.edu.tw
Approaches towards new electro-optical materials
by supramolecular structures have attracted interests
lately. A recent strategy includes the combination of
different non-covalent binding sites bearing
complementary groups within H-bonded systems.
Different functionalities can be introduced in a well
defined way by controlled self-assembled processes to
form supramolecular structures.
containing banana-shaped cores with 5-9 aromatic
rings have been developed in our study. Several ways
to stabilize H-bonded bent-cores were proposed,
where copolymerization of side-chain bent-core
monomers with both H-bonds and covalent bonds by
free radical polymerization will be presented. Some
interesting electro-optical properties, including the
SmCPFE phases, which depend on the molar ratios of
H-bonded and covalent segments, will be discussed.
Several series of novel photoluminescent side-
chain copolymers containing end-capping pyridyl
acceptors were synthesized, which can be H-bonded
with electron-transporting donor dendrimers or with
different isomeric carboxylic acids (para-, meta-, and
ortho-benzoic acids) in supramolecular architectures.
As the light-emitting copolymers were combined with
functionalized gold(Au)-nanoparticles, the emission
concentrations of Au-nanoparticles, which were
attributed to the process of electron transfer from
copolymers to Au-nanoparticles. In TEM studies,
different morphologies were modulated by donor acid
contents in supramolecular architectures. The thermal,
mesogenic, and optical properties of these H-bonded
materials were strongly influenced by the
supramolecular interaction of H-bonds.
properties of the supramolecules can be effectively
adjusted by not only the rigid cores but also by the H-
bonds. The effects of supramolecular interaction (i.e.
hydrogen bonds) on both LC and light-emitting
properties of these supramolecules are crucial.
(1) Lin, H. C.;* Tsai, C. M.; Huang, G. H.; Tao, Y. T. Macromolecules 2006, 39, 557. (2) Wu, C. W.; Lin, H. C.*
Macromolecules 2006, 39, 7985. (3) Chen, Y. Y.; Tao, Y. T.; Lin, H. C.* Macromolecules 2006, 39, 8559.
Hong-Cheu Lin, born in 1961. National Taiwan Univ. (B.S. 1983), Northwester Univ. (M.S.
1986), Univ. of Illinois at Urbana-Champaign (Ph.D. 1992, Prof. S. I. Stupp), Academia Sinica
(Assistant Research Fellow 1992-1998, Associate Research Fellow 1998-2000), Chiao Tung Univ.
(Associate Prof. 2000-2005, Professor 2005-). Research filed: liquid crystalline materials, electro-
optical organics, sensor polymers, and optoelectronic nano-materials.
O O
(CH2)10 O
Chemistry of Nitrogen Oxides Probed by N-Confused Porphyrin Iron Complex
Chen-Hsiung Hung Institute of Chemistry, Academia Sinica; Taipei, Taiwan; chhung@chem.sinica.edu.tw
Nitrate and nitrite reduction are two important
reactions during the denitrification process of the
nitrogen cycle. In the biological system, the
molybdenum containing nitrate reductase converts
nitrate to nitrite ions and cytochrome cd1 is
responsible for the catalytic reduction of the nitrite to
nitric oxide. While the constrain of substrate to an
entatic state is important for an enzymatic reaction,
proper proton supply, hydrogen bonding, and electron
shuttle are all essential for the rapid catalytic reactions.
Except of some complicate systems, there are limited
examples of iron porphyrin systems which were
designed to probe the hydrogen bonding and protons
supplies. Recently, we have found that the N-confused
porphyrins with an inverted pyrrole ring inside the
porphyrin macrocycle exhibited versatile tautomer
forms depending on the metal oxidation state.[1]
More importantly, the inner C-H and outer N-H,
which is the result of the inversion of pyrrole ring,
behave as hydrogen bonding donor and proton donator.
The porphyrin dimer assembled from the outer N-H
demonstrated the hydrogen bonding ability of the
ligand[2] while, more recently, the studies on the
reactions of nitrogen oxides provided unusual
reactivity direct correlating to the proton donation
ability. The reaction of nitrite on the iron N-confused
porphyrin, instead of nitrite coordination, gave an iron
N-confused porphyrin nitrosyl complexes with a
{FeNO}6 electronic structure. The reaction of trityl
nitrosothiols not only transferred nitrosyl group to the
porphyrin center but also cleavaged C-S bond of the
nitrosothiol and inserted sulphur atom to the metal
complex.[3] It is found that a direct nitrate reduction
can not be achieved using the iron N-confused
porphyrin as a starting material. However, in the
presence of an oxo group acceptor, the reduction of
nitrate to nitric oxide was observed. The potential
reaction mechanisms supported by spectroscopic data
will be discussed.
