研究者総覧

高島 弘 (タカシマ ヒロシ)

  • 研究院自然科学系化学領域 准教授
メールアドレス:
hiroshicc.nara-wu.ac.jp
Last Updated :2021/06/22

researchmap

学位

  • 博士(工学), 九州大学, 2000年03月

研究分野

  • ナノテク・材料, エネルギー化学
  • ナノテク・材料, 分析化学
  • ナノテク・材料, 無機・錯体化学
  • ナノテク・材料, 生体化学

経歴

  • 2017年10月 奈良教育大学教育学部非常勤講師(兼任)
  • 2012年04月 奈良女子大学研究院自然科学系准教授
  • 2009年04月 - 2012年03月 奈良女子大学理学部化学科准教授
  • 2008年10月 - 2009年12月 奈良教育大学教育学部非常勤講師(兼任)
  • 2007年04月 - 2009年03月 奈良女子大学理学部化学科助教
  • 2001年04月 - 2007年03月 奈良女子大学理学部化学科助手
  • 2000年06月 - 2001年03月 米国Yale大学分子生物物理化学科研究員
  • 2000年04月 - 2001年03月 日本学術振興会特別研究員(PD)
  • 1999年01月 - 2000年03月 日本学術振興会特別研究員(DC)

学歴

  • - 2000年 九州大学 工学研究科 物質創造工学
  • - 1997年 同志社大学 工学研究科 工業化学
  • - 1995年 同志社大学 工学部 工業化学

委員歴

  • 2015年03月 日本化学会 近畿支部 化学教育協議会委員 society

    学協会

  • 2013年03月 - 2015年02月 日本化学会 近畿支部 幹事 society

    学協会

  • 錯体化学若手の会 世話人 society

    学協会

受賞

  • 日本化学会BCSJ賞, 日本化学会, 2003年07月

論文

  • Photophysical and elecron-transfer reaction properties of tris(2,2’-bipyridine)ruthenium(II)-based inhibitors that covalently bound to the active site of chymotrypsin

    Elsevier, 2021年, Journal of Photochemistry and Photobiology, 6, 100027

  • Structures, DFT calculations and emission properties of protonated adenine, cytosine and guanine bases

    RESEARCH TRENDS, 2020年, Trends in Photochemistry & Photobiology, 19, 1 - 16

  • サイエンス・オープンラボを通した化学(化学発光、金属イオンの色)学習 −大学生による演示実験を動機付けにした高等学校授業開発研究−

    中島隆行; 三方裕司; 梶原孝志; 竹内孝江; 浦康之; 高島弘; 松浦紀之

    2020年03月, 教育システム研究, (15), 99 - 109

    研究論文(大学,研究機関等紀要)

  • Anion Influence of Emission Properties and DFT Calculations of Diprotonated and Triprotonated Terpyridines

    Naokazu Yoshikawa; Shoko Yamazaki; Natsumi Kato; Mika Sawai; Kaoru Noda; Nobuko Kanehisa; Eiji Nakata; Hiroshi Takashima

    2019年12月, ChemistrySelect, 4 (45), 13284 - 13294, doi

    研究論文(学術雑誌)

  • Syntheses, X-ray crystal structures, emission properties and DFT calculations of monoprotonated polypyridines

    Naokazu Yoshikawa; Shoko Yamazaki; Natsumi Kato; Akari Kubota; Mika Sawai; Kaoru Noda; Nobuko Kanehisa; Tsuyoshi Inoue; Eiji Nakata; Hiroshi Takashima

    2019年01月, ChemistrySelect, 4 (1), 59 - 65, doi

  • Study of the triplet excited states and DFT calculations of iridium(III) complexes with mixed ligands

    Naokazu Yoshikawa; Shoko Yamazaki; Natsumi Kato; Nobuko Kanehisa; Tsuyoshi Inoue; Eiji Nakata; Hiroshi Takashima

    Density functional theory (DFT) calculations were performed to examine the excited triplet states of various eight iridium(III) complexes and the relationship between these states and the emission spectra. The complexes investigated were 1 [Ir(NO3)2(phen)2]PF6, 2 [IrCl2(phen)2]PF6, 3 [Ir(NO2)2(dmbpy)2]PF6, 4 [IrCl2(dmbpy)2]PF6, 5 [IrCl2(tmphen)2]PF6, 6 [IrCl2(bqn)(dmbpy)]PF6, 7 [IrCl2(bqn)2]PF6 and 8 [IrCl2(bqn)(phen)]PF6. Here, phen is 1,10-phenanthroline, dmbpy is 4,4’-dimethyl-2,2’-bipyridine, tmphen is 3,4,6,7-tetramethyl-1,10-phenanthroline and bqn is 2,2’-biquinoline. Complexes 1, 3, 5, 6 and 8 were newly synthesized for this study and exhibited pronounced phosphorescent emission for 5, 6 and 8. All complexes were calculated to possess excited triplet states. The excited states of the complexes are primarily associated with metal-to-ligand charge transfer (MLCT) and π-π* transitions., 2018年07月15日, Journal of Molecular Structure, 1164, 164 - 171, doi

    研究論文(学術雑誌)

  • Photoinduced elecron-transfer reactions of tris(2,2’-bipyridine)ruthenium(II)-based carbonic anhydrase inhibitors tethering plural binding sites

    Mikiko Suwa; Narumi Imamura; Pirika Awano; Eiji Nakata; Hiroshi Takashima

    2018年04月, Journal of Physical Organic Chemistry, 31 (9), e3848, doi

  • Syntheses, X-ray crystal structures, and emission properties of protonated tripyridyltriazines and their ruthenium(II) complexes

    Naokazu Yoshikawa; Shoko Yamazaki; Hiroko Kimura; Nobuko Kanehisa; Tsuyoshi Inoue; Hiroshi Takashima

    A series of metal-free compounds, ie, planar triprotonated triazine, triazineH3Cl(PF6)2 (1), planar triprotonated triazineH3Br(PF6)2 (2), and nonplanar monoprotonated triazineHPF6 (3), were prepared. Abbreviations used are triazine = tri-2-pyridyltriazine. Ruthenium complexes [RuCl(bpy)(L)](PF6), [RuCl(bpy)(L)](PF6)2, and [Ru(L)2](PF6)2 were also prepared, where bpy is 2,2′-bipyridine and L's are triazine (4) and monoprotonated triazine (5), respectively. Ruthenium complexes [Ru(triazine)2](PF6)2 (6) were also prepared and crystallized. The X-ray crystal structures of the 3 compounds 1, 2, and 3 and the complex 6 were determined. They were also characterized by electrospray ionization mass spectrometry, UV-vis spectroscopy, and density functional theory calculations., 2018年03月01日, Journal of Physical Organic Chemistry, 31 (3), e3777, doi

    研究論文(学術雑誌)

  • 目で見て実感する化合物の分離・分析実験

    高島弘

    2017年04月, 化学と教育, 65 (4), 184 - 185, doi

  • Emission property and DFT calculation for the (MLCT)-M-3 luminescence of Ru(bpy)(2)(L)(2+) complex

    Naokazu Yoshikawa; Hiroko Kimura; Shinichi Yamabe; Nobuko Kanehisa; Tsuyoshi Inoue; Hiroshi Takashima

    Electronic structures of ruthenium complexes [Ru(bpy)(2)(L)](2+) were studied by DFT calculations, where bpy is 2,2'-bipyridine and L's are its derivatives. They are parent (1) and five complexes with L = 4,4'dimethyl-2,2'-bipyridine (2), 6,6'-dimethy1-2,2'-bipyridine (3), biquinoline (4), 5-nitro-1,10phenanthroline (5) and two acetonitrile molecules (6). These complexes were characterized by ESIMS, 1H NMR, UV vis spectroscopy and elementary analysis. The crystal structures of 3.(PF6)2, 4.(PF6)2, 5.(PF6)2 and 6.(PF6)2 were also determined. Spin densities were analyzed to characterize the excited triplet states in those complexes. It was found that the complexes have three triplet (called here 3MLCT, 3MC1 and 3MC2) states. The 3MC1 and 3MC2 states have elongated Ru N bonds and large spin densities on Ru2. Those states are stable and would lead to the nonradiative relaxation to the ground state. In particular, those of 3, 5 and 6 are very stable, which results in their poor quantum yields (0 < 0.01) of the emissions. In contrast, both 1 and 2 showed the 3MLCT states. Energy gaps between triplet and ground states were compared with energies corresponding to wavelengths of emission spectra of 1-5. Good agreement between the calculated and the experimental energies was found. Moreover, dual emission which depends on the excitation wavelength was observed in complex 4. (C) 2016 Elsevier B.V. All rights reserved., 2016年08月, JOURNAL OF MOLECULAR STRUCTURE, 1117, 49 - 56, doi;web_of_science

