Updated on 2024/04/16

写真a

 
USUI Satoshi
 
Organization
Academic Assembly Institute of Science and Technology CHIKYU SEIBUTSU KAGAKU KEIRETU Associate Professor
Graduate School of Science and Technology Environmental Science and Technology Associate Professor
Faculty of Science Department of Science Associate Professor
Title
Associate Professor
Contact information
メールアドレス
External link

Degree

  • 理学博士 ( 1993.3   九州大学 )

Research Interests

  • ソルボリシス機構の理論的研究

  • 光加溶媒分解反応機構

  • Photosolvolysis Mechanism

  • Photoinduced Electron Transfer

  • 光誘起電子移動

  • Theoretical Studies on Solvolysis Mechanism

Research Areas

  • Life Science / Bioorganic chemistry

  • Nanotechnology/Materials / Structural organic chemistry and physical organic chemistry

  • Nanotechnology/Materials / Fundamental physical chemistry

Research History

  • Niigata University   Faculty of Science Department of Science   Associate Professor

    2017.4

  • Niigata University   Graduate School of Science and Technology Environmental Science and Technology   Associate Professor

    2010.4

  • Niigata University   Graduate School of Science and Technology Environmental Science and Technology   Associate Professor

    2010.4

  • Niigata University   Faculty of Science Department of Environmental Science   Associate Professor

    2004.4 - 2017.3

  • Niigata University   Faculty of Science   Lecturer

    1996.4 - 1999.2

Education

  • Kyushu University   理学研究科   化学

    - 1985

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    Country: Japan

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  • Kyushu University   Graduate School, Division of Natural Science

    - 1985

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  • Kyushu University   Faculty of Science

    - 1983

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  • Kyushu University   School of Sciences   化学

    - 1983

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    Country: Japan

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Professional Memberships

 

Papers

  • CATALYTIC ACTIVITIES OF NOVEL L-HISTIDYL GROUP-INTRODUCED POLYMERS IMPRINTED BY A TRANSITION-STATE ANALOG IN THE HYDROLYSIS OF AMINO-ACID ESTERS Reviewed

    K OHKUBO, Y URATA, S HIROTA, Y FUNAKOSHI, T SAGAWA, S USUI, K YOSHINAGA

    JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL   101 ( 2 )   L111 - L114   1995.8

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:ELSEVIER SCIENCE BV  

    The catalytic activities of L-histidyl group-introduced, cross-linked polymers imprinted by a transition-state analogue (phenyl 1-benzyloxycarbonylamino-3-methylpentylphosphonate) or a ground-state one (N-(N-benzyloxycarbonyl-L-leucinoyl)anthranilic acid) for the esterolysis of a marked substrate of p-nitrophenyl N-benzyloxycarbonyl-L-leucinate were examined in the hydrolysis of amino acid esters; a transition-state analogue recorded polymer possessing a low cross-linker content (8.7%) exhibited the highest catalytic activity for the marked substrate hydrolysis with the positively largest activation entropy and the smallest activation free energy.

    DOI: 10.1016/1381-1169(95)00097-6

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  • High esterolytic activity of a novel water-soluble polymer catalyst imprinted by a transition-state analogue Reviewed

    Katsutoshi Ohkubo, Yoshio Funakoshi, Yasuo Urata, Shogo Hirota, Satoshi Usui, Takashi Sagawa

    Journal of the Chemical Society, Chemical Communications   ( 20 )   2143 - 2144   1995

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    Language:English   Publishing type:Research paper (scientific journal)  

    A novel water-soluble polymer catalyst containing a L-histidyl group as a catalytic site, prepared by imprinting of a transition-state analogue of phenyl 1-benzyloxycarbonyl-3-methylpentyl phosphonate, accelerates the substrate-specific esterolysis of p-nitrophenyl N-(benzyloxycarbonyl)-L- leucinate (Z-L-Leu-PNP) in 10 vol% Me2O-Tris buffer (pH 7. 15) at 293-308 K.

    DOI: 10.1039/C39950002143

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Books

  • 弥彦・角田山から地球環境を考える

    新潟日報事業社  2004 

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  • 分子集合体中における光誘起電子移動反応と後続反応における磁場効果

    エルセビア出版  1991 

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  • "MAGNETIC FIELD EFFECTS ON PHOTOINDUCED ELECTRON TRANSFER AND THE SUCCEEDING PROCESSES IN ORGANIZED MOLECULAR ASSEMBLIES"

    "Photochemical Processes in Organized Molecular Systems"ed. by K. Monda Elsevier  1991 

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MISC

  • 冬季の弥彦山頂における大気および降雪酸性成分の観測

    弥彦山・角田山とその周辺の環境科学   15-23   2003

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  • 弥彦山頂の酸性雪・大気観測期間における気象状況

    弥彦山・角田山とその周辺の環境科学   5-14   2003

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  • Stereoselectivities in AgBF4-catalyzed and photoinduced phenyl-rearrangement of 2-chloropropiophenone

    S Usui, T Matsumoto, K Ohkubo

    TETRAHEDRON LETTERS   39 ( 52 )   9755 - 9758   1998.12

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    Language:English   Publisher:PERGAMON-ELSEVIER SCIENCE LTD  

    (S)-2-Phenylpropionic acid was stereoselectively obtained by the AgBF4- catalyzed phenyl-rearrangement of (S)-2-chloropropiophenone dimethyl acetal, while the photoirradiation of (S)- or (R)-2-chloropropiophenone afforded partially racemized (S)- or (R)-2-phenylpropionic acid, respectively. An intramolecular S(N)2 mechanism is suggested for the former rearrangement. The latter result is indicative of the intervention of an ion or radical intermediate in the photoinduced phenyl-rearrangement. (C) 1998 Elsevier Science Ltd. All rights reserved.

    DOI: 10.1016/S0040-4039(98)02284-9

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  • 2-クロロプロピオフェノンのAgBF<sub>4-</sub>及び光誘起フェニル転位反応における立体選択性

    39   9755   1998

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  • Extremely high stereoselectivity of novel helical ruthenium(II) complexes for photoinduced reduction of racemic-[Co(acac)(3)] (Hacac=pentane-2,4-dione)

    K Ohkubo, M Fukushima, H Ohta, S Usui

    JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY   98 ( 3 )   137 - 140   1996.8

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    Language:English   Publisher:ELSEVIER SCIENCE SA LAUSANNE  

    A photocatalyst M(C-3)-Delta-[Ru(menbpy)(3)](2+) (menbpy = 4,4'-bis{(1R,2S,5R)-(-)-methoxycarbonyl}-2,2'-bipyridine; M(C-3) = minus (counterclockwise) helical arrangement along the C-3 symmetry axis) possessing a lang lifetime tau and the low quantum yield of photoracemization Phi(rac) (tau = 1500 ns and Phi(rac) = 4.0 x 10(-6) in EtOH at 298 K) facilitated the asymmetric reduction of racemic Delta,Lambda-[Co(acac)(3)] (Hacac = pentane-2,4-dione) at 298 K in deaerated 90% v/v EtOH-H2O; it exhibited extremely high stereoselectivity with the enantiomer rate ratio k(Delta)/k(Lambda) = 14.79 (in the absence of Hacac) -91.9 (in the presence of Hacac).

