Kyushu University Academic Staff Educational and Research Activities Database
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Nobuo Kimizuka Last modified date:2019.06.18

Professor / Biofunctional Chemistry
Department of Applied Chemistry
Faculty of Engineering


Graduate School
Other Organization
Administration Post
Diredtor of the International Reseach Center for Molecular Systems


E-Mail
Homepage
http://www.chem.kyushu-u.ac.jp/~kimizuka/
Kimizuka Laboratory .
http://www.chem.kyushu-u.ac.jp/~cms/
International Research Center for Molecular Systems
.
Academic Degree
Doctor of Engineering
Field of Specialization
Molecular Systems Chemistry
Outline Activities
[Research]
(1) Development of Molecular Systems Chemistry
(2) Molecular design and development of photon-upconversion materials based on self-assembly
(3) Molecular design and development of supramolecular solar thermal fuels
(4) Molecular design and development of self-assembling coordination polymers and their functions
(5) Molecular self-assembly under far-from-equilibrium conditions and development of dissipative nanostructures
(6) Self-assembly in ionic liquids
(7) Interfacial chemistry in ionic liquids and development of nano-interfacial materials
(8) Molecular informatics based on molecular self-assembly
(9) Design and development of molecular learning systems

[Awards]
1993 Young Researcher Award, The Society of Polymer Science (SPSJ), Japan
1999 Kao Research Initiative Award, The Kao Foundation of Arts and Sciences.
2003 Wiley Award, The Society of Polymer Science, Japan (SPSJ)
2007 The Chemical Society of Japan Award for Creative Work
2012 The Award of the Society of Polymer Science, The Society of Polymer Science,
Japan (SPSJ)
2013 Prizes for Science and Technology, The Minister of Education, Culture, Sports,
Science and Technology.
Research
Research Interests
  • Development of Photon Upconversion system based on molecular self-assembly
    keyword : photon upconversion, self-assembly, triplet, triplet-triplet annihilation
    2012.04.
  • Development of Molecular Systems Chemistry
    keyword : Molecular Systems Chemistry
    2007.04.
  • Construction of Functional Bio-Nanoarchitectures based on the Molecular Pairing Technique
    keyword : Nucleotides, Peptides, Dyes, Lanthanide ions
    1999.04~2013.03.
  • Self-Assembly of One-Dimensional Metal Complexes at Interfaces and Their Functions
    keyword : mixed valence complexes, self-assembly
    2007.04~2013.03.
  • Self-Assembly of Mixed Valence Metal Complexes on Surfaces and their Application to Molecular Memory Systems
    keyword : mixed valence complex, self-assembly, atomic force microscopy
    2007.04~2013.03.
  • Development of Ferroelectric Nanomaterials based on Self-Assembly
    keyword : mixed valence complexes, charge transfer, ferroelectricity
    2007.04.
  • Design of Molecular Information Processing by using Self-Assembled Metal Complexes
    keyword : Spin Crossover, Molecular Information, Self-Assembly
    1998.04.
  • Bottom-up Synthesis of Metaloxide Nanocorals and their Functions
    keyword : Metal oxide, Titanium dioxide, Zinc oxide, Nanoreef
    2007.04~2013.03.
  • Synthesis of Protein Hollow Microcapsules at the Ionic Liquid/Water Interfaces and their Spatial Functions
    keyword : Ionic Liquid, Protein, Peptide, Enzyme, Nucleic Acid
    2000.04~2010.03.
  • The Integration of Bottom-up and Top-down Nanomanufacturing Approaches at the Nano-Interfaces
    keyword : Nano-Interface, Self-Assembly
    2007.06~2013.03.
  • Development of Biomolecular Self-Assemblies and Their Functions
    keyword : Peptides, Proteins, Nucleic Acids, Sugars
    1999.04~2013.03.
  • Supramolecular and Interfacial Chemistry in Ionic Liquids and their Applications
    keyword : Ionic Liquid, Self-Assembly, Sugar, Proteins, Hollow Microcapsules, Bilayer Membrane
    1999.04~2015.03.
  • Development of Self-Assembling Metal Nanoparticle Systems
    keyword : self-assembly, metal nanoparticles, ferrocene
    1999.04~2013.03.
  • Development of Self-Assembling Molecular Wires based on Linear Metal Complexes as Main Chains
    keyword : One-Dimensional Metal Complex, Supermolecules
    1997.04.