    研究論文(学術雑誌)

  • Syntheses, X-ray crystal structures, and emission properties of diprotonated tetrapyridylpyrazine and triprotonated terpyridine

    Naokazu Yoshikawa; Shinichi Yamabe; Nobuko Kanehisa; Tsuyoshi Inoue; Hiroshi Takashima

    A series of metal-free compounds, that is, planar diprotonated tetraH(2)(PF6)(2) (1), planar monoprotonated bppzHPF(6) (2), nonplanar diprotonated bppzH(2)(PF6)(2) (3), and planar triprotonated terpyH(3)Cl(PF6)(2) (4), were prepared and characterized by electrospray ionization mass spectrometry, Ultraviolet-visible spectroscopy and cyclic voltammetry. Abbreviations used are tetra = tetra-2-pyridylpyrazine, bppz = 2,3-bis(2-pyridyl)pyrazine, and terpy = 2,2':6',2 ''-terpyridine. The X-ray crystal structures of the four compounds 1, 2, 3, and 4 were determined. Both protonated pyridine rings are hydrogen bonded intramolecularly to the adjacent pyridine ring in compounds 1 and 3. The pi-pi* absorption bands in the ultraviolet region for 1, 2, 3, and 4 in acetonitrile were red-shifted relative to those of the corresponding neutral unprotonated compounds. All the cyclic voltammetry for the protonated species, 1, 2, 3, and 4, showed the first reduction waves from -0.37 to -1.18 V, that were more positive than those of the neutral ones. Density functional theory was applied to interpret the planarity in 1. The attachment of two protons to the two terminal tetra nitrogens in 1 leads to the remarkable emission (Phi = 0.031). The attachment of three protons to the three terpy nitrogens in 4 also gives the large quantum yield (Phi = 0.48). Copyright (C) 2015 John Wiley & Sons, Ltd., 2016年06月, JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 29 (6), 269 - 275, doi;web_of_science

    研究論文(学術雑誌)

  • Transition states of the (MLCT)-M-3 to (MC)-M-3 conversion in Ru(bpy)(2)(phen derivative)(2+) complexes

    Naokazu Yoshikawa; Shinichi Yamabe; Shigeyoshi Sakaki; Nobuko Kanehisa; Tsuyoshi Inoue; Hiroshi Takashima

    Electronic structures of ruthenium complexes [Ru(bpy)(2)(L)](2+) were studied by DFT calculations, where bpy is 2,2'-bipyridine and L's are 1,10-phenanthroline (phen) derivatives. They are parent (1) and eight complexes with L = 4-phenyl-phen (2), 4,7-diphenyl-phen (3), 2,9-dimethyl-4,7-diphenyl-phen (4), 2, 9-dimethyl-phen (5), 3,4,7,8-tetramethyl-phen (6), 5-amino-phen (7), 5-methyl-phen (8), and 3-phenylethynyl-phen (9). Those complexes except 7, and 9 were prepared and characterized. Three triplet (called here (MLCT)-M-3, (MC1)-M-3 and (MC2)-M-3) states were obtained in all the complexes. (MC1)-M-3 and (MC2)-M-3 states were found to have the elongated Ru-N bonds and large spin densities on Ru2+. The geometry optimization of the triplet state of ruthenium complexes leads to the elongation of two trans Ru N bonds confirming the (MC)-M-3 character. The correlation between quantum yields and ((MLCT)-M-3 - (MC2)-M-3) energy gaps was examined and discussed. Successive conversion paths of ((MLCT)-M-3 -> (MC1)-M-3) and ((MC1)-M-3 -> (MC2)-M-3) of 1 and 5 were determined. Their activation energies were calculated to be very small. (C) 2015 Elsevier B.V. All rights reserved., 2015年08月, JOURNAL OF MOLECULAR STRUCTURE, 1094, 98 - 108, doi;web_of_science

    研究論文(学術雑誌)

  • A DFT Study of the Triplet Excited States of Iridium(III) Complexes with Terpyridine Ligands

    Naokazu Yoshikawa; Shinichi Yamabe; Shigeyoshi Sakaki; Nobuko Kanehisa; Tsuyoshi Inoue; Hiroshi Takashima

    2014年01月, Canadian Chemical Transactions, 2, 134 - 148, doi

  • Photoinduced Elecron-Transfer Reactions of Carbonic Anhydrase Inhibitor Containing tris(2,2’-Bipyridine)ruthenium(II) Analogue

    Hiroshi Takashima; Misa Fukuda; Fumie Nakagaki; Tomoko Ogata; Keiichi Tsukahara

    A ruthenium(II) complex-based carbonic anhydrase (CA) inhibitor, [Ru(bpy)2(bpybs)]2+ {bpy = 2,2′-bipyridine and bpybs = 4′-methyl-2,2′-bipyridinyl-4-carboxylic acid (2-{2-[(4- sulphamoylbenzoylamino)ethoxy]ethoxy}ethyl)amide}, tethering a benzenesulfonamide group and a [Ru(bpy)3]2+ moiety has been prepared. The CA activity was effectively suppressed by a synthetic [Ru(bpy)2(bpybs)]2+ inhibitor, and the dissociation constant at pH 7.2 and at 25 C was determined to be KI = 1.9 ± 0.2 μM. Next, in the presence of CA and a sacrificial electron acceptor, such as pentaamminechlorocobalt(III) complex, the photoexcited triplet state of 3([Ru(bpy)2(bpybs)]2+)* was quenched through an intermolecular photoinduced ET mechanism to form the oxidized [Ru(bpy)2(bpybs)]3+, followed by the intramolecular electron abstraction from an amino-acid residue near the active site of CA. The resulting oxidized CA was catalytically inactive. Kinetic experiments also revealed that the second-order rate constant for the initial step and the first-order rate constant for the second step under our experimental conditions were kq = 4.8 × 107 M-1 s-1 and kIET = 6.6 × 104 s-1, respectively. Thus, the intramolecular ET between CA and [Ru(bpy)2(bpybs)] 3+ is a crucial event to regulate CA activity by the visible light irradiation of a synthetic [Ru(bpy)3]2+-type inhibitor. © 2013 American Chemical Society., 2013年03月07日, The Journal of Physical Chemistry, B, 117 (9), 2625 - 2635, doi

    研究論文(学術雑誌)

  • Differences of Structures and Electronic Properties in the Triplet States between Dibromo and Dichloro Mononuclear Polypyridine Iridium(III) Complexes

    Naokazu Yoshikawa; Shinichi Yamabe; Nobuko Kanehisa; Tsuyoshi Inoue; Hiroshi Takashima; Keiichi Tsukahara

    Emission and electronic properties of eight iridium(III)-centered polypyridine complexes were studied systematically. A crystal structure of [IrBr2(phen)(2)]PF6 was obtained by X-ray diffraction study, where phen is 1,10-phenanthroline. Those in the triplet states were also determined by DFT calculations to investigate the source of emission spectra. Two triplet structures of [IrX2(bpy)(2)](+) and [IrX2(bpy)(2)](+) and the transition state of interconversion were obtained with X- = Cl- and Br-. Here, bpy is 2,2'-bipyridine. For the chloro complexes, two triplet species have nonequivalent bpy and phen ligands through pseudo-Jahn-Teller geometric distortion. The dichloro complexes with asymmetric spin density distributions were found to correspond to stronger emission spectra than those for the dibromo compounds. Energies (E's) corresponding to the observed emission wavelengths (E-em's) are in good agreement with the theoretical S-0-T-1, energy differences (Delta E's). For [IrBr2(bpy)(2)](+), E-em = 2.29eV and Delta E= 2.26 eV. For [IrCl2(bpy)(2)](+), E-em = 2.29 eV and Delta E= 2.33 eV. For [IrBr2(phen)(2)](+), E-em = 2.26 eV and Delta E= 2.28 eV. For [IrCl2(bpy)(2)](+), E-em = 2.28 eV and Delta E= 2.34 eV. For all the four complexes, 1A, 1B, 3A, and 3B, DFT calculations indicate lr-N bond rupture. T-c with a small S-0-T-1 energy-gap would undergo nonradiative relaxation. T, indicates a triplet state which is a five-coordinate species with triplet metal-centered character. Coexistence of the triplet state species are discussed in terms of their electronic structures., 2011年12月, BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 84 (12), 1347 - 1354, doi;web_of_science