    DOI: 10.1016/1010-6030(95)04286-5

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  • The role of membrane-promoted multi-point hydrophobic interactions between peptide catalysts and enantiomeric substrates in highly stereoselective hydrolyses of amino acid esters

    K Ohkubo, K Urabe, J Yamamoto, S Usui, T Sagawa

    JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL   110 ( 1 )   L1 - L4   1996.7

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    Language:English   Publishing type:Rapid communication, short report, research note, etc. (scientific journal)   Publisher:ELSEVIER SCIENCE BV  

    The 500 MHz(1)H NMR NOESY spectra of membrane-promoted multi-point hydrophobic interactions between peptide catalysts and enantiomeric amino acid esters were detected for clarifying the role of muti-point interactions between the reactants in the highly stereoselective hydrolysis reactions in a vesicular membrane.

    DOI: 10.1016/1381-1169(96)00157-4

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  • Novel photocatalytic asymmetrical synthesis of Delta (or Lambda)-[Co(acac)(3)] (acac, pentane-2,4-dione) from [Co(acac)(2)(H2O)(2)] and Hacac with helical ruthenium(II) complexes

    K Ohkubo, M Watanabe, H Ohta, S Usui

    JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY   95 ( 3 )   231 - 233   1996.5

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    The photocatalytic asymmetrical synthesis of Delta (or Lambda)-[Co(acac)(3)] (acac, pentane-2,4-dione) from [Co(acac)(2)(H2O)(2)] and Hacac was successfully performed with novel helical ruthenium(II) complexes of Delta-[Ru(Menbpy)(3)](2+) (1; Menbpy, 4,4'-bis{(1R,2S,5R)-(-)-menthoxycarbonyl}-2,2'-bipyridine), Delta-[Ru(R-PhEtbpy)(3)](2+) (2a), Lambda-[Ru(S-PhEtbpy)(3)](2+) (2b) (R- or S-PhEtbpy, 4,4'-bis[(R)-(+)- or (S)-(-)-1-phenylethylaminocarbonyl]-2,2'-bipyridine) and Delta-[Ru(bpy)(3)](2+) (3; bpy, 2,2'-bipyridine); photocatalyst 1 possesses the most efficient extent of minus (counterclockwise) M(C-3) helicity along the C-3 symmetry axis, resulting in a maximum enantiomeric excess (37% e.e.) of Lambda-[Co(acac)(3)] in 50% v/v EtOH-H2O at 298 K.

    DOI: 10.1016/1010-6030(95)04263-6

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  • The role of the membrane-assisted hydrophobic interaction between di-, tri-, or tetrapeptide catalysts and amino acid esters for the enhancement of stereoselective hydrolysis reactions

    K Ohkubo, K Urabe, S Usui, T Sagawa

    MACROMOLECULAR RAPID COMMUNICATIONS   17 ( 2 )   109 - 116   1996.2

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    Language:English   Publisher:HUTHIG & WEPF VERLAG  

    The peptide catalyst having the amino acid sequence (Z-L-Leu (or Phe)-L-His) was found to be the most stereoselective among the L-histidyl group-containing di-, tri-, or tetrapeptide catalysts in the hydrolysis of enantiomeric amino acid substrates in vesicular membranes. The role of the membrane-assisted hydrophobic interaction between the peptide catalyst and enantiomeric substrates for the improvement of the hydrolysis stereoselectivity was demonstrated by means of direct measurements of nuclear Overhauser effect spectroscopy (NOESY) spectra of the interaction system and by the extremely high stereoselectivity itself obtained by intensifying the membrane-promoted hydrophobic interaction between the catalyst and the substrates.

    DOI: 10.1002/marc.1996.030170206

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  • アセチルアセトンとヘリカルルテニウム錯体(II)によるΔ-(あるいはΛ-)[Co(acac)<sub>3</sub>]の[Co(acac)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]からの新規な光触媒的不斉合成

    93   231   1996

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  • ペプチド触媒と光学活性基質との二分子膜中での多点相互作用による高立体選択的アミノ酸エステルの加水分解反応

    110   L1   1996

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  • 新規ヘリカルルテニウム(II)錯体による[Co(acac)<sub>3</sub>]ラセミ体の高立体選択的光還元反応

    98   137   1996

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  • ジ、トリ、テトラペプチド触媒とアミノ酸エステルの二分子膜による水素結合相互作用による立体選択的加水分解反応

    17   109   1996

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  • NOVEL STEREOSELECTIVE INCORPORATION AND HYDROLYSIS OF LONG-CHAIN AMINO-ACID SUBSTRATES BY VESICULAR MEMBRANE SYSTEMS WHICH INCLUDE TRI-PEPTIDE OR TETRA-PEPTIDE CATALYSTS

    K OHKUBO, K URABE, J YAMAMOTO, T SAGAWA, S USUI

    JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1   ( 23 )   2957 - 2959   1995.12

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    Language:English   Publishing type:Article, review, commentary, editorial, etc. (scientific journal)   Publisher:ROYAL SOC CHEMISTRY  

    In the vesicular membrane systems comprising N,N-didodecyl-N,N-dimethylammonium bromide and tri- or tetra-peptide catalysts (pH 7.68; ionic strength mu = 0.15; 298 K), Z-L-Leu-L-His-L-Leu (or Z-L-Leu-L-His-L-Leu-L-Leu), having a hydrophobic terminal L-leucine (or L-leucyl-L-leucine) unit, contributed to the stereoselective binding of long-chain p-nitrophenyl N-hexadecanoyl-L (and D)-phenyalanates with the remarkably high binding ratio K-b(L/D) = 11 (or 7.3) and overall stereoselectivity [k(cat)(L/D) = 35 (or 8.1)].

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  • EFFICIENT MULTIPOINT INTERACTION BETWEEN PEPTIDE CATALYSTS AND AMINO-ACID ESTERS IN A BILAYER VESICULAR MEMBRANE FOR HIGHLY STEREOSELECTIVE HYDROLYSIS REACTIONS

    K OHKUBO, K URABE, J YAMAMOTO, H ISHIDA, S USUI, T SAGAWA

    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS   ( 22 )   2301 - 2302   1995.11

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    The H-1 NMR NOESY spectra of the multi-point interaction between N-(N-benzyloxycarbonyl-L-leucyl)-L-histidine-[(Z)-L-Leu-L-His] and methyl N-hexanoyl-L-phenylalanate in a N,N-bisdodecyl-N,N-dimethylammonium bromide membrane confirms that the membrane-assisted, hydrophobic interaction between the peptide catalyst and enantiomeric substrates enhances the stereoselective hydrolysis of p-nitrophenyl N-acetyl (or decanoyl)-L (or D)-phenylalanate with (Z)-L-Leu-L-His (most effective in di-, tri- or tetra-peptide catalysts with an introduced L-histidyl group).

    DOI: 10.1039/c39950002301

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  • EFFECTS OF PARAMAGNETIC LANTHANIDE IONS ON DECAY PROCESS OF PHOTOGENERATED RADICAL PAIRS IN PORPHYRIN-VIOLOGEN LINKED COMPOUNDS AT REVERSED MICELLAR SURFACES

    A TOKI, H YONEMURA, S USUI, H NAKAMURA, T MATSUO

    RESEARCH ON CHEMICAL INTERMEDIATES   21 ( 8-9 )   951 - 960   1995

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    Language:English   Publishing type:Book review, literature introduction, etc.   Publisher:VSP BV  

    Radical pairs were generated in reversed micelles by laser excitation of zinc tetraphenylporphyrin-viologen linked compounds (ZPnV) with a polymethylene spacer (-(CH2)(n)-; n = 4, 6 and 8). The optical transient-absorption and chemically induced dynamic electron polarization (CIDEP) spectra indicated that paramagnetic lanthanide ions invariably accelerated the decay process of the radical pairs at 0.3 T. The typical E/A/E/A spectra for the ZP6V and ZP8V systems were explained as due to S-T-0 mixing and electron-spin relaxation between Zeeman-splitted triplet sublevels. In the case of ZP4V, the paramagnetic Gd3+ ion accelerated the radical decay process even at zero-magnetic field, and strong emissive CIDEP spectra evolved with the elapsed time after laser excitation. Appreciable contribution of S-T level crossing in the radical decay process was suggested to account for the novel features of the ZP4V system.