Current and Past Project
  • This project aims to develop new molecular self-assembly and self-organization techniques to engineer new functional exploitable materials with varied nano-interface architectures. Fabrication of nano-interface architectures by interdisciplinary molecular self-assembly is a key feature of the project, and their components are widely selected from organic, inorganic, metal complexes to biomolecules. It will provide a new platform for designing molecular-system memories, nano-dielectrics, surface sensors and bio-nanodevices.
Academic Activities
Papers
1. Kazuma Mase, Yoichi Sasaki, Yoshimitsu Sagara, Nobuyuki Tamaoki, Christoph Weder, Nobuhiro Yanai, Nobuo Kimizuka, Stimuli-Responsive Dual-Color Photon Upconversion
A Singlet-to-Triplet Absorption Sensitizer in a Soft Luminescent Cyclophane, Angewandte Chemie - International Edition, 10.1002/anie.201712644, 57, 11, 2806-2810, 2018.03, Reversible emission color switching of triplet–triplet annihilation-based photon upconversion (TTA-UC) is achieved by employing an Os complex sensitizer with singlet-to-triplet (S-T) absorption and an asymmetric luminescent cyclophane with switchable emission characteristics. The cyclophane contains the 9,10-bis(phenylethynyl)anthracene unit as an emitter and can assemble into two different structures, a stable crystalline phase and a metastable supercooled nematic phase. The two structures exhibit green and yellow fluorescence, respectively, and can be accessed by distinct heating/cooling sequences. The hybridization of the cyclophane with the Os complex allows near-infrared-to-visible TTA-UC. The large anti-Stokes shift is possible by the direct S-T excitation, which dispenses with the use of a conventional sequence of singlet–singlet absorption and intersystem crossing. The TTA-UC emission color is successfully switched between green and yellow by thermal stimulation..
2. Nobuo Kimizuka, Keita Ishiba, 野口 誉夫, Masa-aki Morikawa, K. Kaneko, Hiroaki Iguchi, Photoresponsive Nanosheets of Polyoxometalates Formed by Controlled Self-Assembly Pathways, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 10.1002/anie.201612473, 56, 11, 2974-2978, 2017.03, Anionic Keggin polyoxometalates (POMs) and ether linkage‐enriched ammonium ions spontaneously self‐assemble into rectangular ultrathin nanosheets in aqueous media. The structural flexibility of the cation is essential to form oriented nanosheets; as demonstrated by single‐crystal X‐ray diffraction measurements. The difference in initial conditions exerts significant influence on selecting for self‐assembly pathways in the energy landscape. Photoillumination of the POM sheets in pure water causes dissolution of reduced POMs, which allowed site‐specific etching of nanosheets using laser scanning microscopy. By contrast, photoetching was suppressed in aqueous AgNO3 and site‐selective deposition of silver nanoparticles occurred as a consequence of electron transfer from the photoreduced POMs to Ag+ ions on the nanosheet surface..
3. R. Kuwahara, S. Fujikawa, K. Kuroiwa, N. Kimizuka,, Controlled Polymerization and Self-Assembly of Halogen-Bridged Diruthenium Complexes in Organic Media and Their Dielectrophoretic Alignment
, J. Am. Chem. Soc, 10.1021/ja208958t, 134, 1192-1199 , 2012, 2012.01, Lipophilic paddlewheel biruthenium complexes [Ru2(μ-O2CR)3X]n (O2CR = 3,4,5-tridodecyloxybenzoate, X = Cl, I) self-assemble in organic media to form halogen-bridged coordination polymers. The polymerization is accompanied by spectral changes in π(RuO,Ru2) → π*(Ru2) and π(axial ligand) → π*(Ru2) absorption bands. These polymeric complexes form lyotropic liquid crystals in n-decane at concentrations above 100 unit mM. The bridging halogen axial ligands (X = Cl or I) exert significant influences on their electronic structures and self-assembling characteristics: the chloride-bridged polymers give hexagonally aligned ordered columnar structure (columnar hexagonal phase, Colh), whereas the iodide-bridged polymers form less ordered columnar nematic (Coln) phase, as revealed by small-angle X-ray diffraction measurements. Chloro-bridged coordination polymers dispersed in n-decane are thermally intact even at the elevated temperature of 70 °C. In contrast, iodo-bridged polymers show reversible dissociation and reassembly phenomena depending on temperature. These halogen-bridged coordination polymers show unidirectional alignment upon applying alternating current (ac) electric field as investigated by crossed polarizing optical microscopy and scanning electron microscopy. The unidirectionally oriented columns of chloro-bridged polymers are accumulated upon repetitive application of the ac voltage, whereas iodo-bridged coordination polymers show faster and reversible alignment changes in response to turning on-and-off the electric field. The controlled self-assembly of electronically conjugated linear complexes provide a potential platform to design electric field-responsive nanomaterials..