    研究論文(学術雑誌)

  • The key Cl- ligand for metal-to-ligand charge transfer in mononuclear terpyridine ruthenium(II) and binuclear ruthenium(II) tetrapyridylpyrazine complexes

    N. Yoshikawa; S. Yamabe; N. Kanehisa; T. Inoue; H. Takashima; K. Tsukahara

    Electronic structures of binuclear ruthenium complexes [Ru-2(terpy)(2)(tppz)](4+) (1A) and [Ru2Cl2(L)(2)(tppz)](2+) {L = bpy (2A), phen (3A), and dpphen (4A)} were studied by density functional theory calculations. Abbreviations of the ligands (Ls) are bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline, dpphen = 4,7-diphenyl-1,10-phenanthroline, terpy = 2,2':6',2(n)-terpyridine, and tppz = tetrakis(2-pyridyl)pyrazine. Their mononuclear reference complexes [Ru(terpy)(2)](2+) (1B) and [RuClL(terpy)](+) {L = bpy (2B), phen (3B), and dpphen (4B)} were also examined. Geometries of these mononuclear and binuclear Ru(II) complexes were fully optimized. Their geometric parameters are in good agreement with the experimental data. The binuclear complexes were characterized by electrospray ionization mass spectrometry, UV-Vis spectroscopy, and cyclic voltammograms. Hexafluorophosphate salts of binuclear ruthenium complexes of 3A and 4A were newly prepared. The crystal structure of binuclear complex 1A(PF6)(4) was also determined. Orbital interactions were analyzed to characterize the metal-to-ligand charge-transfer (MLCT) states in these complexes. The Cl- ligand works to raise the orbital energy of the metal lone pair, which leads to the low MLCT state. Copyright (C) 2011 John Wiley & Sons, Ltd., 2011年11月, JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 24 (11), 1110 - 1118, doi;web_of_science

    研究論文(学術雑誌)

  • Photophysical and DNA-Binding Properties of Cytochrome c Modified with a Platinum(II) Complex

    Hiroshi Takashima; Miho Kitano; Chiharu Hirai; Hiroshi Murakami; Keiichi Tsukahara

    Cytochrome c (cyt c) derivatives modified with a platinum(II) complex at the lysine residue, cyt c(III)-[Pt(bpy)(dapap)](1) {bpy = 2,2'-bipyridine, and dapap = 3-(2,3-diaminopropionylamino)propionic acid}, have been prepared. The modified residues are Lys8, Lys13, Lys55, Lys60, Lys73, and Lys88. In the case of the cyt c(III)-[Pt(bpy)(dapap)](1) dyad, the photoexcited singlet state of (1)([Pt(bpy)(dapap)](1))* was quenched by the heme Fe(III) moiety through the intramolecular photoinduced energy-transfer reaction via a through-space mechanism. Next, in the presence of calf thymus (CT)-DNA, the DNA-responsive fluorescence properties of cyt c(III)-(Pt(bpy)(dapap)](1) isomers were investigated. The order of the obtained binding constants between the cyt c(III)-[Pt(bpy)(dapap)](1) isomer and CT-DNA in an aqueous solution suggested that the electrostatic interaction is one of the important factors to stabilize the cyt c-DNA complex. Finally, we discussed the rotational motion of the [Pt(bpy)(dapap)](2+) moiety at the surface of cyt c by fluorescence anisotropy measurement. The increase in the anisotropy parameter, r, for each cyt c isomer clearly revealed that the noncovalent recognition of the [Pt(bpy)(dapap)](2+) moiety by CT-DNA is an essential event in the formation of the cyt c-DNA complex and generation of DNA-sensitive fluorescence signals., 2010年11月, JOURNAL OF PHYSICAL CHEMISTRY B, 114 (43), 13889 - 13896, doi;web_of_science

    研究論文(学術雑誌)

  • Remarkable emissions in diprotonated 2,2 ':6 ',2 ''-terpyridine derivatives

    Naokazu Yoshikawa; Shinichi Yamabe; Nobuko Kanehisa; Tsuyoshi Inoue; Hiroshi Takashima; Keiichi Tsukahara

    A series of new metal-free blue emission compounds, i.e., diprotonated terpyH(2)CIPF(6) (1), tterpyH(2)CIPF(6) (2), ClterpyH(2)CIPF(6) (3), and BterpyH(2)(PF(6))(2) (4), were prepared and characterized by electrospray ionization mass spectrometry, UV-vis spectroscopy, and cyclic voltammetry (CV). Abbreviations used are terpy = 2,2':6',2 ''-terpyridine, tterpy = 4'-(4-tolyl)-2,2':6',2 ''-terpyridine, Clterpy = 4'-chloro-2,2':6',2 ''-terpyridine, and Bterpy = 4,4',4 ''-tert-butyl-2,2':6',2 ''-terpyridine. The X-ray crystal structures of the three new compounds 1, 2, and 4 were determined. Both protonated pyridine rings of the terpyridine derivatives are hydrogen bonded intermolecularly to the adjacent Cl(-) ion in compounds 1, 2, and 3. The pi-pi* absorption bands in the UV region for 1, 2, 3, and 4 in acetonitrile were red-shifted relative to those of the corresponding neutral compounds. All the compounds exhibited stronger emissions (around 400 nm) than their neutral counterparts. All the CVs for the diprotonated species, terpyH(2)(2+), tterpyH(2)(2+), ClterpyH(2)(2+), and BterpyH(2)(2+), showed the first reduction waves around -0.6 V, which were more positive than those of the neutral ones. Density functional theory was applied to interpret the remarkable differences in the interaction of the Cl(-) ion. The attachment of two protons to the two terminal Bterpy nitrogens in 4 elicits remarkable characteristics. Both positive charges on the nitrogens are delocalized over the conjugated pyridine systems and the tertiary carbonium ions are stabilized to lead to stronger emission (Phi = 0.35) than the corresponding neutral Bterpy (Phi = 0.045). CCDC 732045-732047 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif Copyright (C) 2010 John Wiley & Sons, Ltd., 2010年05月, JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 23 (5), 431 - 439, doi;web_of_science

    研究論文(学術雑誌)

  • Direct Comparison of Chiral Substituent Effects for Viologens in Stereoselective Photoinduced Electron-Transfer Reactions with Zinc Myoglobin

    Hiroshi Takashima; Satomi Shibata; Yuka Sekiguchi; Yoshitane Imai; Keiichi Tsukahara

    In order to understand the detailed mechanisms of stereoselective photoinduced electron-transfer (ET) reactions of zinc-substituted myoglobin (ZnMb) with optically active viologens by flash photolysis, we prepared new optically active agents, such as (R,R)- and (S,S)-1,1'-bis(3-hydroxy-2-methylpropyl)-4,4'-bipyridinediylium dichloride ([BMV]Cl-2). The photo-excited triplet state of ZnMb, (3)(ZnMb)*, was successfully quenched by (R,R)- and (SS)-[BMV](2+) ions to form the radical pair of ZnMb cation (ZnMb(center dot+)) and (R,R)- and (S,S)-[BMV](center dot+), followed by a thermal back ET reaction to the ground state. The ratio of the rate constants (k(q)) for ET quenching at 25 degrees C, k(q)(R,R)/k(q)(S,S) = 1.1, indicates that the (R,R)-[BMV](2+) preferentially quenches (3)(ZnMb)*. The selectivity of the rate constants (k(b)) for the back ET from (R,R)- and (SS)-[BMV](center dot+) to ZnMb(center dot+) at 25 degrees C was k(b)(R,R)/k(b)(S,S) = 0.83. The highest stereoselectivity of 1.3 for [BMV](center dot+) was found at low temperature (10 degrees C) in the thermal back ET reaction, where Delta Delta H not equal(R-S) = 6.2 +/- 1.9 kJ mol(-1) and Delta Delta S not equal(R-S) = 19 +/- 2 J mol(-1) K-1 were obtained. The structural differences between [BMV](2+) and the other viologens imply that the bulky aromatic substituent seems to be more important than the distance from the chiral center to the viologen moiety in order to enhance the ET stereoselectivity., 2009年10月, BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 82 (10), 1250 - 1257, doi;web_of_science