[1] Rachlewicz, K.; Wang, S.-L.; Ko, J.-L.; Hung, C.-H.; Latos-grazynski, L. J. Am. Chem. Soc. 2004, 126, 4420-
4431. [2] Hung, C.-H.; Chang, C.-H.; Ching, W.-M.; Chuang, C.-H. Chem. Comm., 2006, 1866. [3] Hung, C.-H.;
Ching, W.-M.; G.-F. Chang; Chuang, C.-H.; Chu, H.-W.; Lee, W. Z. submitted.
Chen-Hsiung Hung, b 1964 in Nantou, Taiwan. Chung Yuan Christian University. (BS 1986; MS
1988), Univ. of Wyoming (Ph.D. 1997, Prof. D. S. Bohle), North Carolina State University
(Postdoc. 1997, Prof. J. S. Lindsey), National Changhua University of Education (Assistant Prof.,
1998-2003; Associate Prof., 2003-2005), Academia Sinica (Associate Research Fellow, 2005-).
Research field: Porphyrin Synthesis, Nitric Oxide Chemistry, and Molecular Sensing.
36
Hsiu-Fu Hsu,* Hsiu-Hui Chen, and Chung-Hao Kuo
Department of Chemistry, Tamkang University; Tamsui, Taiwan; hhsu@mail.tku.edu.tw
Controlling the long range molecular order is a key
for successful molecular-based optoelectronic devices.
Through proper design, aggregations of molecules can
be attained; however, domain boundaries often cannot
be avoided. Herein, a new concept is introduced by
combing self-assembling liquid crystals and self-
assembled monolayers (SAMs) for achieving
homeotropic molecular alignment (Figure 1).
Materials with various geometrical molecular
shapes were designed and prepared for achieving
different degree of self-assembling ability. As a result,
different molecular packing motifs were accomplished.
As for the target SAM, thiol surfactants used are
designed to incorporate a terminal group showing
strong interactions with materials to be layered on top
of the SAM surface. Induction of homeotropic
molecular alignment was achieved for the layered
liquid crystal materials on top of the tailored-made
SAM surface. Beyond the interface, intermolecular
interactions among liquid crystalline molecules took
place to result in a long range homeotropic molecular
alignment as detected under polarized optical
microscope.
Fig. 1. Proposed molecular alignment on SAM surface. Fig. 2. Optical texture of LC materials on top of SAM
surface
(1) Chen, C.-T.; Lin, J.-S.; Murthy, M.; Chem. Commun. 2005, 3980. (2) Chen, C.-T.; Wei, Y.; Lin, J.-S.; Moturu, M.
V. R. K.; Chao, W.-S.; Tao, Y.-T.; Chien, C.-H. J. Am. Chem. Soc. 2006, 128(33), 10992. (3) Chen, C.-T.; Wei, Y. J.
Am. Chem. Soc. 2007, 129(24), 7478.
Hsiu-Fu Hsu, b 1966 in Taipei, Taiwan. National Sun Yat-Sen Univ. (BS 1988), Univ. of Illinois
at Urbana-Champaign (Ph.D. 1997, Prof. J. Shapley), Massachusetts Institute of Technology
(Postdoc. 1999, Prof. T. Swager) Assistant Prof. (1999), Associate Prof. (2003), Professor
(2007-). Research filed: organometallic chemistry, liquid crystals, and nano-materials.