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  • 逆ミセル中の光照射により生成した亜鉛ポルフィリンービオロゲンラジカル対の減衰反応に対する常磁性ランタニドイオンの効果

    21   951   1995

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  • 気相中の塩化物イオン移動物平衝反応における置換基効果

    68   3199   1995

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  • 高立体選択的加水分解反応のための二分子膜中におけるペプチド触媒とアミノ酸エステル間の他点相互作用

    1995   2301   1995

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  • Catalytic and Stereoselective Molecular Recognition Abilities of Supramolecules Which Include Peptide Catalysts and a Vesicular Membrane

    Katsutoshi Ohkubo, Junji Yamamoto, Takashi Sagawa, Satoshi Usui, Kenji Urabe

    KOBUNSHI RONBUNSHU   52 ( 10 )   650 - 656   1995

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    The molecular composition and reaction circumstances of supramolecules which include a simple peptide and a double-chain surfactant vesicle were determined for the highly efficient catalytic and stereoselective esterolysis of enantiomeric amino acid esters through the effective multi-hydrophobic substrate-peptide interaction. In the simple peptides (1, 2a~g, and 3a~c) including L-histidine residue and cationic double-chain surfactants (4a, b), a supramolecule composed of 2c and 4b incorporated short-chain substrates (5a) into its vesicular membrane efficiently. It hydrolyzed 5a stereoselectively with an enantiomer rate ratio of L/D=167 though a suitable multi-point interaction between 2c and 5a in the esterolyses of the substrates (5a~f) in 3 vol% MeCN/Tris-KCl buffer (pH 7.68, μ= 0.01) at 298 K. © 1995, The Society of Polymer Science, Japan. All rights reserved.

    DOI: 10.1295/koron.52.650

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  • Molecular Design of Transition-State Analogue-Imprinted Polymer Catalysts-Stereoselective Esterolysis of Amino Acid Esters

    Katsutoshi Ohkubo, Yasuo Urata, Shyogo Hirota, Satoshi Usui, Takashi Sagawa, Yoshio Funakoshi, Kohji Yoshinaga

    KOBUNSHI RONBUNSHU   52 ( 10 )   644 - 649   1995

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    Molecular design of polymer catalysts for the esterolysis of a marked amino acid ester substrate Z-L-Leu-PNP (PNP=p-nitrophenol) was performed. Either a transition-state analogue of Z-Leu-PP (phenyl l-benzyloxycarbonly-3-methylpentylphosphonate) or a ground-state analogue of Z-L-Leu-AA (ethyl N-benzyloxycarbonyl-L-leucine- anthranilate) was used as a template molecule. In the esterolyses of amino acid esters in 10 vol% dimethyl sulfoxide (DMSO)-Tris buffer (pH 7.15) at 293~308 K, several water-soluble or insoluble polymer catalysts containing a L-histidine catalytic site, which were synthesized by the radical polymerization with acrylamide derivatives, incorporated the marked substrate into their reaction cavities effectively. An ammonium-chain containing water-soluble polymer catalyst exhibited a remarkable acceleration of the present reaction. The free energy of activation (23.9 kcal/mol at 303 K) of the uncatalyzed reaction decreased 7.0 kcal/mol. © 1995, The Society of Polymer Science, Japan. All rights reserved.

    DOI: 10.1295/koron.52.644

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  • トリ、テトラペプチド含有ベシクル膜による長鎖アミノ酸の取り込みと立体選択的加水分解

    ( 23 )   2957   1995

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  • CATALYTIC AND STEREOSELECTIVE MOLECULAR RECOGNITION ABILITIES OF SUPRAMOLECULES WHICH INCLUDE PEPTIDE CATALYSTS AND A VESICULAR MEMBRANE

    K OHKUBO, K URABE, J YAMAMOTO, T SAGAWA, S USUI

    KOBUNSHI RONBUNSHU   52 ( 10 )   650 - 656   1995

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    Language:Japanese   Publisher:SOC POLYMER SCIENCE JAPAN  

    The molecular composition and reaction circumstances of supramolecules which include a simple peptide and a double-chain surfactant vesicle were determined for the highly efficient catalytic and stereoselective esterolysis of enantiomeric amino acid esters through the effective multi-hydrophobic substrate-peptide interaction. In the simple peptides (1, 2a similar to g and 3a similar to c) including L-histidine residue and cationic double-chain surfactants (4a, b), a supramolecule composed of 2c and 4b incorporated short-chain substrates (5a) into its vesicular membrane efficiently. It hydrolyzed 5a stereoselectively with an enantiomer-rate ratio of L/D=167 though a suitable multi-point interaction between 2c and 5a in the esterolyses of the substrates (5a similar to f) in 3 vol% MeCN/Tris-KCl buffer (pH 7.68, mu=0.01) at 298 K.

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  • MOLECULAR DESIGN OF TRANSITION-STATE ANALOG-IMPRINTED POLYMER CATALYSTS-STEREOSELECTIVE ESTEROLYSIS OF AMINO-ACID ESTERS

    K OHKUBO, Y FUNAKOSHI, Y URATA, S HIROTA, S USUI, T SAGAWA, K YOSHINAGA

    KOBUNSHI RONBUNSHU   52 ( 10 )   644 - 649   1995

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    Language:Japanese   Publisher:SOC POLYMER SCIENCE JAPAN  

    Molecular design of polymer catalysts for the esterolysis of a marked amino acid ester substrate Z-L-Leu-PNP (PNP=p-nitrophenol) was performed. Either a transition-state analogue of Z-Leu-PP (phenyl 1-benzyloxycarbonly-3-methylpentylphosphonate) or a ground-state analogue of Z-L-Leu-AA (ethyl N-benzyloxycarbonyl-L-leucine-anthranilate) was used as a template molecule. In the esterolyses of amino acid esters in 10 vol% dimethyl sulfoxide (DMSO)-Tris buffer (pH 7.15) at 293 similar to 308 K, several water-soluble or insoluble polymer catalysts containing a L-histidine catalytic site, which were synthesized by the radical polymerization with acrylamide derivatives, incorporated the marked substrate into their reaction cavities effectively. An ammonium-chain containing water-soluble polymer catalyst exhibited a remarkable acceleration of the present reaction. The free energy of activation (23.9 kcal/mol at 303 K) of the uncatalyzed reaction decreased 7.0 kcal/mol.

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  • "Subtituent Effect on Chloride Ion Transfer Equilibria in the Gas Phase"

    Bull Chem Soc Jpn   68   3199   1995

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  • ENANTIOSELECTIVE AND PHOTOCATALYTIC OXIDATION OF 1,1'-BI-2-NAPHTHOL WITH A CHIRAL RUTHENIUM COMPLEX WHICH INCLUDES MOLECULAR HELICITY

    T HAMADA, H ISHIDA, S USUI, K TSUMURA, K OHKUBO

    JOURNAL OF MOLECULAR CATALYSIS   88 ( 1 )   L1 - L5   1994.2

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    Language:English   Publishing type:Rapid communication, short report, research note, etc. (scientific journal)   Publisher:ELSEVIER SCIENCE BV  

    1,1'-Bi-2-naphthol was oxidized catalytically and enantioselectively (less-than or-equal-to 15.2% e.e.), by using the chiral ruthenium complex, DELTA-[Ru(menbpy)3]2+ (menbpy = 4,4'-dimenthoxycarbonyl-2,2'-bipyridine) as a photocatalyst and [Co(acac)3] (Hacac = pentane-2,4-dione) as an oxidant under photoirradiation.