    研究論文(学術雑誌)

  • A metal free blue emission by the protonated 2,2 ':6 ',2 ''-terpyridine hexafluorophosphate

    Naokazu Yoshikawa; Shinichi Yamabe; Nobuko Kanehisa; Hiroshi Takashima; Keiichi Tsukahara

    Mono-protonated 2,2':6',2 ''-terpyridine (terpy) compound, 2,2':6',2 ''-terpyridinium hexafluorophosphate {[terpyH]PF(6)}, was prepared and characterized by electrospray ionization mass spectrometry, UV-Vis and emission spectroscopies, cyclic voltammogram (CV), and X-ray crystallography. The proton is located at the central pyridine nitrogen atom of terpy and was found in electron density difference map, which is completely different from the previously reported mono-protonated species, such as [terpyH]ReO(4) and [terpyH]CF(3)SO(3). The H(+) in the latter species is located at the terminal pyridine nitrogen. A small difference of proton positions was found to give a drastic difference of crystal patterns. For [terpyH]PF(6) in CH(3)CN, a new pi-pi* band in the UV region and a blue emission (Phi = 0.052 at room temperature) appeared whose maxima were red-shifted relative to those of the corresponding neutral terpy ligand. CV for the proton adduct showed the first reduction wave at around -0.6 V, being more positive than that of the neutral species. Finally, the density-functional theory (DFT) approach was used to investigate isomerization processes of the protonated terpy. Copyright (C) 2008 John Wiley & Sons, Ltd., 2009年05月, JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 22 (5), 410 - 417, doi;web_of_science

    研究論文(学術雑誌)

  • Detailed Description of the Metal-to-Ligand Charge-Transfer State in Monoterpyridine Ir-III Complexes

    Naokazu Yoshikawa; Shinichi Yamabe; Nobuko Kanehisa; Tsuyoshi Inoue; Hiroshi Takashima; Keiichi Tsukahara

    We synthesized four Ir-III terpyridine complexes with three Cl- anions by using microwave irradiation. By introducing three Cl- anions to the Ir3+ cation, it can be expected that the absorption and emission properties of the complexes change from pi-pi* to metal-to-ligand charge transfer (MLCT). These complexes having intrinsic C-2v symmetry are suitable for analyzing orbital interactions. This symmetry has four irreducible representations, a(1), a(2), b(1), and b(2), which results in no degenerate orbitals. Charge transfers (CTs) from three nitrogen lone-pair orbitals to the 5d(z2) and 5d(x2-y2) atomic orbitals give three Ir-N coordination bonds in the in-plane molecular orbital (MO) overlap of a(1) symmetry. These CTs are described by the 60th and 66th MOs in the [IrCl3(terpy)] complex, (terpy = 2,2':6',2 ''-terpyridine). The antibonding combination of the 5d(xz) and the lone-pair orbital of Cl- gives rise to the high-lying HOMO in b(1) symmetry. The back CT, the highest occupied molecular orbital (HOMO) (b(1)) -> the lowest unoccupied molecular orbital (LUMO) (b(1)), corresponds to MLCT, and the small-energy excitation is confirmed by the long wavelength lambda(max) approximate to 500 nm in the absorption spectroscopy. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009), 2009年05月, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 14 (14), 2067 - 2073, doi;web_of_science

    研究論文(学術雑誌)

  • Structures of polypyridine mononuclear Ir-III complexes in the ground state and the lowest triplet state

    Naokazu Yoshikawa; Shinichi Yamabe; Nobuko Kanehisa; Yasushi Kai; Hiroshi Takashima; Keiichi Tsukahara

    The structures of eight Ir-III centered polypyridine complexes were determined by density-functional-theory calculations. The differences in the optimized geometries between the ground state and the lowest excited triplet state were mainly considered. A crystal structure of [IrCl(bpy)(terpy)](PF6)(2) was also obtained by the X-ray diffraction study, where bpy is 2,2'-bipyridine and terpy is 2,2':6',2 ''-terpyridine. The computed geometries are in good agreement with the experimental ones. Those in the triplet biradical states were determined to evaluate the energy difference between the triplet and the ground states. The resulted values correlate well with the observed emission energies. To investigate the nature of the electronic transition involving the ground and the. first excited triplet states, a Mulliken population analysis of the spin densities on the eight complexes was performed. The geometric changes from free tterpy ligand {tterpy = 4'-(4-tolyl)-2,2':6',2 ''-terpyridine} to the IrIII complexed ligand, and then to triplet biradical were examined. The planarity enhanced the pi-pi* excitation in the ligand and consequently gave the stable triplet biradical of the complex. It was found that efficient phosphorescence should be impacted by the presence of one coplanar polypyridine ligand. (C) 2008 Elsevier B.V. All rights reserved., 2009年01月, INORGANICA CHIMICA ACTA, 362 (2), 361 - 371, doi;web_of_science

    研究論文(学術雑誌)

  • Metal Ion-Dependent Fluorescent Dynamics of Photoexcited Zinc-Porphyrin and Zinc-Myoglobin Modified with Ethylenediaminetetraacetic Acid

    Hiroshi Takashima; Hiroe Kawahara; Miho Kitano; Satomi Shibata; Hiroshi Murakami; Keiichi Tsukahara

    The reconstituted zinc - myoglobin (ZnMb) dyads, ZnMb-[M(II)(edta)], have been prepared by incorporating a zinc-porphyrin (ZnP) cofactor modified with ethylenediaminetetraacetic acid (H(4)edta) into apo-Mb. In case of the monomeric ZnP(edta) cofactor coordinated by one pyridine molecule, ZnP(py)(edta), a spontaneous 1: 1 complex with a transient metal ion was formed in an aqueous solvent, and the photoexcited singlet state of ZnP, (1)(ZnP)*, was quenched by the [Cu(II)(edta)] moiety through intramolecular photoinduced electrontransfer (ET) reaction. The rate constant for the intramolecular quenching ET (k(q)) at 25 degrees C was successfully obtained as k(q) = 5.1 x 10(9) s(-1). In the case of Co(2+), Ni(2+), and Mn(2+), intersystem crossing by paramagnetic effect was mainly considered between (1)(ZnP)* and the [M(II)(edta)] complex. For the ZnMb-[M(II)(edta)] systems, the intramolecular ET reaction between the excited singlet state of (I)(ZnMb)* and the [Cu(II)(edta)] moieties provided the slower quenching rate constant, k(q) = 2.1 x 10(8) s(-1), compared with that of the ZnP(py)(edta) one. Kinetic studies also presented the efficient fluorescence quenching of the (1)(ZnMb)*-[Co(II)(edta)] dyad. Our study clearly demonstrates that wrapping of the ZnP cofactor by the apoprotein matrix and synthetic manipulation at the Mb surface ensure metal ion-sensitive fluorescent dynamics of ZnMb and provides valuable information to elucidate the complicated mechanism of the biological photoinduced ET reactions of hemoproteins., 2008年12月, JOURNAL OF PHYSICAL CHEMISTRY B, 112 (48), 15493 - 15502, doi;web_of_science

    研究論文(学術雑誌)

  • Synthesis and photophysical properties of zinc myoglobin appending an ethidium ion as a DNA intercalator

    Hiroshi Takashima; Yukiko Matsushima; Yasuyuki Araki; Osamu Ito; Keiichi Tsukahara

    In order to elucidate the intramolecular photoinduced electron-transfer or energy-transfer mechanisms of the zinc myoglobin (ZnMb) dyad and to construct a photoreaction system within a Mb-DNA complex, we newly prepared ZnMb appending an ethidium ion (Et+). The steady-state fluorescence of ZnMb-Et+ at 600 nm and its lifetime (2.2 ns) indicate that the excited singlet state of (1)(ZnMb)* is not quenched by the Et+ moiety, whereas the lifetime of the excited triplet state of (3)(ZnMb)*-Et+ was shorter (tau = 4.3 ms) than those of ZnMb and the intermolecular (ZnMb + ethidium) system. Upon photoirradiation of Et+, fluorescence studies indicated the intramolecular quenching reactions from the excited singlet state, (1)(Et+)*, to ZnMb, the process of which is likely the photoinduced energy-transfer reaction via a through-space mechanism. We also demonstrate the photophysical and spectroscopic properties of ZnMb-Et+ in the presence of calf thymus (CT) DNA. The changes in the absorption and fluorescence spectra of ZnMb-Et+ on the addition of CT-DNA up to 15 equiv were very small, indicating that there are no major changes in the heme pocket. However, we observed a longer lifetime of (3)(ZnMb)*-Et+ in the presence of CT-DNA (tau = 5.3 ms) by single flash photolysis. This was induced by noncovalent interactions between Et+ and CT-DNA, followed by a conformational change of Et+ at the surface of ZnMb, where the donor-acceptor distance was probably elongated by CT-DNA. The synthetic manipulation at the Mb surface, by using a DNA intercalator coupled with photoinduced reaction, may provide a sensitive transient signal for DNA and valuable information to construct new Mb-DNA complex., 2008年02月, JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY, 13 (2), 171 - 181, doi;web_of_science