37
Yun-Ming Wang
A smart contrast agent for magnetic resonance
imaging (MRI) can be used to exploit an enzymatic
activity specific to the tissue or disease state signified
by converting an MRI-inactivated agent to an
activated MRI agent. In this study, the β-
galactopyranose and β-glucuronic acid-containing[1]
gadolinium(III) complexes [Gd(DOTA-FPG)(H2O)]
synthesized and characterized as being potentially
suitable for the bioactivated MRI contrast agents. The 17O NMR experiments[2][3] were conducted to
estimate the water exchange rate 298 exk and rotational
correlation time 298 Rτ . The rotational correlation time
values of [Gd(DOTA-FPG)(H2O)] and [Gd(DOTA-
FPβG)(H2O)] are dramatically longer than those of
[Gd(DOTA)(H2O)]−. Relaxometric studies show that
the percentage change in the 1r values of
[Gd(DOTA-FPG)(H2O)] and [Gd(DOTA-
β-galactosidase and β-glucuronidase, and human
serum albumin. The r1 change percentages of
[Gd(DOTA-FPG)(H2O)] and [Gd(DOTA-
Egad. The signal intensity of the MR image for
[Gd(DOTA-FPG)(H2O)] in the presence of human
serum albumin and β-galactosidase (2670 ± 210) is
significantly higher than that of [Gd(DOTA-
FPG)(H2O)] in the sodium phosphate buffer solution
(1490 ± 160). In addition, the MR images of
[Gd(DOTA-FPG)(H2O)] show a higher intense
enhancement in CT26/β-gal tumor with β-
galactosidase gene expression but not for the CT26
tumor without β-galactosidase gene expression. We
conclude that [Gd(DOTA-FPG)(H2O)] and
for the bioactivated MRI contrast agents in tracing
gene expression[4].
HO OH
protein(HSA) or β-galactosidase
[Gd(DOTA-FP)(H2O)]-HSA [1] Duimstra, J. A.; Femia, F. J.; Meade, T. J. J. Am. Chem. Soc. 2005, 127, 12847-12855. [2] Ou, M.-H.; Tu, C.-H.;
Tsai, S.-C.; Lu, W.-K.; Lee, W.-T.; Liu, G.-C.; Wang, Y.-M. Inorg. Chem. 2006, 45, 244-254. [3] Wang, Y. M.; Li, C.
R.; Huang, Y. C. ; Ou, M. H. ; Liu, G. C. Inorg. Chem., 2005, 44, 382-392. [4] Chang, Y. T.; Cheng, C. M.; Su, Y. Z.;
Lee, W. T.; Hsu, J. S.; Liu, G. C.; Cheng, T. L.; Wang, Y. M. Bioconjugate Chem. (2007)(in press).
Yun-Ming Wang, b 1952 in Kaohsiung, Taiwan. Chung Cheng Institute of Technology (BS 1975;
MS 1980), National Tsing-Hua Univ. (Ph.D. 1990, Prof. C. S. Chung), Massachusetts General
Hospital (Postdoc. 1992, Prof. R. Weissleder) Associate Prof. (1993), Professor (1998-). Research
field: Bioinorganic chemistry, Paramagnetic metal complex, bio-activated metal complex and iron
oxide nanoparticles for magnetic resonance imaging.
38
Top 5 Program (WPI) in Japan and Evaluation of Research Accomplishments
Yoshinori Yamamoto
Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan
yoshi@mail.tains.tohoku.ac.jp
(issued by Cabinet, March 28, 2006) and
"Comprehensive Strategy for Creating Innovation"
(issued by Council for Science and Technology
Policy, June 14, 2006), the World Premier
International Research Center (WPI) Initiative
was established by Japan's Ministry of Education,
Culture, Sports, Science and Technology (MEXT)
in FY2007. The program, so called “top five”
program, provides priority support for projects
aimed at creating top world-level research centers
staffed at their core with the world's most leading
researchers. By achieving a very high research
standard and providing an excellent research
environment, the centers should possess a level of
"global visibility" that attracts top researchers from
around the world.
Atom-Molecule-Materials” was accepted as one of
the five WPI research centers. The main objective
of the Center is to promote the development of new
materials under a world-leading organization for
interdisciplinary research in functional materials,
by use of an innovative method of atomic and
molecular control, departing from the typical
approaches and moving towards the next generation.
In addition to basic research, the Center will pursue
(1) the creation of new compounds and materials
with innovative functions which exceed existing
ones, (2) the construction of devices based upon a
new fundamental paradigm, and (3) the promotion
of applied research projects on materials and
system architecture that will generate direct societal
impacts. In addition, the Center will establish
innovations in understanding diverse material
functions through the creation of new basic
materials and compounds which brings significant
benefits for the future of humanity.
I will talk about the WPI issue, and evaluation of
research accomplishments based on publication. If I
have enough time, I will talk about my own
chemistry; gold-catalyzed new transformations and
their application for the synthesis of biologically
active compounds and of fused aromatic systems.
Yoshinori Yamamoto, b 1942 in Kobe, Japan. Osaka University (BS 1965; MS 1967; Ph.D.