4. J. Liu, M-A. Morikawa, N. Kimizuka, , Conversion of Molecular Information by Luminescent Nanointerface Self-Assembled from Amphiphilic Tb(III) Complexes, J. Am. Chem. Soc, 10.1021/ja2057924, 133, 43, 17370-17374, 2011, 2011.09, A novel amphiphilic Tb3+ complex (TbL+) having anionic bis(pyridine) arms and a hydrophobic alkyl chain is developed. It spontaneously self-assembles in water and gives stable vesicles that show sensitized luminescence of Tb3+ ions at neutral pH. This TbL+ complex is designed to show coordinative unsaturation, i.e., water molecules occupy some of the first coordination spheres and are replaceable upon binding of phosphate ions. These features render TbL+ self-assembling receptor molecules which show increase in the luminescence intensity upon binding of nucleotides. Upon addition of adenosine triphosphate (ATP), significant amplification of luminescent intensity was observed. On the other hand, ADP showed moderately increased luminescence and almost no enhancement was observed for AMP. Very interestingly, the increase in luminescence intensity observed for ATP and ADP showed sigmoidal dependence on the concentration of added nucleotides. It indicates positive cooperative binding of these nucleotides to TbL+ complexes preorganized on the vesicle surface. Self-assembly of amphiphilic Tb3+ receptor complexes provides nanointerfaces which selectively convert and amplify molecular information of high energy phosphates linked by phosphoanhydride bonds into luminescence intensity changes..
5. Ryuhei Nishiyabu,Carole Aime,Ryosuke Gondo,Takao Noguchi,Nobuo Kimizuka, Confining molecules within aqueous coordination nanoparticles by adaptive molecular self-assembly , Angew. chem. Int. ED, , 10.1002/anie.200904124, 9, No.50,, 9465-9468, 2009.11.
6. Tetsuro Soejima, Masa-aki Morikawa, Nobuo Kimizuka, Holey Gold Nanowires Formed by Photoconversion of Dissipative Nanostructures Emerged at the Aqueous-Organic Interface, small, 10.1002/smll.200900348, 5, , No.18,, 2043-2047 , 2009.07.
7. Tetsuro Soejima,, Nobuo Kimizuka, One-Pot Room-Temperature Synthesis of Single-Crystalline Gold Nanocorolla in Water, J. Am. Chem. Soc, 5, , No.18,, 2043-2047 , 2009.07.
Presentations
1. Nobuo Kimizuka, Photon Upconversion based on Energy Migration in Molecular Assemblies, 9th International Symposium on Nano & Supramolecular Chemistry (9th ISNSC), 2017.09, Triplet-triplet annihilation-based photon upconversion (TTA-UC) is a promising methodology which can be applied to many sunlight-based energy conversion systems. To date, efficient TTA-UC has been achieved in solution based on the molecular diffusion of excited triplet molecules. However, the diffusion of chromophores in such low-viscosity solvent is not high enough to maximize the UC quantum yield at low solar irradiance. To solve these problems, we introduced the concepts of energy migration in ordered molecular self-assemblies1 to achieve efficient TTA-UC in molecular systems.2-10 Interestingly, some of the molecular self-assemblies dispersed in solution or organogels revealed oxygen barrier properties, which allowed TTA-UC even under aerated conditions.2,3,5,8-10 In this talk, our recent development on the supramolecular TTA-UC in varied molecular systems will be discussed..
2. Development of Functional Molecular Systems Based on Self-Assembly.
Membership in Academic Society
  • Photo Chemistry
  • The American Association for the Advancement of Science
  • American Chemical Society
  • The Chemical society of Japan
  • Division of Surface colloid and Chemistry
  • The society of polymer Science Japan
  • The society of Synthetic Organic Chemistry Japan
Awards
  • Development of Functional Molecular Systems Based on SelfAssembly
Educational
Educational Activities
(1)Protein Chemistry, (2)Nucleic Acid Chemistry, (3)Molecularly Organized Chemistry for Graduate students
(4) Synthetic Polymer Chemistry for undergraduate students.
Other Educational Activities
  • 2015.03.
  • 2014.03.
  • 2004.07.