    研究論文(学術雑誌)

  • Synthesis and Spectroscopic Properties of Reconstituted Zinc-Myoglobin Appending a DNA-Binding Platinum(II) Complex

    Hiroshi Takashima; Emi Fujimoto; Chiharu Hirai; Keiichi Tsukahara

    A reconstituted zinc-myoglobin (ZnMb) dyad, ZnMb-[Pt(bpy)(en)](2+), has been prepared by incorporating chemically-modified zinc-porphyrin, being capable of DNA-binding of the Pt complex, [Pt(bpy)(en)](2+), where bpy and en are 2,2'-bipyridine and ethylenediamine, respectively. The steady-state fluorescence of the cofactor, [Pt(bpy)(mu-enPP)Zn]Cl-2, in MeOH indicates that the excited singlet state of zinc-porphyrin was almost quenched, probably because of the strong hydrophobic and pi-pi stacking interactions between the [Pt(bpy)(mu-enPP)Zn](2+) ions. In the reconstituted ZnMb[Pt(bpy)(en)](2+), the quenching reaction of (1)(ZnMb)* with the [Pt(bpy)(en)](2+) moiety does not occur, indicating apo-Mb matrix is essential. On the other hand, when the [Pt(bpy)(en)](2+) moiety was excited, the enhancement of the fluorescence from ZnMb unit was observed. It is suggested that the energy transfer from (1)([Pt(bpy)(en)](2+))* to ZnMb occurs. The spectroscopic changes of ZnMb-[Pt(bpy)(en)](2+) in the presence of calf-thymus DNA were also provided. Soret band at 428 nm gradually decreased, and isosbestic points at 321, 414, and 432 nm were observed with increasing the DNA concentration. When the Pt-II moiety was excited at lambda(ex) 321 nm, the fluorescence signal around 600 nm similarly decreased. The synthetic manipulation of ZnMb by using a DNA-binding Pt-II complex demonstrates sensitive fluorescent signal for DNA and valuable information to study photoinduced electron transfer within a Mb-DNA complex., 2008年, CHEMISTRY & BIODIVERSITY, 5 (10), 2101 - 2112, doi;web_of_science

    研究論文(学術雑誌)

  • エチレンジアミン四酢酸を修飾した亜鉛ミオグロビンの光ダイナミックス

    高島 弘; 川原裕恵; 北野美穂; 塚原敬一; 村上 洋

    2008年, 第8回光量子科学研究シンポジウム論文集, 69-72

  • Synthesis, characterization, and DFT investigation of Ir-III tolylterpyridine complexes

    Naokazu Yoshikawa; Shinichi Yamabe; Nobuko Kanehisa; Yasushi Kai; Hiroshi Takashima; Keiichi Tsukahara

    Three new polypyridine iridium(III) complexes [(IrCl)-Cl-III(L)-(tterpy)](PF6)(2) (L = phen (1), dpphen (2), and dmbpy (3)) were prepared. Reference complexes [(IrCl)-Cl-III(bpy)(tterpy)](PF6)(2) (4) and [Ir-III(L)(2)](PF6)(3) (L = tterpy (5) and terpy (6)) were also prepared. Abbreviations of the ligands used here are phen = 1,10-phenanthroline, dpphen = 4,7-diphenyl-1,10-phenanthroline, bpy = 2,2'-bipyridine, dmbpy = 4,4'-dimethyl-2,2'-bipyridine, tterpy = 4'-(4-tolyl)-2,2':6',2"-terpyridine, and terpy = 2,2':6',2"-terpyridine. The syntheses, which were accomplished in typical reaction times of fifteen minutes by using a microwave oven, were easier than a previous method. The complexes were characterized by electrospray mass spectrometry, UV/Vis spectroscopy, and cyclic voltammetry (CV). The X-ray structures of the two complexes 5 and 6 were also obtained. Cyclic voltammograms of all the [(IrCl)-Cl-III(L)(tterpy)](2+) complexes showed that the first reduction occurred at around -0.67 V, which is attributed to the reduction of the tterpy ligand in [(IrCl)-Cl-III(L)(tterpy)](2+). The electronic properties of complexes 5 and 6 were studied by using B3LYP functional calculations, and their optimized geometries were compared to those of the experimentally observed ones. Excited triplet and singlet states are also examined by using time-dependent density functional theory (TDDFT). The calculated energies of the lowest singlet and triplet states in the two complexes are in good agreement with the experimental absorption and phosphorescence spectra. In this study, it was found that [(IrCl)-Cl-III(L)(tterpy)](2+) emits an intense phosphorescence at room temperature. Since the lowest unoccupied molecular orbitals (LUMOs) of all [(IrCl)-Cl-III(L)-(tterpy)](2+) complexes are composed of the pi*-system contribution of the tterpy ligand, the spectroscopic and electrochemical results are discussed comparatively, ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)., 2007年05月, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 13 (13), 1911 - 1919, doi;web_of_science

    研究論文(学術雑誌)

  • Photoinduced intramolecular electron-transfer reactions of reconstituted met- and zinc-myoglobins appending acridine and methylacridinium ion as DNA-binders

    Hiroshi Takashima; Chisako Tara; Sachiko Namikawa; Tomoko Kato; Yasuyuki Araki; Osamu Ito; Keiichi Tsukahara

    Three types of reconstituted met- and zinc-myoglobin (metMb and ZnMb) dyads, ZnMbAc(4)Me+, ZnMbAc(6)Me+, and metMbAc(6) have been prepared by incorporating chemically modified metalloporphyrin cofactor appending an acridine (Ac) or a methylacridinium ion ([AcMe](+)) into apo-Mb. In the bimolecular system between ZnMb and [AcMe](+), the photoexcited triplet state of ZnMb, (3)(ZnMb)*, was successfully quenched by [AcMe](+) to form the radical pair of ZnMb cation (ZnMb(center dot+)) and reduced methylacridine ([AcMe](center dot)), followed by a thermal back ET reaction. The rate constants for the intermolecular quenching ET (k(q)) and the back ET reaction (k(b)) at 25 degrees C were successfully obtained as k(q) = (8.8 +/- 0.4) x 10(7) M-1 s(-1) and k(b) = (1.2 +/- 0.1) x 10(8) M-1 s(-1), respectively. On the other hand, in case of the intramolecular photoinduced ET reactions of ZnMbAc(4)Me+ and ZnMbAc(6)Me+ dyads, the first-order quenching rate constants (k(ET)) of (3)(ZnMb)* by [AcMe](+) moiety were determined to be k(ET) = 2.6 x 10(3) and 2.5 x 10(3) s(-1), respectively. When such ET occurs along the alkyl spacer via through-bond mechanism at the surface of Mb, the obtained k(ET) is reasonable to provide decay constant of beta (1.0-1.3 A(-1)). Upon photoirradiation of [AcMe](+) moiety, kinetic studies also presented the intramolecular quenching reactions from the excited singlet state, (1)([AcMe](+))*, whose likely process is the photoinduced energy-transfer reaction. For metMbAc(6) dyad, steady-state fluorescence was almost quenched, while the signal around 440 nm gradually appeared in the presence of various concentrations of DNA. Our study implies that synthetic manipulation at the Mb surface, by using an artificial DNA-binder coupled with photoinduced reaction, may provide valuable information to construct new Mb-DNA complex and sensitive fluorescent for DNA., 2006年12月, JOURNAL OF PHYSICAL CHEMISTRY B, 110 (51), 26413 - 26423, doi;web_of_science

  • Syntheses, characterization, and DFT investigation of new mononuclear acetonitrile- and chloro-ruthenium(II) terpyridine complexes

    Naokazu Yoshikawa; Shinichi Yamabe; Nobuko Kanehisa; Yasushi Kai; Hiroshi Takashima; Keiichi Tsukahara