1970), Osaka University ( Assistant Prof. 1970-76), Purdue Univ. (Postdoc. 1970-72, Prof. H. C.
Brown), Kyoto University (Associate Prof. 1977-85), Tohoku University (Professor 1986-).
Research filed: development of new synthetic reactions using transition metal and Lewis acid
catalysts, and their application to complicated natural products.
39
Understanding How the Thiolate Contributes to the Function of the Non-Heme Iron Enzyme Superoxide Reductase
Julie Kovacs,* Terutaka Kitagawa, Santiago Toledo, Elaine Nam, Priscilla Lugo-Mas, Lisa M.
Brines, Pauline Alokolaro, Gloria Villar
Department of Chemistry, University of Washington; Seattle, Washington, USA; kovacs@chem.washington.edu
Superoxide reductases (SOR) are cysteinate-ligated
non–heme iron enzymes that reduce superoxide (O2 –)
to H2O2 in anaerobic microbes. The cysteinate of
SOR is trans to the O2 – binding site, and is proposed
to play an important role in promoting the catalytic
reaction.[1] The proposed SOR mechanism involves
the oxidative addition of O2 – to the open site of the
square pyramidal FeIIN4 HisSCys active site to afford a
trans Scys-ligated FeIII-peroxo intermediate. Biomimetic analogues of this site will be described
which provide insight as to why nature utilizes a trans
thiolate to promote SOR function. Synthetic
analogues containing a thiolate either cis or trans to
the superoxide binding site will be described, which
convert superoxide to H2O2 via the first reported
examples of thiolate-ligated peroxo intermediates,
cis-[FeIII(SMe2N4(tren))(OOH)]+ [2, 3] and trans-
[FeIII(cyclam–PrS)(OOH)]+.[4] These compounds
provide important benchmark parameters for the
identification of biological intermediates. The
thiolate ligand and its trans positioning are shown to
contribute significantly to the catalyst's function, by
lowering the redox potential, changing the spin state,
and dramatically lowering the Fe-O stretching
frequency and force constant well-below that of any
other reported iron-peroxo.[1, 4]
(1) *Kovacs, J. A.; Brines, L. M. Acc. Chem. Res. 2007, 40, 501-509. (2) Shearer, J.; Scarrow, R. C.; *Kovacs, J. A.
J. Am. Chem. Soc. 2002, 124, 11709–11717. (3) Theisen, R. M.; *Kovacs, J. A. Inorg. Chem. 2005, 44, 1169-1171.
(4) Kitagawa, T.; Dey, A.; Lugo-Mas, P.; *Solomon, E. I.; *Kovacs, J. A. J. Am. Chem. Soc. 2006, 128, 14448-14449.
Julie Kovacs, b 1959 in E. Lansing, Michigan, USA. Michigan State University (BS 1981),
Harvard University (Ph.D. 1986, Prof. Richard Holm), UC Berkeley (Postdoc. 1988, Prof.
Robert Bergman). Associate Prof. (1994), Professor (2001- ). Research areas: synthetic
inorganic and bioinorganic chemistry, thiolate-ligated non-heme iron enzyme mimics.
40
Shie-Ming Peng Department of Chemistry, National Taiwan University, Taipei, Taiwan
Tel.: 886-2-23638305; Fax.: 886-2-83693765
Synthesis, Structure, Bonding
II. Potential Application as Molecular Metal Wires & Molecular Switches 4
STM Study on the Conductivity of Metal Strings C-AFM Measurements of Single Metal String Molecules Comparative Study on the I-V Characterisics (Theory V.S. Experiment)
III. Tuning of the Metal Strings 5,6
Naphthyridyl Amino Ligands: Low Oxidation Mixed Metal Strings Asymmetrical Ligands: Toward Molecular Rectifier Heteronuclear Metal String Complexes
IV. Conclusion Reference:
1. C.-Y. Yeh, C.-C. Wang, Y.-H. Chen and S.-M. Peng, in Redox Systems Under Nano-Space Control, Ed: T, Hirao, Springer, Germany, 2006, Ch. 5.
2. S.-Y. Lai, T.-W. Lin, Y.-H. Chen, C.-C. Wang, G.-H. Lee, M.-H. Yang, M.-K. Leung and S.-M. Peng, J. Am. Chem. Soc., 1999, 121, 250.