    DOI: 10.1016/0304-5102(93)E0271-H

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  • Substituent Effects on the Photosolvolysis of 2-Chloropropio phenones in 2, 2, 2-Trifluoroethanal

    Chemistry Letters   ( 11 )   2015   1994

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  • 分子ヘリシティーを有する不斉ルテニウム錯体を用いた立体選択的および光触媒的1,1'-ビー2-ナフトールの酸化反応

    88   L1-L5   1994

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  • 2-クロロプロピオフェノンの2,2,2-トリフルオロエタノール中の光加溶媒分解反応における置捩基効果

    ( 11 )   2015   1994

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  • LASER-INDUCED PHOTOIONIZATION OF 2-ELECTRON-REDUCED VIOLOGEN

    S USUI, H INOUE, H ISHIDA, K OHKUBO

    CHEMISTRY LETTERS   12,2089 ( 12 )   2089 - 2092   1993.12

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    Language:English   Publisher:CHEMICAL SOC JAPAN  

    Laser photolysis of two-electron-reduced 1,1'-bis(3-sulfonatepropyl)-4,4'-bipyridinium (pVS2-) produced by the reduction of PVS0 with Na2S2O4 in the cationic micelles of hexadecyltrimethylammonium chloride induced the photoionization of PVS2- to generate comparable amounts of PVS-. and hydrated electrons. Pyrene with a considerably negative reduction potential of -2.09 vs. SCE was observed to be reduced in the system.

    DOI: 10.1246/cl.1993.2089

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  • A NOVEL PHOTOCATALYTIC ASYMMETRIC-SYNTHESIS OF (R)-(+)-1,1'-BI-2-NAPHTHOL DERIVATIVES BY OXIDATIVE COUPLING OF 3-SUBSTITUTED-2-NAPHTHOL WITH DELTA-[RU(MENBPY)3]2+ [MENBPY = 4,4'-DI(1R,2S,5R)-(-)-MENTHOXYCARBONYL-2,2'-BIPYRIDINE], WHICH POSSESSES MOLECULAR HELICITY

    T HAMADA, H ISHIDA, S USUI, Y WATANABE, K TSUMURA, K OHKUBO

    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS   11,909 ( 11 )   909 - 911   1993.6

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    Language:English   Publisher:ROYAL SOC CHEMISTRY  

    The asymmetric synthesis of (R)-(+)-1,1'-bi-2-naphthol [or (R)-(+)-1,1'-bi-3-methoxy-2-naphthol] from 2-naphthol (or 3-methoxy-2-naphthol) is performed photocatalytically by using the chiral ruthenium complex, M(C3)-DELTA-[Ru(menbpy)3]2+ [M(C3) = counterclockwise molecular helicity along the C3 axis, menbpy = 4,4'-di(1R,2S,5R)-(-)-menthoxycarbonyl-2,2'-bipyridine] as a photosensitizer and [Co(acac)3] (acac- = acetylacetonato) as an oxidant.

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  • TIME-RESOLVED ELECTRON-SPIN-RESONANCE SPECTRA OF LINKED RADICAL PAIRS ON LASER EXCITATION OF ZINC TETRAPHENYLPORPHYRIN VIOLOGEN SYSTEMS

    H NAKAMURA, S USUI, Y MATSUDA, T MATSUO, K MAEDA, T AZUMI

    JOURNAL OF PHYSICAL CHEMISTRY   97 ( 3 )   534 - 536   1993.1

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    Language:English   Publishing type:Rapid communication, short report, research note, etc. (scientific journal)   Publisher:AMER CHEMICAL SOC  

    Photoinduced electron transfer from the zinc tetraphenylporphyrin moiety to the viologen unit in linked compounds in reversed micelles generated radical pairs, which afforded chemically induced dynamic electron polarization (CIDEP) spectra at room temperature. The CIDEP spectra varied with the number of methylene groups (n) in the alkyl spacer of the linked compounds. In the case of longer spacers (n = 6 and 8), common E/A/E/A patterns were observed throughout the measurement (0.7-5 mus). The signal pattern could be simulated by a formula for the well-known spin-correlated radical pair mechanism, and the corresponding exchange coupling (J) was evaluated (-0.4mT). In the case of ZP4V, the CIDEP signals rapidly changed with elapsed time (O.5-3 mus) from the absorptive to emissive mode. The observation was explained on the basis of a strong contribution of the triplet mechanism in the photogeneration of the radical pair in the early period of measurement.

    DOI: 10.1021/j100105a002

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  • 分子不斉を有するルテニウム錯体を用いた1,1'-ビチフトール誘導体の光触媒的不斉合成反応

    11,909   1993

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  • 亜鉛ポルフィリン-ビオロゲン間のレーザー光励起により生成したラジカル対の時間分割ESRスペクトル

    97 ( 3 )   534   1993

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  • ビオロケン二電子還元体のレーザー光イオン化反応

    12,2089   1993

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  • DESIGN OF A HYBRID OF 2 ALPHA-HELIX PEPTIDES AND RUTHENIUM TRISBIPYRIDINE COMPLEX FOR PHOTOINDUCED ELECTRON-TRANSFER SYSTEM IN BILAYER-MEMBRANE

    H MIHARA, N NISHINO, R HASEGAWA, T FUJIMOTO, S USUI, H ISHIDA, K OHKUBO

    CHEMISTRY LETTERS   9,1813 ( 9 )   1813 - 1816   1992.9

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    Two strands of an amphiphilic alpha-helical 22-peptide were anchored on ruthenium trisbipyridine complex. The hybrid was equipped with the triad of the ruthenium complex, anthraquinone, and viologen as photo-induced electron transfer system embedded in bilayer membrane.

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  • SUBSTITUENT EFFECT ON THE SOLVOLYSIS OF 2,2-DIMETHYLINDAN-1-YL CHLORIDES

    M FUJIO, K NAKATA, Y TSUJI, T OTSU, Y TSUNO

    TETRAHEDRON LETTERS   33 ( 3 )   321 - 324   1992.1

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    The substituent effect on the solvolysis of 2,2-dimethylindan-1-yl chlorides was analyzed in terms of the LArSR Eq., to give rho = -5.81 and r = 1.14. The coplanarity of alpha-t-butylbenzyl cation system was discussed.