    A series of mononuclear acetonitrile complexes of the type [Ru(CH3CN)(L)(terpy)](2+) {L = phen (1), dpbpy (3), and bpm (5)}, and their reference complexes [RuCl(L)(terpy)](+) {L = phen (2), dpbpy (4), and dpphen (6)} were prepared and characterized by electrospray ionization mass spectrometry, U-V-vis spectroscopy, and cyclic voltammograms (CV). Abbreviations of the ligands (Ls) are phen = 1,10-phenanthroline, dpbpy=4,4'-diphenyl-2,2'-bipyridine, bpm=2,2'-bipyrimidine, dpphen=4,7-diphenyl-1,10-phenanthroline, bpy= 2,2'-bipyridine, and terpy=2,2':6',2"-terpyridine. The X-ray structures of the two complexes 2 and 3 were newly obtained. The metal-to-ligand charge transfer (MLCT) bands in the visible region for 1, 3, and 5 in acetonitrile were blue shifted relative to those of the reference complexes [RuCl(L)(terpy)](+). CV for all the [Ru(CH3CN)(L)(terpy)](2+) complexes showed the first oxidation wave at around 0.95 V, being more positive than those of [RuCI(L)(terpy)](+). The time-dependent-density-functional-theory approach (TDDFT) was used to interpret the absorption spectra of 1 and 2. Good agreement between computed and experimental absorption spectra was obtained. The DFT approach also revealed the orbital interactions between Ru(phen)(terpy) and CH3CN or Cl-. It is demonstrated that the HOMO-LUMO energy gap of the acetonitrile ligand is larger than that of the Cl- one. (c) 2006 Elsevier B.V. All rights reserved., 2006年11月, INORGANICA CHIMICA ACTA, 359 (14), 4585 - 4593, doi;web_of_science

    研究論文(学術雑誌)

  • Syntheses, structures, and mesomorphic properties of two series of oxovanadium(IV) salen and salpn complexes with 4-substituted long alkoxy chains

    Yuriko Abe; Kyoko Nakabayashi; Nahoko Matsukawa; Hiroshi Takashima; Masayasu Iida; Tomoaki Tanase; Makiko Sugibayashi; Hidetomo Mukai; Kazuchika Ohta

    Two series of oxovanadium(IV) salen and salpn complexes containing 4-substituted alkoxy chains of aromatic rings, [VO((4-CnH2n+1O)(2)salen)] (n = 3 (1), 4 (2), 6 (3), 8 (4), 10 (5), 12 (6), 14 (7), 16 (8), 18 (9), and 20 (10) and salen = N,N'-ethylenebis(salicylideneiminato)), and [VO((4-CnH2n+1O)(2)salpn)] (n = 8 (11), 10 (12), 12 (13), 14 (14), 16 (15), and 18 (16) and salpn = N,N'-propylenebis(salicylideneiminato)), have been prepared and their mesomorphic properties have been investigated. The crystal structures of 1-9 except for 7 by an X-ray crystallographic analysis have been revealed. Complexes 4-9 in the solid state have been confirmed as novel bilayer crystal structures composed of only the VO(IV) complex without linear chains via the V=O units. The VO(IV) complexes with longer alkoxy chains of 8-10 transferred from the bilayer crystal to the bilayer metallomesogens (liquid crystals). Based on the X-ray analyses and the precise extinction rules for 8-10 with the bilayer metallomesogens, complexes 8-10 were identified as the liquid crystalline (M(Pa2(1))) phase derived from 80 layer groups, On the other hand, the 4-alkoxysalpn complexes of 14-16 showed the unusual rectangular columnar mesophase (Col(Gamma)) with the linear chain via the V=O units supported by the existence of the V=O stretching band characteristic of weak linear chain formation via the V=O units in the liquid crystal. (c) 2006 Elsevier B.V. All rights reserved., 2006年09月, INORGANICA CHIMICA ACTA, 359 (12), 3934 - 3946, doi;web_of_science

    研究論文(学術雑誌)

  • Syntheses, structures, and mesomorphism of a series of Ni(II) salen complexes with 4-substituted long alkoxy chains

    Yuriko Abe; Hiroko Akao; Yukiko Yoshida; Hiroshi Takashima; Tomoaki Tanase; Hidetomo Mukai; Kazuchika Ohta

    A series of nickel(II) salen complexes containing 4-substituted alkoxy chains of aromatic rings, [Ni((4-CnH2n+1O)(2)salen)] (n = 3 (1), 4 (2), 6 (3), 8 (4), 10 (5), 12 (6), 14 (7), 16 (8), 18 (9), and 20 (10)), and their parent complex, [Ni((4-HO)(2)salen)] (11) (salen = N,N'-ethylenebis(salicylideneiminato)), have been prepared and mesomorphic properties have been investigated. An X-ray crystallographic analysis revealed that complex 11 (.) 2DMF has one-dimensional stacking structure supported by the pi-pi interaction between the six-membered chelate and aromatic rings with the Ni-Ni distances of alternatively 3.3957 and 3.7224 angstrom and that complex 3 is formed by one-dimensional stacking by weak C-H center dot center dot center dot 0 type hydrogen bonded interaction between the five-membered chelate ring and phenoxo atoms of the dramatically distorted salen moieties with the Ni-Ni distance of 5.994 angstrom. Complexes 1-6 did not exhibit any mesophases. On the other hand, complexes 7-10 with longer alkoxy chains of n = 14-20 showed an unusual metallomesogen of a lamello-columnar mesophase within the smectic layers with an interlamellar distance of 31.1 angstrom (7), 33.6 angstrom (8), 37.1 angstrom (9), and 39.5 angstrom (10) and nearly constant stacking distance of 6.19-6.24 angstrom between the inter-dimers, irrespective of the variation of the alkoxy chain lengths by the X-ray diffraction measurements of the liquid crystal. The relationship between molecular assemblies and mesomorphic properties is discussed. (c) 2006 Elsevier B.V. All rights reserved., 2006年07月, INORGANICA CHIMICA ACTA, 359 (10), 3147 - 3155, doi;web_of_science

    研究論文(学術雑誌)

  • Stereoselective and driving-force-dependent photoinduced electron-transfer reactions of zinc myoglobin with optically active N,N '-dimethylcinchoninium and N,N '-dimethylcinchonidinium ions

    H Takashima; A Araki; K Takemoto; N Yoshikawa; K Tsukahara

    In order to understand the detailed mechanism of the stereoselective photoinduced electron-transfer (ET) reactions of zinc-substituted myoglobin (ZnMb) with optically active molecules by. ash photolysis, we designed and prepared new optically active agents, such as N,N'-dimethylcinchoninium diiodide ([MCN] I-2) and N,N'-dimethylcinchonidinium diiodide ([MCD] I-2). The photoexcited triplet state of ZnMb, (3)(ZnMb)*, was successfully quenched by [MCN](2+) and [MCD](2+) ions to form the radical pair of ZnMb cation (ZnMb(+)) and reduced [MCN](+) and [MCD](+), followed by a thermal back ET reaction to the ground state. The rate constants (k(q)) for the ET quenching at 25 degrees C were obtained as k(q)(MCN)=( 1.9 +/- 0.1) x 10(6) M-1 s(-1) and k(q)(MCD) = (3.0 +/- 0.2) x 10(6) M-1 s(-1), respectively. The ratio of k(q)(MCD)/ k(q)(MCN)= 1.6 indicates that the [MCD](2+) preferentially quenches (3)(ZnMb)*. The second-order rate constants (k(b)) for the thermal back ET reaction from [MCN](+) and [MCD](+) to ZnMb + at 25 degrees C were k(b)(MCN)=(0.79 +/- 0.04) x 10(8) M-1 s(-1) and k(b)(MCD)= (1.0 +/- 0.1) x 10(8) M-1 s(-1), respectively, and the selectivity was k(q)(MCD)/ k(q)(MCN)= 1.3. Both quenching and thermal back ET reactions are controlled by the ET step. In the quenching reaction, the energy differences of Delta Delta H not equal (MCD - MCN) and Delta Delta S-not equal (MCD - MCN) at 25 degrees C were obtained as - 1.1 and 0 kJ mol(-1), respectively. On the other hand, Delta Delta H-not equal (MCD - MCN)= 11 +/- 2 kJ mol(-1) and T Delta Delta S-not equal (MCD - MCN)= - 10 +/- 2 kJ mol(-1) were given in the thermal back ET reaction. The highest stereoselectivity of 1.7 for [MCD](+) found at low temperature (10 degrees C) was due to the Delta Delta S-not equal value obtained in the thermal back ET reaction., 2006年04月, JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY, 11 (3), 316 - 324, doi;web_of_science