3. S.-J. Shieh, C.-C. Chou, G.-H. Lee, C.-C. Wang and S.-M. Peng, Angew. Chem. Int. Ed. Engl., 1997, 36, 56. 4. I.-W. P. Chen, M.-D. Fu, W.-H. Tseng, J.-Y. Yu, S.-H. Wu, C.-J. Ku, C.-H. Chen, and S.-M. Peng, Angew.
Chem. Int. Ed. Engl., 2006, 5414. 5. (a) C.-H. Chien, J.-C. Chang, C.-Y. Yeh, G.-H. Lee, J.-M. Fang and S.-M. Peng, Dalton Trans., 2006, 2106.
(b) C.-H. Chien, G.-H. Lee, Y. Song and S.-M. Peng, Dalton Trans., 2006, 3249. 6. M.-M. Rohmer, I. P.-C. Liu, J.-C. Lin, M.-J. Chiu, C.-H. Lee, G.-H. Lee, M. Benard, X. Lopez, S.-M. Peng,
Angew. Chem. Int. Ed. Engl., 2007, 46, 3533.
N N N N N
M M M M MX X
4
m
M = Ni, Co, Cr m = 0, 1, 2, 3 X = Cl, NCS
Shie-Ming Peng, Born 1949. B.S., 1970, National Taiwan Univ.; Ph.D., 1975, Univ. of Chicago.
Research Associate, 1975-76, Northwestern Univ. Associate Professor, 1976-80; Professor, 1980-
; Chairman, 1987-90, Dept. of Chemistry, NTU. Humboldt Research Fellow of Germany, 1983-
84. Research Fellow, 1982-; Acting Director, 1985-87, Institute of Chemistry, Academia Sinica;
Academician, 1998, Academia Sinica. Vice President, 1999-2002, National Taiwan University.
41
Cooperative Catalysis in the Catalytic Subunits of Xanthine Oxidase.
Kuo Chu Hwang*, Lin Ai Tai, and Hsin-Yin Lee Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan.
E-mail: kchwang@mx.nthu.edu.tw.
Xanthine oxidase (XOD) consists of two identical subunits. For the past 50 years or so, it was assumed that the two subunits carry out catalysis independently. We will present experimental data to show that the presence of 6-formylpterin (6FP), or other substrates (such as, xanthine or xanthopterin), at one of the two active sites affects the binding affinity and catalysis rate of 6FP at the other. When the two XOD active sites were occupied by two 6FPs simultaneously, the conversion rate (2.8 x 10-3 s-1) of 6FP to 6CP is 2.95 fold faster than the conversion rate (0.95 x 10-3 s-1) in the case of single 6FP bound condition. The presence of xanthine can accelerate the catalysis rate of 6FP by XOD as well as the activity-recovering rate of alloxanthine-inhibited XOD. Our experimental observations demonstrate unambiguously that the two XOD subunits are strongly cooperative in both binding and catalysis. The inhibition constant (Ki) of
6FP towards XOD was measured by a stopped-flow method to be 0.94 nM.
We will also present data to show that replacement of one single atom at the active site, namely replacing Mo=S by Mo=O, at one of the two active sites will lead to inactivation of the catalytic subunit. Single atom mutation at one of the active site could have dramatic effects on affecting the enzyme conformation, catalytic properties of the adjacent active site of ~ 50 away. Although the inactive catalytic subunit could not effectively contribute to the catalysis of enzyme substrates, it plays an important role in regulating the catalysis activity of the other subunit. All the results indicate that there exist very strong cooperative interactions between the two XOD catalytic subunits
Kuo Chu Hwang, born in 1959; BS in Chemistry, National Cheng Kung University
(1981); MS in Chemistry, National Tsing Hua University (1983); Ph.D. in Chemistry,
Columbia University, New York, U.S.A (1985~1990).; Postdoctoral research fellow,
Rockfeller University(1990~1992); Chareles H. Revson Biomedical Fellow, Rockfeller
University (1992~1993); Associate Professor, National Tsing Hua University
(1993~2000), Professor (2000-). Research fields: Enzyme kinetics, Carbon Nanotubes/
Nanoparticles/ Nanomaterials and Photochemistry.