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  • 二分子膜透過型光誘起電子移動反応を示すルテニウムトリスビピリジン錯体ハイブリッドα-ヘリカルペプチドの分子設計

    9,1813   1992

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  • 2,2-ジメチルインダニル塩化物シスにおける溶媒効果

    18,297   1992

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  • MAGNETIC-FIELD EFFECTS ON THE DECAY-RATES OF PHOTOGENERATED GEMINATE RADICAL PAIRS IN REVERSED MICELLES

    A UEHATA, H NAKAMURA, S USUI, T MATSUO

    JOURNAL OF PHYSICAL CHEMISTRY   93 ( 25 )   8197 - 8203   1989.12

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    DOI: 10.1021/j100362a012

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  • REACTION CONTROL OF PHOTOINDUCED ELECTRON-TRANSFER BY THE USE OF MOLECULAR ASSEMBLIES AND MAGNETIC-FIELD

    S USUI, A UEHATA, H BABA, H NAKAMURA, T MATSUO

    NIPPON KAGAKU KAISHI   8,1477 ( 8 )   1477 - 1485   1989.8

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  • SUBSTITUENT EFFECT ON THE STABILITY OF 1-PHENYLETHYL CATION IN THE GAS-PHASE

    M MISHIMA, S USUI, M FUJIO, Y TSUNO

    NIPPON KAGAKU KAISHI   8,1269 ( 8 )   1269 - 1274   1989.8

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  • STABILITIES OF ALPHA-CUMYL CATIONS IN THE GAS-PHASE

    M MISHIMA, S USUI, H INOUE, M FUJIO, Y TSUNO

    NIPPON KAGAKU KAISHI   8,1262 ( 8 )   1262 - 1268   1989.8

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  • 逆ミセル中で生成した光誘起ラジカル対の減滾速度に対する磁場効果

    93 ( 25 )   8197   1989

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  • Stabilities of α-Cumyl Cations in the Gas Phase

    Masaaki Mishim, Saitoshi Usui, Hiroki Inoue, Mizue Fujio, Yuho Tsuno

    NIPPON KAGAKU KAISHI   1989 ( 8 )   1262 - 1268   1989

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    The gas-phase basicities (GB) of 2-(m, p-substituted phenyl)propenes were determined based on proton-transfer equilibrium method using a pulsed ion cyclotron resonance (TCR) mass spectrometer. The substituent effect on the GB was correlated linearly by σ∗ to give a ρ of, -13.0. The correlation which, Covered a wide range of 35 kcal.mol-1 from p-NMe2 to 3,5-(CF3)2 group revealed that σ∗ values determined in solution for most of substituents were applicable to the gas-phase substituent effects without modification accounting for solvation of substituents. This result suggested that the resonance demand (r) of LArSR Eq. (1) for the gas-phase stability of α-cumyl (1-methyl-1-Phenylethyl) cation was identical with an r of 1.00 for the solvolysis of a-cumyl chlorides. The identity of the r value between in the gas phase and in solution was also observed for basicities of a series of benzoyl compounds. The charge derealization in the aryl ring within a cation will remain essentially the same in the gas phase as in solution. The solvation of cation reduces the central charge to lower the response to substituent perturbation, essentially without change in intramolecular charge derealization. The present result leads us to the conclusion that the charge derealization in the SN 1 transition state in the solvolysis should be quite close to that of the carbocation intermediate. The same conclusion was given by the results for a series of relevant benzylic systems. On the basis of the substituent effect on the gas-phase stability of α-cumyl cation, the substituent effects of gas-phase basicities of benzaldehydes and chloride ion affinities of benzyl cations were analyzed to give r values of 1.00 and 1.29, respectively. The exalted r value of 1.29 for benzyl cation might be attributed to the lower stability than α-cumyl cation. The variation of the r value with the system is in complete agreement with the basic concept of varying resonance demand, supporting the validity of the LArSR Eq. © 1989, The Chemical Society of Japan. All rights reserved.

    DOI: 10.1246/nikkashi.1989.1262

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  • Reaction Control of Photoinduced Electron Transfer by the Use of Molecular Assemblies and Magnetic Field

    Satoshi Usui, Akihiro Uehata, Hisashi Baba, Hiroshi Nakamura, Taku Matsuo

    NIPPON KAGAKU KAISHI   1989 ( 8 )   1477 - 1485   1989

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  • Substituent Effect on the Stability of 1-Phenylethyl Cation in the Gas Phase

    Masaaki Mishima, Satoshi Usui, Mizue Fujio, Yuho Tsuno

    NIPPON KAGAKU KAISHI   1989 ( 8 )   1269 - 1274   1989

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    The gas-phase basicities (GS) were determined for a series of styrenes based on proton-transfer equilibrium method using a pulsed ion cyclotron resonance (ICR) mass spectrometer. The LArSR analysis of the substituent effect on the GB gave an r of 1.14 and a ρ of-13.6. The r value higher than unityt indicated clearly a greater resonance demand for 1-phenylethyl cation than that for α-cumyl cation while the ρ value was comparable to that of the latter. The exalted resonance demand might be attributed to the lower stability of 1-phenylethyl cation than α-cumyl cation. This trend in the r value is consistent with the observations for the relevant benzylic carbocations. Most importantly, the r value for gas-phase stability of the 1-phenylethyl cation has been found to be identical in magnitude with the r value for the solvdlysis of the corresponding substrates (r=1.15). The same is generally true for a series of benzylic carbocations. The identity of the r value between the SN 1 solvolysis and gas-phase carbocation stability suggests that the intramolecular charge derealization in the, transition state should be quite close to that of the carbocation intermediate. It is concluded that the r value of 1.15 for the 1-phenylethyl solvolysis must be intrinsic resonance demand characteristic of the parent 1-phenylethyl cation itself. The LArSR correlation with r=l.15 fpr the solvolysis in aq. ethanol and aq. acetone suggests a mechanistic involvement of solvent nucleophilic assistance for substrates less reactive than m-cyano derivative. © 1989, The Chemical Society of Japan. All rights reserved.

    DOI: 10.1246/nikkashi.1989.1269

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  • External Magnetic Field Effects on Photoinduced Electron Transfer Reactions in Organized Moleculer Systems

    MRS International Meeting on Advanced Materials   12,339   1988

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  • 分子集合体中の光誘起電子移動反応における外部磁場効果

    12,339   1988

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  • EFFECTS OF EXTERNAL MAGNETIC-FIELDS ON LASER-INDUCED ELECTRON-TRANSFER REACTIONS IN PORPHYRIN-VIOLOGEN PAIRS AT THE SURFACE OF MOLECULAR BILAYERS

    S USUI, H NAKAMURA, T OGATA, A UEHATA, A MOTONAGA, T MATSUO

    CHEMISTRY LETTERS   9,1779 ( 9 )   1779 - 1782   1987

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    DOI: 10.1246/cl.1987.1779

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  • 分子集合体表面上のポルフィリン-ビオロゲン対中のレーザー誘起電子移動反応における外部磁場の効果

    9,1779   1987

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  • ベンジルカチオンの気相中.安定性に対する置換基効果

    6,1047   1987

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  • SUBSTITUENT EFFECT ON THE STABILITY OF BENZYL CATION IN THE GAS-PHASE

    M MISHIMA, K ARIMA, S USUI, M FUJIO, Y TSUNO

    CHEMISTRY LETTERS   6,1047 ( 6 )   1047 - 1050   1987

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    Language:English   Publisher:CHEMICAL SOC JAPAN  

    DOI: 10.1246/cl.1987.1047

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Works

  • Studies on the photosolvolysis mechanisms of phenacyl sulfonates by the aid of LASER Flash photolysis

    2000

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  • Photosolvolysis mechanism of 1-albyloxy-2-pyridone.

    2000

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  • 1-アルコキシ-2-ピリドンの光分解反応機構

    2000

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  • フェナシルスルホナートの光加溶媒分解反応機構のレーザーフラッシュホトリシスによる研究

    2000

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  • Photosolvolysis Mechanism of 3-Phenyl-2-chloropropiophenone.