    研究論文(学術雑誌)

  • Selective and monofunctional guanosine 5 '-monophosphate binding by chloro[3-(2,3-diaminopropionylamino)propionic acid](dimethyl sulfoxide)platinum(II) complex

    H Takashima; C Hirai; K Tsukahara

    A new complex of chloro[3-(2,3-diaminopropionylamino)propionic acid](dimethyl sulfoxide)platinum(II) ([PtCl-(dmso)(Hdapap)]CF3CO2 center dot 2H(2)O) was synthesized and characterized. Among a series of nucleic acids, the selective and 1:1 binding between [PtCl(dapap)(dmso)] and a guanosine 5'-monophosphate ion (Hgmp(-)) in an aqueous solution at pH 4.0 (20 mmol dm(-3), each) was achieved by conducting ESI-MS and NMR experiments. This reaction included the initial chloride ion displacement by H2O, followed by metal coordination to the N7-position of the guanine base. The latter step was not affected in the case of guanosine-3',5'-cyclic monophosphate ion (cgmp(-)), indicating that the phosphate-Pt binding can be ruled out in this system. In order to monitor the binding reaction of [PtCl(dapap)(dmso)] with several nucleic acids, time-course H-1 and P-31 NMR experiments were performed at 25 degrees C. Changes in the NMR chemical shifts of H8, H1', and phosphate signals in Hgmp- upon the addition of [PtCl(dapap)(dmso)] revealed that two products finally remained. Since the synthetic dapap ligand could regulate the reactivity of a ligand coordinated to the Pt-center in [PtCl(dapap)(dmso)], this may arise from the presence of cis- and trans-isomers of [PtCl(dapap)(dmso)] in solution., 2005年09月, BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 78 (9), 1629 - 1634, doi;web_of_science

    研究論文(学術雑誌)

  • Chloro(4,7-diphenyl-1,10-phenanthroline)(2,2 : 6 ',2 ''-terpyridine)ruthenium(II) hexafluorophosphate

    N Yoshikawa; N Kanehisa; Y Kai; H Takashima; K Tsukahara

    The title compound, [RuCl(C24H16N2)(C15H11N3)]PF6, consists of a monomeric Run complex cation and a hexafluorophosphate anion. The coordination environment about the Run atom is distorted octahedral, where the 2,2:6'2"-terpyridine (terpy) ligand is coordinated in a meridional fashion, the 4,7-diphenyl-1,10-phenanthroline (dpphen) ligand is coordinated in a cis fashion and the Cl atom is trans to one of the dpphen N atoms. The Ru-N bond distances are in the range 1.956 (5)-2.096 (5) Angstrom and the Ru-Cl distance is 2.403 (2) Angstrom., 2005年03月, ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 61 (3), M545 - M547, doi;web_of_science

    研究論文(学術雑誌)

  • Acetonitrile(1,10-phenanthroline)(2,2 ': 6 ',2 ''-terpyridine)ruthenium(II) bis(hexafluorophosphate)

    N Yoshikawa; A Ichimura; N Kanehisa; Y Kai; H Takashima; K Tsukahara

    The asymmetric unit of the title compound, [Ru(C2H3N)(phen)(terpy)](PF6)(2) [phen is 1,10-phenanthroline (C12H8N2) and terpy is 2,2': 6',2"-terpyridine (C15H11N3)] contains a monomeric [Ru(CH3CN)(phen)(terpy)](2+) cation and two hexafluorophosphate anions. The ligand environment about the Ru atom is distorted octahedral. The Ru-N distances are in the range 1.933 (5)-2.083 (5) Angstrom and the Ru-N(acetonitrile) distance is 2.016 (7) Angstrom., 2005年01月, ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 61 (1), M55 - M56, doi;web_of_science

    研究論文(学術雑誌)

  • Electrochemical and luminescent properties of new mononuclear ruthenium(II) and binuclear iridium(III)-ruthenium(II) terpyridine complexes

    N Yoshikawa; T Matsumura-Inoue; N Kanehisa; Y Kai; H Takashima; K Tsukahara

    Hexafluorophosphate salts of mononuclear complexes [(RuCl)-Cl-II(L)(terpy)](+) (L = dmbpy (1); dpbpy (2), sambpy (3), and dpp (7), and binuclear complexes [(Ru2Cl2)-Cl-II(dpp)(terpy)(2)](2+) (8) and [(IrRuCl2)-Ru-III-Cl-II(dpp)(terpy)(2)](3+) (9) were prepared and characterized. Abbreviations of the ligands are bpy = 2,2'-bipyridine, dmbpy = 4,4'-dimetyl-2,2'-bipyridine, dpbpy = 4,4'-diphenyl-2,2'-bipyridine, dpp = 2,3-bis(2-pyridyl)pyrazine, sambpy = 4,4'-bis((S)-(+)-alpha-1-phenylethylamido)-2,2'-bipyridine, and terpy = 2,2':6',2"-terpyridine. The absorption spectra of 8 and 9 are dominated by ligand-centered bands in the UV region and by metal-to-ligand charge-transfer bands in the visible region. The details of their spectroscopic and electrochemical properties were investigated. In both binuclear complexes, it has been found that the HOMO is based on the Ru metal, and LUMO is dpp-based. [(IrRuCl2)-Ru-III-Cl-II(dpp)(terpy)(2)](3+), indicating intense emission at room temperature, and a lifetime of 154 ns. The long lifetime of this bimetallic chromophore makes it a useful component in the design of supramolecular complexes., 2004年12月, ANALYTICAL SCIENCES, 20 (12), 1639 - 1644, doi;web_of_science

    研究論文(学術雑誌)

  • cis-dichlorobis(di-2-pyridylamine)iridium(III) hexafluorophosphate

    N Yoshikawa; J Sakamoto; N Kanehisa; Y Kai; H Takashima; K Tsukahara

    The crystal structure of the title compound, [IrCl2(C10H9N3)(2)] PF6, contains a monomeric [IrCl2(bpya)(2)](+) cation (bpya is di-2-pyridylamine) and a hexafluorophosphate anion. The iridium(III) ion is coordinated by four N atoms from two bpya ligands [mean Ir - N distance = 2.049 ( 6) Angstrom] and two Cl atoms [Ir - Cl = 2.344 (2) Angstrom], forming a distorted octahedral environment., 2004年05月, ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 60, M546 - M547, doi;web_of_science

    研究論文(学術雑誌)

  • cis-Dibromobis(4,4ユ-dimethyl-2,2'-bipyridine)manganese(II)

    高島弘; Jun Sakamoto; Naokazu Yoshikawa; Hiroshi Takashima; Keiichi Tsukahara; Nobuko Kanehisa; Yasushi Kai; Keiko Matsumura

    The title compound, [MnBr2(C12H12N2)(2)], has a twofold axis, and the Mn-II atom is coordinated by four N atoms from two 4,4'-dimethyl-2,2'-bipyridine (dmbpy) ligands and two bromide anions, forming a distorted octahedral environment. The Mn-N and Mn-Br bond distances are 2.261 (2)-2.297 (3) and 2.6193 (5) Angstrom, respectively. The dihedral angle between the pyridine rings of each dmbpy ligand is 16.09 (9)degrees., 2004年04月, Acta Crystallographica, 60 (4), M352 - M353, doi;web_of_science

    研究論文(学術雑誌)

  • Electrochemical and phosphorescent properties of new Ir(III) complexes coordinated by various bipyridine derivatives

    N Yoshikawa; J Sakamoto; T Matsumura-Inoue; H Takashima; K Tsukahara; N Kanehisa; Y Kai