Enhanced Charge Carrier Mobility Derived from Cyclization of a Silene Unit on Silole Derivatives: Syntheses, Photophysical Properties and Device Fabrication of Spiro-Siloles
Ho-Jin Son, Won-Sik Han, Ji-Yun Chun, Soon-Nam Kwon, Jaejung Ko, and Sang Ook Kang*
Department of Material Chemistry, Korea University; Chochiwon, Chung-Nam, South Korea; sangok@korea.ac.kr
As an extension of our effort to improve charge-
transporting capability on silole derivatives,
introduction of cyclic ring on the bridge-head 1,1’-
position of the silole ring has been attempted. Indeed,
resultant exo-cyclic ring substituted siloles exhibited
increased charge-carrier mobility based on the TOF
measurement. In order to explore the origin of
enhanced mobility, solid state structural studies on a
series of exo-cyclic ring substituted siloles were
performed. Strong intermolecular interaction between
adjacent siloles ring was observed in solid state
packing when compared with non-cyclic siloles.
Constrained geometry on silole silicon atom renders
such an impressive improvement on charge carrier
mobility, thereby allowing to manufacture advanced
devices both on OLEDs and OTFTs. Unique feature
regarding to silole modification along with new
concept of device fabrication will be presented.
(1) H.-J. Son, W.-S. Han, J-Y. Chun, C.-J. Lee, J.-I. Han, J. Ko, S. O. Kang, Organometallics 2007, 26, 519.
Sang Ook Kang, b 1958 in Che-Ju, South Korea. Korea Univ. (BS 1980; MS 1982), Univ. of
Pennsylvania (Ph.D. 1988, Prof. Larry. G. Sneddon), M. I. T. (Postdoc. 1989, Prof. Dietmar
Seyferth) Associate Prof. (1989), Professor (1993). Research field: Polyolefin catalyst, Organic
Electronics (OLEDs and OTFT), Boron delivery system for Neutron Capture Therapy,
Carborane Chemistry, Hydrogen Storage.
Leonard V. Interrante
Our efforts over the past 20+ years on the synthesis
and study of polycarbosilanes [1] has led to the
development of a precursor for SiC that is now being
produced and used commercially to fabricate ceramic
composites for a variety of applications, on earth, such
as friction materials (brakes) for motorcycles and
other land vehicles, and in space, in an emergency
repair kit on the U.S. space shuttle [2]. The basic
research that led to the discovery of this precursor (a
hyperbranched) polycarbosilane), as well as the
applications that have resulted, will be described,
along with the results of our more recent efforts to
employ a novel series of cyclolinear polycarbosilanes
[3] as a source of low-k materials for integrated
circuits [4].
[1] Q. Shen and L.V. Interrante, “Polycarbosilanes”, Chapter 10, in “Silicon-Containing Polymers: The Science and
Technology of Their Synthesis and Applications”, Kluwer Publ. Co., W. Ando, J. Chojnowski and R. Jones, eds.,
(2000), pp. 247-274.
[2] Starfire Systems, Inc. Saratoga Technology and Energy Park, 10 Hermes Rd., Suite 100, Malta, NY 12020 USA;
http://www.starfiresystems.com/
[3] Z. Wu, et. al., Macromolecules, 37(14), 5257 (2004); P.-I. Wang, Z. Wu, T.-M. Lu and L.V. Interrante, J.
Electrochem. Soc., 153(4), G267 (2006); J.-Y. Hyun, J. Han, C.Y. Ryu, L.V. Interrante, Macromolecules 39(25),
8684-8691 (2006).
Leonard V. Interrante, b 1939 in New York, U.S.A.; U. Calif. Riverside (AB 1960);
Univ. of Illinois at Urbana-Champaign (Ph.D. 1964, Prof. J. Bailar), Univ. College
London (NSF Postdoct. Fellow. 1964, Prof. R. Nyholm) Asst. Prof. (1964-8), U.C.
Berkeley; Research Staff, GE Corp. Res. Devel., Schenectady, NY (1968-85);
Professor, Rensselaer Polytechnic Institute (1985-),. Research field: organosilicon
polymer chemistry; ceramic precursors; synthesis, properties and applications of
polycarbosilanes low-k dielectric materials for electronics.