    1999

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  • フェナシルスルホナートの光加溶媒分解反応における脱離基効果

    1999

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  • 3-フェニル-2-クロロプロピオフェノンの光加溶媒分解反応機構

    1999

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  • Leaving Group Effect on the Photosolvolysis of Phenacyl Sulfonate

    1999

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  • Substituent Effect on the Stereoselectivity of Photoinduced Phenyl-rearrangement of 2-Chloropropiophenone

    1998

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  • Photochemical Reactions of 4'-Alkyloxy-1-methylstilbazolium Ion in the presence of Nucleophiles

    1998

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  • Substituent Effect on the Photosolvolysis of Phenacyl Sulfonate

    1998

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  • 2-クロロプロピオフェノンの光フェニル転位反応の立体選択性における置換基効果

    1998

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  • 求核剤存在下での4'-アルコキシ-1-メチルスチルバゾリウム塩の光反応

    1998

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  • フェナシルスルホナートの光加溶媒分解反応における置換基効果

    1998

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  • "Theoretical Study on the k<sub>S</sub>-k<sub>Δ</sub> Solvolysis of 2-Phenylethyl System"

    1997

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  • 2-フェニルエチルソルボリシスにおけるk<sub>S</sub>-k<sub>Δ</sub>機構の理論研究

    1997

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  • Substituent Effect on the Photosolvolysis Products of α-Chloroacetophenone in Trifluoroethnol

    1996

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  • Enantioselectivities in the Phenyl-rearrangements of 2-Chloropropiophenones

    1996

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  • 2-クロロプロピオフェノンのフェニル転位反応における立体選択性の検討

    1996

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  • トリフルオロエタノール中のα-クロロアセトフェノンのフォトソルボリシス生成物比に対する置換基効果

    1996

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  • "STEREOSELECTIVE PHOTOINDUCED PHENYL-REARRANGEMENT REACTION OF 2-CHLOROPROPIOPHENONE IN 2,2,2-TRIFLUOROETHANOL"

    1995

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  • 2-クロロプロピオフェノンのトリフルオロエタノール中での光フェニル転位反応における立体選択性

    1995

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  • Stereoselective Photosolvolysis of 2-Chloropropiophenone

    1994
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    1996

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  • 2-クロロプロピオフェノンの立体選択的光加溶媒分解反応

    1994
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    1996

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  • Electron-Transfer from Photoexcited State of Two-Electron-Reduced Viologen

    1993

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  • α-クロロプロピオフェノンの光フェニル転位反応における置換基効果

    1993

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  • ビオロゲン二電子還元体を増感剤として用いた電子移動反応

    1993

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  • ペプチド鎖に連結したルテニウム錯体を用いた光誘起電子移動反応

    1993

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  • Photo-Induced Electron Transfer Reaction by Ruthenium Complexes Bound to Peptioles

    1993

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  • Substituent Effect on the Photoinduced Pheyl Migration of α-chloropropiophenone

    1993

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  • 二階段励起によるAuポルフィリン-ピレン間の光誘起電子移動反応

    1991
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    1992

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  • Two Step Photoinduced Electron Transfer Reactions between Gold Porphyrim and Pyrene Derivatives

    1991
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    1992

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  • ルチニウム錯体を光触媒とするナフトール誘導体の酸化的二量化反応

    1991
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    1992

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  • Photo-Oxidative Coupling of Naphthol Derivatives by the Use of Ruthenium Complex

    1991
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    1992

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  • キラルルテニウム(II)錯体を触媒としたコバルト(III)錯体の立体区別光還元反応

    1990
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    1996

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  • Enontioselective Photoreduction of Co(III)Complexes by the Use of Chiral Ruthenium(II)Complex

    1990
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    1996

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  • 電子受容性ペプチド鎖を有するルテニウム錯体の光電子移動反応

    1990
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    1993

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  • Photoinduced Electron Transfer Reactions in Ruthenium Complex with Peptide Chain Containing Electron Acceptor

    1990
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    1993

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  • Enontioselective Photoreduction of Co(III)Complexes by the Use of Chiral Ruthenium(II)Complex

    1990
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    1992

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  • キラルルテニウム(II)錯体を光触媒としたコバルト(III)錯体の立体区別光還元反応

    1990
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    1992

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  • 亜鉛ポルフィリン-ビオロゲン間の光誘起電子移動反応の時間分割ESRスペクトルによる研究

    1989
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    1990

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  • Photochemical Carbon Dioxide Reductions Cataleyzed by[Ru(bpy)<sub>2</sub>(CO)<sub>2</sub>)<sup>2+</sup>

    1989
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    1990

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  • Time Resolved ESR Spectroscopic Study on Photoinduced Electron Transfer Reactions between Zinc Porphynate and Viologen

    1989
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    1990

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  • [Ru(bpy)<sub>2</sub>(CO)<sub>2</sub>]<sup>2+</sup>を光触媒とする光化学的二酸化炭素還元反応

    1989
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    1990

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  • ビオロゲン-シクロデキストリン錯体が関与する光誘起電子移動反応II:ベンジルビオロゲン及びヘキシルビオロゲン系に関する検討

    1988
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    1990

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  • Photoinduced Electron Transfer Reactions Involving Viologen-Cyclodextrin Complex2 : Studies of Benzyl-and Hexylviolegen Systems

    1988
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    1990

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  • ポルフィリン-ビオロゲン間の光誘起電子移動反応とその磁場効果(1)meso-位のピリジニウム基の効果

    1988
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    1989

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  • Effects of External Magnetic Fields on Photoinduced Electron Transfer between Porphysin and Viologens(1). Effects of Pyridiniun Group at meso-Position

    1988
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    1989

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Research Projects

  • 弥彦山頂における乾性・湿生沈着の観測による新潟県山晴雨発生機構の解明

    2000

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    Grant type:Competitive

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  • 炭素陽イオン中間体を経る光フェニル転位反応機構の研究

    Grant number:06740499

    1994

    System name:科学研究費助成事業

    Research category:奨励研究(A)

    Awarding organization:日本学術振興会

    臼井 聡

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    Grant amount:\900000 ( Direct Cost: \900000 )

    光によりフェニル転移反応を示し、非アルカロイド系抗炎症剤合成の中間体となる2-Phenyl-propionic acidを与える2-Phenylpropiophenone(1)のフォトソルボリシス機構を2,2,2-Trifluoroethanol(TFE)中において検討した。1の無置換体の光反応生成物をHPLCならびに^1H-NMRで解析したところ、フェニル転移生成物(2)79.8%、求核置換反応性生成物(3)7.2%、脱離反応性生物(4)9.2%ならびにフェナシルラジカルの還元生成物(5,6)3.8%が得られた。本光反応の特徴は反応の定量性が高い事のみならず、一般のα-haloketoneのフォトソルボリシスとは異なりラジカル生成物が少なくイオン反応が選択的に進行している事にある。この結果は反応溶媒であるTFEの高極性に起因していると思われる。1のフォトソルボリシスにおける2および3の生成物比を種々の置換体について調べたところ、無置換体では0.091であった3/2比はm-CN体では0.0065、p-OMe体では0.92と、フェニル環への電子吸引性置換基の導入が2の生成を促進させることが明らかとなった。この結果は類似したフェニル転移-求核置換競争反応を示す3-Phenyl-2-butylbrosylateの熱反応が電子吸引性置換基により求核置換反応を促進させている事とは対照的であり、光フェニル転移反応の特異性を表すものである。またm-位に電子吸引性置換基を導入したp-OMe置換体においてもp-OMe体と同等の3/2比が、さらにm-OMe置換体では大きな3/2比12が得られており、本光反応のカルボカチオン生成過程においてベンゼン環から塩素原子への電子移動の重要性が示唆された。

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  • キラル遷移金属錯体を光触媒として用いた新規不斉合成

    Grant number:05234224

    1993

    System name:科学研究費助成事業

    Research category:重点領域研究

    Awarding organization:日本学術振興会

    大久保 捷敏, 臼井 聡, 石田 斉

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    Grant amount:\2400000 ( Direct Cost: \2400000 )