44
Hong-Ping Lin*, Chang-Chien, Chun-Yi, Hsu, Chun-Han, Tsung-Ying Lee, Che-Wei Liu,
Sheng-Ho Wu Department of Chemistry, National Cheng Kung University, Tainan, Taiwan, 701. hplin@mail.ncku.edu.tw
Mesoporous carbon of high surface area, porosity
and good electric conductivity has been widely used
as the material for supercapacitor and electrode of the
direct methanol fuel cell. To avoid the complicated
process including synthesis of surfactant-silica
composite, surfactant-removal, carbon source
source-silica nanocomposite in one step by usung
phenol formaldehyde-silica gelling polymer blend as
the template. The resulting mesoporous carbons
possess a high surface area of 1000-1600 m2g-1 and
large pore size of 2.0-8.0 nm. In addition, the
morphology of the mesoporous carbons can be
tailored to fibers, rods, hollow spheres, and foams by
using different silica-gelling polymer.
carbons of high surface area can be considered as
good material for preparing the supercapacitor and
support of Pt-Ru alloy nanoparticles. The mesoporous
carbons exhibit electric capacity of 120-200 Fg-1 in
2.0 M H2SO4 electrolyte solution at scan rate of 5-
3000 mVs-1. The Pt-Ru nanoparticles less than 5.0 nm
were well dispersed on the mesoporous carbons that
can be used as a high-efficiency electrode in direct
methanol fuel cell. In addition, the thermal stable
mesoporous carbon was used as solid nanotemplate to
prepare different metal oxides hollow spheres. After
impregnation of proper metal-oxides precursors and
calcination, the γ-Al2O3, anatase-TiO2, α-Fe2O3, ZrO2, MgO, and CeO2 hollow spheres composed of
nanoparticles have been readily synthesize.
(1) Chang-Chien, C. Y., Hsu C. H., Lee, T. Y., Liu C. W., Wu, S. H. Lin, H P, Tang, C. Y., Lin, C. Y. Eur. J. Inorg.
Chem. 2007, 29, 3798. (2) Wu, S. H., Lin, Y. C., Liu, C. W., Lin, H. P., Huang, C. W., Deng, S., Yang, M. C., Tang, C.
Y., Lin, C. Y., Journal of Solid State Electrochemistry, 2007, in press.
Hong-Ping Lin, b 1969 in Taichun, Taiwan. National Cheng Kung Univ. (BS 1991; MS 1993),
National Taiwan Univ. (Ph.D. 1997, Prof. C. Y. Mou), Institute of Atomic and Molecular Sciences,
Academia Sinica. (Postdoc. 1997, Prof. B. S. B. Liu) Assistant Prof. (2002), Associate Professor
(2005-). Research filed: Material Chemistry, Physical Chemistry, Porous Material.
200 nm 200 nm
Jiann T’suen Lin
Integration of segments capable of electron-
transporting and segments capable of hole-
transporting in the same molecule has been found to
be an efficient strategy for the development of
compounds exhibiting ambipolar transport
mobilities were measured by the time-of-flight (TOF)
transient photocurrent technique. Some of the
compounds exhibit a very high electron mobility
ranging from ~10-4 – 10-3 cm2V-1s-1. These ambipolar
transport materials were subjected to organic light-
emitting diodes (OLEDs) fabrication. Double-layered
devices in which the ambipolar transport molecules
are used as electron-transporting and emitting layer, or
as hole-transporting and emitting layer have been
successfully fabricated and exhibited good
performance. Of particularly interesting is that
molecules with comparable electron and hole
mobilities can be fabricated as single component,
single-layered devices. Both green- and blue-emitting
single component, single-layered devices of high
performance will be demonstrated. Upon doping with
phosphorescent materials, high performance single-
layered phosphorescent OLEDs can also be achieved.
S OO
N N
Electron Hole
Electron Hole
M ob
ili ty
(c m
E1/2 (V/cm)1/2
(1) Justin Thomas, K. R.; Velusamy, M.; Lin, J. T.; Y.-T. Tao, Y.-T.; Chuen, C.-H. Adv. Funct. Mater. 2004, 14, 387.
(2) Huang, T.-H.; Lin, J. T.; Chen, L.-Y.; Lin, Y.-T.; Wu, C.-C. Adv. Mater. 2006, 18, 602. (3) Lai, M.-Y.; Chen, C.-H.;
Huang, W.-S.; Lin, J. T.; Ke, T.-H.; Chen, L.-Y.; Tsai, M.-H.; Wu C.-C. Angew. Chem. Int. Ed. 2007, accepted.
Jiann T’suen Lin, b 1952 in Taiwan. National Tsing-Hua Univ. (BS 1975), Univ. of Minnesota
(Ph.D. 1983, Prof. J. E. Ellis), University of Michigan (Postdoc. 1983, Prof. R. L. Kuczkowski),
Associate Research Fellow. (1984), Research Fellow (2000-). Research filed: organic and
organometallic optoelectronic materials for light-emitting diodes, solar cells, two-photon
absorption, and field-effect transistors.
Playing with Fire: the Mechanism of Copper-Catalyzed Azide-Alkyne Cycloaddition
Valentin O. Rodionov, Stanislav Presolski, Valery V. Fokin, and M.G. Finn*
Department of Chemistry, The Scripps Research Institute, La Jolla, CA 92037, USA; mgfinn@scripps.edu
CuI-catalyzed azide-alkyne cycloaddition has
2002. Kinetics measurements performed in the
presence and absence of accelerating ligands such as
the ones shown below left, have revealed an
adjustable mechanism that responds to changes in
reaction conditions to maintain high rates and perfect
stereoselectivity. Highly effective ligands share the
features of a central tertiary nitrogen center
surrounded by heterocyclic donors of weak-to-
moderate affinity for CuI. It is proposed that these
properties help to insure the existence of kinetically
labile metal centers that allow the assembly of a
binuclear interaction presenting azide to an activated
σ,π-bound acetylide ligand (below, right). The
relative merits of different classes of accelerating
ligands will also be discussed, as well as the
performance of various catalyst formulations under
demanding conditions of low catalyst loading and
bioconjugation applications involving low
Z Z Z N
Z
ligand
NN
(1) Rodionov, V.O.; Presolski, S.; Gardinier, S.; Lim, Y.-H.; Finn, M.G. J. Am. Chem. Soc. 2007, ASAP.
(2) Rodionov, V.O.; Presolski, S.; Díaz, D.D.; Fokin, V.V.; Finn, M.G. J. Am. Chem. Soc. 2007, ASAP.
M.G. Finn, b 1958. California Institute of Technology (BS 1980), Massachusetts Institute of
Technology (Ph.D. 1986, Prof. K.B. Sharpless), Stanford University (Postdoc, 1988, Prof. J.P.
Collman). University of Virginia, Assistant Prof. (1988), Assoc. Prof. (1994). The Scripps
Research Institute (1998-). Research interests: chemistry, biology, and materials science with
viruses; click reaction development, application, and mechanism; asymmetric catalysis;
traditional and combinatorial synthesis of biologically active compounds; molecular evolution.
47
Institute of Organic Chemistry, RWTH Aachen University; 52056 Aachen, Germany;
Carsten.Bolm@OC.RWTH-Aachen.de
have recently been developed in our group, will be
discussed [1]. Representative examples are:
Asymmetric iron-catalyzed sulfoxidations with
meric excesses (up to 96% ee) can be obtained by
asymmetric iron-catalyzed oxidations with hydrogen
peroxide as oxidant [2].
sulfides with sulfonylamides in the presence of
iodinanes provide an effective (stereospecific) access
to sulfoximines and sulfilimines, respectively [3].
Iron-catalyzed cross-couplings4
and appropriate ligands N- and O-arylations can be
performed to provide N-aryl heteroarenes 7 and
diarylethers 8, respectively [4].
[1] For a review on iron-catalyzed reactions, see: Bolm, C.; Legros, J.; Le Paih, J.; Zani, L. Chem. Rev. 2004, 104,
6217. [2] (a) Legros, J.; Bolm, C. Angew. Chem. Int. Ed. 2003, 42, 5487. (b) Legros, J.; Bolm, C. Angew. Chem. Int.
Ed. 2004, 43, 4225. (c) Legros, J.; Bolm, C. Chem. Eur. J. 2005, 11, 1086. (d) Korte, A.; Legros, J.; Bolm, C. Synlett
2004, 2397. [3] (a) García Mancheño, O.; Bolm, C. Org. Lett. 2006, 8, 2349. (b) García Mancheño, O.; Bolm, C.
Chem. Eur. J. 2007, 13, 6674. [4] (a) Correa, A.; Bolm, C. Angew. Chem. in press. (b) Bistri, O.; Correa, A.; Bolm, C.
Angew. Chem. accepted for publication.
Carsten Bolm, b 1960 in Braunschweig, Germany. Univs. Braunschweig and Madison (Dipl.,
MS 1984), Univ. of Marburg (Ph.D. 1987, Prof. M. T. Reetz), M.I.T (Postdoc. 1998, Prof. B.
Sharpless), Ass