    本研究は長寿命化した分子ヘリシティを有する新規ルテニウム(II)錯体触媒を分子設計し、基質との直接的結合(配位など)を経ない遠距離相互作用による光触媒的不斉合成を試みた。分子力学解析から、DELTA-[Ru(Men-bpy)_3]^<2+>(Menbpy=4,4'-ビス[(1R,2S,5R)-(-)-メントキシカルボニル]-2,2'-ビピリジン)の分子構造は、DELTA-体のメンチル部位がC_3対称軸に対して反時計廻りのMinus分子ヘリシティ(M(C_3)-DELTA-型)を有することになり、4,4'-ビス[S(-)またはR(+)-1-フェニルエチルアミノカルボニル]-2,2'-ビピリジン(SまたはR-PhEtbpy)配位子を有するRu(II)錯体では、唯一安定な時計廻りPlusヘリシティのP(C_3)-LAMBDA-[Ru(S-PhEtbpy)_3]^<2+>とM(C_3)-DELTA-[Ru(S-PhEtbpy)_3]^<2+>構造が決定された。これらヘリカルRu(II)錯体の光化学的特性は、三重項Metal to Ligand Charge Transfcr (^3MLCT)-[Ru(bpy)_3]^<2+>(bpy=2,2'-ビピリジン)励起体に比して励起波長はほぼ同じであるが、励起寿命は長くなり、また光異性および光分解の量子収率は著しく低下して光安定性の向上がみられた。ヘリカルRu(II)錯体の不斉光触媒機能について、C_3軸対称のP(C_3)-DELTA,M(C_3)-LAMBDA-[Co(acac)_3](acacH=ペンタン-2,4-ジオン)の光学分割・不斉合成から調べると、とりわけM(C_3-DELTA-[Ru(Menbpy)_3]^<2+>はラセミ[Co(acac)_3]の消光反応よりも光学分割において基質分子認識力が強く発揮され、その他の触媒と同じくヘテロヘリカル(M(C_3))-PC-(_3))触媒・基質相互作用が優先される。^3MLCT Ru(II)錯体より生成したヘリカルRu(III)錯体は、[Co(acac)_3]の還元生成物Co(acac)_3(H_2O)/acacHの不斉酸化を触媒し、他のM(C_3型)触媒と同様にM(C_3)-DELTA-[Ru(Menbpy)_3]^<3+>はホモヘリカル対のM(C_3)-LAMBDA-[Co(acac)_3]を優先不斉合成する。不斉認識力序列 DELTA-[Ru(Menbpy)_3]^<2+>]>>LAMBDA)AまたはDELTA)-[Ru(S(またはR)-PhEtbpy)_3]^<2+>>>DELTA-[Ru(bpy)_3]^<2+>はC_3対称軸に対する触媒分子ヘリシティの拡がりに反映し、本反応は新規不斉増殖型光触媒反応であることが明白になった。

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  • 金属酵素機能を有する新規な固定化抗体触媒による蛋白質の位置選択的切断に関する研究

    Grant number:03650681

    1991

    System name:科学研究費助成事業

    Research category:一般研究(C)

    Awarding organization:日本学術振興会

    大久保 捷敏, 佐川 尚, 臼井 聡, 石田 斉

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    Grant amount:\1700000 ( Direct Cost: \1700000 )

    酵素機能を有する抗体触媒による蛋白質の位置選択的切断にあたって、まず多点相互作用によりアミノ酸エステル基質を分子認識して反応するペプチド型加水分解酵素モデルの分子設計を試みた。すなわち活性部位となるヒスチジン誘導体と抗原分子を結合したアンカ-型触媒を合成し、別途作製したモノクロ-ナル抗体と溶液中混合することによって抗原ー抗体反応を利用して抗体内部に効率よく触媒部位を導入した抗体ハイブリッド触媒を用いて光学活性アミノ酸エステルの加水分解反応を行なった。その結果、反応は立体選択的に進行し、抗体のもつ不斉環境を利用した抗体ハイブリッド触媒の有用性が示された。また、加水分解反応の遷移状態が四面体構造をとることから遷移状態類似体をハプテンとし、遷移状態を安定化して反応する抗体触媒の開発を以下のように進めた。すなわち電荷の異なる遷移状態類似体としてリン酸エステル(アニオン性)およびアンモニウム塩誘導体(カチオン性)をそれぞれ合成し、これらをハプテンとする抗体触媒の反応性の比較から抗体結合部位での電荷の影響が明らかとなる。アニオン性ハプテンの免疫は現在進めており、これまでにカチオン性ハプテンに対するモノクロ-ナル抗体のL体アミノ酸エステル加水分解反応を調べたところ、中性から弱アルカリ領域では反応の加速がみられなかったものの、弱酸性領域では加速がみられ、そのpH依存性より至適pH〜6であることが示された。同条件下でD体基質を用いたところ反応加速はみられずL体基質に対する高い選択性が示された。さらに、金属酵素機能を有する抗体触媒の開発にあたって、これまでにヒスチジン誘導体へのルテニウム、コバルト等の遷移金属イオン添加効果から、錯形成した触媒の構造と活性および立体選択性の相関を調べており、ペプチド結合切断反応の遷移状態に相当する安定な錯体を用いた遷移状態類似体のハプテンの合成を現在検討している。

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  • Application of Photoinduced Electron Transfer Reaction Across the Water-Organic Interface

    Grant number:01550628

    1989 - 1990

    System name:Grants-in-Aid for Scientific Research

    Research category:Grant-in-Aid for General Scientific Research (C)

    Awarding organization:Japan Society for the Promotion of Science

    NAKAMURA Hiroshi, YONEMURA Hiroaki

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    Grant amount:\1900000 ( Direct Cost: \1900000 )

    1. Photoinduced electron transfers from porphyrin (at the interface) to various type of viologen (as an acceptor) were investigated by the use of molecular assemblies such as a synthetic bilayer which provided a water-organic interface. In case of reactions at a positively charged bilayer, the yield of photoreduced viologen increased in the application of External Magnetic Field, when negatively charged viologen was used as an electron acceptor. This suggested that the radical pair kept a certain distance in the reaction time, and an electron spin-spin interaction remained. On the other hand, the positively charged viologen rapidly left away from the surface of the bilayer after the electron transfer, and a magnetic field effect was not observed.
    2. The photoinduced electron transfer from the amphiphilic porphyrin to the water soluble viologen in the AOT reversed micelles was investigated with External Magnetic Field Effect. The result clearly showed that the AOT micro-water pool gave a special microenvironment such as a "Cage" in the radical reactions and that the pseudo-linked system was observed.
    3. The biphotonic ionization of amphiphilic donor compound on the surface of AOT reversed micelles was also studied. The ionization efficiency was controlled by the size of the water pool. The Electron Spin Echo study also showed that the geometry of the donor position on the water-organic interface was controlled by the microenvironment of the micelles such as water pool size.

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  • 生体系モデル物質を用いる電子移動の制御と光変換への応用

    Grant number:62550593

    1987

    System name:科学研究費助成事業

    Research category:一般研究(C)

    Awarding organization:日本学術振興会

    中村 博, 臼井 聡

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    Grant amount:\1000000 ( Direct Cost: \1000000 )

    本年度は, 光合成のモデルとしての光誘起電子移動反応を, ポルフィリンを電子トナー, ビオローゲンを電子アクセプターとして, 均一系および, 逆ミセル系および二分子膜系を用いて行い, ミクロ環境と外部磁場の効果について検討した. まず水溶性ポルフィリンと各種電荷の異なるビオローゲンの組合せで, 表面電荷の異なる二分子膜系において逆電子移動速度, および電荷分離効率に及ぼす磁場の効果をみた. その結果, 正の表面電荷をもつ二分子膜では, 正の電荷をもつビオローゲンの電荷分離効率は大きくなるが磁場によって変化を受けない. 一方負の電荷をもつビオローゲンでは, 0磁場では効率は小さいが, 0.2T以上の磁場を加えることによって逆電子移動速度の減少とともに, 分離効率が上昇した. これらは膜表面と還元体の静電相互作用が分離効率やそれに対する磁場の影響を支配していることを示す.
    一方, 油中水滴型ミクロエマルジョンである逆ミセル中でも水溶性ポルフィリンおよび界面活性剤型ポルフィリンとビオローゲンの組合せで光誘起電子移動反応を行った. この系では有機層中の界面活性剤濃度と水の量の他により水滴の径をコントロールできることが分っており, 水の量を種々変化させて実験を行った. その結果, 同時にポルフィリン分子と, ビオローゲン分子が, この逆ミセル中に入る確率はPoisson分布に従い, その時だけ電子移動が起ることが認められた. このことはまた, 同じ逆ミセル中にある励起ドナー, アクセプターの対は, 100%の確率で電子移動が起ることを示す. 逆電子移動の速度は逆ミセルの大きさが大きくなるほど遅くなり, 一次の動力学に従う. このことから逆ミセル自身が一つのケージとしての役割を果していると考えられる. 以上のことは, 磁場の効果によっても認められた. すなわち, 磁場を加えることにより逆電子移動速度は遅くなったが, その効果はミセルの大きさが小さくなるほど大きい.

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  • Reaction Control of Photochemical Processes in Liquid Crystalline Phases

    Grant number:60470082

    1985 - 1986

    System name:Grants-in-Aid for Scientific Research

    Research category:Grant-in-Aid for General Scientific Research (B)

    Awarding organization:Japan Society for the Promotion of Science

    MATSUO Taku, USUI Satoshi, NAKAMURA Hiroshi

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    Grant amount:\6900000 ( Direct Cost: \6900000 )

    Attempts have been made to control reaction rates of photochemical processes, such as energy-transfer and electron-transfer, in liquid crystals and bilayer-membrane systems.
    (1) Remarkable electric field effects were observed with sensitized fluorescence intensities of a perylene derivative, when rectangular AC waves (up to 10 <V_(0-p)> ) were applied to liquid crystal cells containing a sensitizer and an acceptor (the perylene derivative) as the guest molecules. Measurements of the fluorescence lifetime of the sensitizer indicated that the rates of energy transfer were independent of the electric fields. The electric field effects completely changed the sign when the intensity variation detected at vertical direction was compared with that at the horizontal direction with respect to the plane of the liquid crystal cell. The observed electric field effects on the sensitized fluorescence were consequently ascribed to the orientation control of transition dipolemoment of the acceptor through molecular alignments of the liquid crystal.
    (2) As to the electron-transfer in bilayer membrane systems, effects of external magnetic fields on laser-induced electron-transfer rates were investigated by the use of porphyrin-viologen linked systems. Rates of reverse electron transfer in the photogenerated intramolecular ion radical pair, as originated from quenching of porphyrin triplet by viologen, were remarkably suppressed at above 0.1 T. In addition, amphiphilic viologen molecular assemblies were found to help charge-separation of the photoinduced, intramolecular electron transfer in sensitizer-acceptor linked system incorporated into the molecular assemblies. Construction of hole-transport system was also attempted by the use of double-chain ammonium amphiphile with carbazole moiety, which afforded extremely long-living charge-separated states on laser excitation. All of these phenomena were ascribed to cooperativity effects of aligned acceptor (or donor) units, which permit electron (or hole) migration via electron exchange mechanism.

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  • Mechanistic Studies on the Photosolvolysis of α-Haloketones

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    Grant type:Competitive

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  • 有機化合物の光転位反応における立体選択性

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    Grant type:Competitive

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  • 分子軌道計算による有機反応における溶媒効果解析

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    Grant type:Competitive

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  • α-ハロケトンの光加溶媒分解反応機構

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    Grant type:Competitive

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  • キラルルテニウム錯体を光触媒とした不斉認識電子移動反応と不斉合成

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    Grant type:Competitive

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  • Photoinduced Enantio differential Electron Transfer by Using Chiral Ruthenium Complex

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    Grant type:Competitive

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  • Stereoselectivity in the Photo-rearrangement of Organic Conpounds

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Teaching Experience

  • 自然環境科学 IV

    2023
    Institution name:新潟大学

  • 自然環境科学研究演習

    2023
    Institution name:新潟大学

  • 理学基礎演習

    2022
    Institution name:新潟大学

  • 環境汚染論

    2021
    Institution name:新潟大学

  • 自然環境科学

    2021
    Institution name:新潟大学

  • 課題研究B

    2021
    Institution name:新潟大学

  • 理学スタディ・スキルズ

    2021
    Institution name:新潟大学

  • 課題研究C

    2021
    Institution name:新潟大学

  • 課題研究(自然環境)A

    2020
    Institution name:新潟大学

  • 課題研究

    2020
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    2021
    Institution name:新潟大学

  • 化学基礎実習b

    2020
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    2021
    Institution name:新潟大学

  • 環境経済システム論Ⅰ

    2020
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  • 環境経済システム論I

    2020
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  • 安全教育

    2020
    Institution name:新潟大学

  • 自然環境科学総論

    2018
    Institution name:新潟大学

  • 自然環境科学実験C2

    2017
    Institution name:新潟大学

  • 自然環境科学実験C1

    2017
    Institution name:新潟大学

  • 化学基礎実習a

    2017
    Institution name:新潟大学

  • 理学スタディ・スキルズ

    2017
    -
    2021
    Institution name:新潟大学

  • 課題研究C

    2017
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    2021
    Institution name:新潟大学

  • 課題研究A

    2017
    -
    2021
    Institution name:新潟大学

  • 課題研究B

    2017
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    2021
    Institution name:新潟大学

  • 専門力アクティブ・ラーニング

    2017
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    2020
    Institution name:新潟大学

  • 自然科学基礎実験

    2016
    Institution name:新潟大学

  • 環境科学スタディスキルズ

    2016
    Institution name:新潟大学

  • 自然科学総論Ⅴ

    2016
    Institution name:新潟大学

  • 課題研究(自然環境)

    2015
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  • グリーンケミストリー概説

    2014
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    2014
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    2018
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    2013
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    2015
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    2013
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    2012
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    2015
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    2012
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    2015
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  • 環境科学総合演習Ⅰ

    2012
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    2015
    Institution name:新潟大学

  • 環境科学特定研究Ⅰ

    2012
    Institution name:新潟大学

  • エネルギー物質科学

    2011
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  • 物質反応化学

    2010
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  • 環境化学特論Ⅰ

    2008
    Institution name:新潟大学

  • 基礎化学実験

    2008
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    2016
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  • 大型機器分析技術

    2008
    Institution name:新潟大学

  • 環境学入門

    2007
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  • 環境化学要論III

    2007
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  • 自然環境科学実験C

    2007
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    2016
    Institution name:新潟大学

  • 自然環境科学概論C

    2007
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    2016
    Institution name:新潟大学

  • 化学実験

    2007
    -
    2015
    Institution name:新潟大学

  • エネルギー変換論

    2007
    -
    2011
    Institution name:新潟大学

  • 化学物質反応論

    2007
    -
    2009
    Institution name:新潟大学

  • 環境化学特論I

    2007
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