    Four useful polypyridine iridium(III) complexes in the form of [IrCl2L2](+) were prepared and their spectroscopic and electrochemical properties as well as X-ray crystallography were investigated. The ligands used were L = 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 4,4'-diphenyl-2,2'-bipyridine, 1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, and 2,2'-biquinoline. Synthetic methods were developed by a sequential ligand-replacement, which occurred in the reaction vessel using a microwave oven. All complexes showed that LUMOs are based on the pi-system contribution of the polypyridine ligand for [IrCl2(bpy)(2)](+), [IrCl2(dmbpy)(2)](+), [IrCl2(dpbpy)(2)](+), [IrCl2(phen)(2)](+), [IrCl2(dpphen)(2)](+) and [IrCl2(bqn)(2)](+). The HOMOs are also localized on the polypyridine ligand in the iridium complexes. It was found that [IrCl2L2](+) emits intense phosphorescence at room temperature. In particular, the use of dpbpy as ancillary ligands extends the lifetime (660 ns) of the (3)(pi-pi*) excited states of Ir(III) polypyridine complexes. The complex [IrCl2(bqn)(2)](+) with electron acceptor substituents shows a large red-shift to 622 nm. It is noticed that iridium polypyridine complexes show intense emissions at various colors, such as yellow for [IrCl2(dmbpy)(2)](+) and red for [IrCl2(bqn)(2)](+), which can be applied to photosensitizers. The spectroscopic and electrochemical details are also reported herein., 2004年04月, ANALYTICAL SCIENCES, 20 (4), 711 - 716, doi;web_of_science

    研究論文(学術雑誌)

  • (11R)-(-)-N,N '-Dimethylcinchonidinium diiodide

    N Yoshikawa; K Takemoto; J Sakamoto; N Kanehisa; Y Kai; H Takashima; K Tsukahara

    The title compound, (-)-4-[hydroxy(1-methyl-5-vinyl-1-azoniabicyclo[2.2.2]oct-2-yl)methyl]-1-methylquinolinium diiodide, C21H28N2O2+.2I(-), is formed from optically active (11R)-(-)-cinchonidine and methyl iodide. The N-Me bond lengths are in the range of 1.476 (7)-1.497 (6) Angstrom., 2004年02月, ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 60 (2), O281 - O282, doi;web_of_science

    研究論文(学術雑誌)

  • (11S)-(+)-N,N '-dimethylcinchoninium diiodide

    N Yoshikawa; K Takemoto; J Sakamoto; N Kanehisa; Y Kai; H Takashima; K Tsukahara

    The title compound, (+)-4-[hydroxy(1-methyl-5-vinyl-1-azoniabicyclo[2.2.2]oct-2-yl)methyl]-1-methylquinolinium diiodide, C21H28N2O2+.2I(-), is formed from optically active (11S)-(+)-cinchonine and methyl iodide. The N-Me bond lengths are in the range 1.48 (1)-1.49 (1) Angstrom., 2004年01月, ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 60 (1), O17 - O18, doi;web_of_science

    研究論文(学術雑誌)

  • cis-dichlorobis(1,10-phenanthroline)iridium(111) hexafluorophosphate

    N Yoshikawa; J Sakamoto; N Kanehisa; Y Kai; K Matsumura; H Takashima; K Tsukahara

    The crystal structure of the title compound, [IrCl2(C12H8N2)(2)] PF6, contains a monomeric [IrCl2(phen)(2)](+) cation (phen is 1,10-phenanthroline) and a hexayuorophosphate anion. The iridium( III) ion is coordinated by four N atoms from two phen ligands [mean Ir - N distance 2.050 (5) Angstrom] and two Cl atoms [Ir - Cl = 2.343 (1) Angstrom], forming a distorted octahedral environment., 2003年11月, ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 59 (11), M972 - M974, doi;web_of_science

    研究論文(学術雑誌)

  • Intramolecular electron-transfer pathway for deoxy and zinc myoglobins modified with N,N,N ',N '',N ''-diethylenetriaminepentaacetatocobaltate(III)

    K Tsukahara; M Nishimine; Y Shioyama; H Takashima; J Hirose

    Horse heart metmyoglobin (metMib), whose N-terminal Glyl is linked by an N,N,N',N'',N''-diethylenetriamine-pentaacetatocobaltate(M) ion ([Co-III(dtpa)]) with an amide bond, was prepared and characterized. A one-electron reduced protein, [deoxyMb{Co-III(dtpa)}], was prepared by reduction with a methylviologen-radical cation, which was produced in situ by a photoreduction using a tris(2,2'-bipyridine)ruthenium(II) ion in the presence of disodium dihydrogen ethylenediaminetetraacetate at 25 degreesC, pH 7.5 (a 0.010 mol dm(-3) tris(hydroxymethyl)aminomethane-HCl buffer), and an ionic strength of 0.50 mol dm(-3) (NaCl). The reaction of [deoxyMb{Co-III(dtpa)}] to form [metMb{Co-II(dtpa)}] obeyed a first-order rate law on the protein concentration. The first-order rate constant was dependent on the concentration of the protein, indicating that both intra- and intermolecular electron-transfer (ET) processes simultaneously occur. The latter is the reaction with excess [metMb{Co-III(dtpa)}] remaining. Both intra- and intermolecular ET rates could be explained by the Marcus theory, including the distance dependence of the rate of the reaction, and might arise mainly from the very large reorganization energy for the Co(III)/Co(II) couple. Zinc-substituted myoglobin, [ZnMb{Co-III(dtpa)}], was also prepared and the photoinduced ET reaction from the excited triplet state of zinc myoglobin to the Co(M) moiety was examined. The observed ET quenching rate constant is reasonably explained by the Marcus theory through the same ET pathway as that for [deoxyMb{Co-III(dtpa)}]. It is suggested that the ET occurs with through-bond and van der Waals interactions from the heme edge to the Co(III) edge via Phe 138 and Len 137 over 18.8 Angstrom (1 Angstrom = 1 x 10(-10) m) both in deoxy and zinc myoglobins., 2003年11月, BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 76 (11), 2135 - 2142, doi;web_of_science

    研究論文(学術雑誌)

  • (4,4 '-dimethyl-2,2 '-bipyridine)chloro-(2,2 ': 6 ',2 ''-terpyridine)-iridium(III) hexafluorophosphate

    N Yoshikawa; J Sakamoto; N Kanehisa; Y Kai; T Matsumura-Inoue; H Takashima; K Tsukahara

    In the title compound, [IrCl(C12H12N2)(C15H11N3)](PF6)(2), the ligand environment about the Ir atom is distorted octahedral. The 2,2':6',2"-terpyridine (terpy) ligand is coordinated in a meridional fashion, the 4,4'-dimethyl-2,2'-bipyridine (dmbpy) ligand coordinated in a cis fashion and the Cl atom is trans to one of the dmbpy N atoms. Ir-N bond distances are 1.971 (5)-2.065 (6) Angstrom and the Ir-Cl distance is 2.357 (2) Angstrom., 2003年10月, ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 59 (10), M830 - M832, doi;web_of_science

    研究論文(学術雑誌)

  • Intramolecular electron transfer of cytochrome c modified with N,N,N ',N '',N ''-diethylenetriaminepentaacetatocobaltate(III)

    K Tsukahara; N Iida; Y Kaida; H Takashima; M Mizobe; R Arakawa

    Horse heart cytochrome c (cytc) modified with an N,N,N',N",N"-diethylenetriaminepentaacetatocobaltate(III) ion, [cytc(III)Co(III)(dtpa))], was prepared and characterized. The major component of singly modified [cytc(III)Co(III)(dtpa))] contains a [Co-III(dtpa)] ion at Lys13, of which the epsilon-amino group is linked with a carboxylate ion of dtpa. A one-electron reduced protein, [cytc(II)(Co-III(dtpa)}], was prepared by reduction with a methylviologen-radical cation, which was produced in situ by a photoreduction using a tris(2,2'-bipyridine)ruthenium(II) ion in the presence of disodium dihydrogen ethylenediaminetetraacetate at 25 degreesC, pH 7.5 (0.010 mol dm(-3) tris(hydroxymethyl)aminomethane-HCl buffer), and an ionic strength of 0.50 mol dm(-3) (NaCl). The reaction of [cytc(II){Co-III(dtpa))] to form [cytc(III)[Co-II(dtpa))] was very slow, and was followed by conventional spectrophotometry. The reaction was of first order in the protein and the first-order rate constant ((3.1 +/- 0.5) x 10(-4) s(-1)) was independent of the concentration of the protein, indicating that the intramolecular electron-transfer (ET) process is predominant. The reaction mechanism is discussed on a through-bond or through-space pathway. The slow intramolecular ET rate might arise not only from the long distance. but also from the large reorganization energy for the Co(III)/Co(II) couple., 2003年07月, BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 76 (7), 1323 - 1328, doi;web_of_science

    研究論文(学術雑誌)

  • cis-Dichlorobis(2,2 '-biquinoline)iridium(III) hexafluorophosphate

    N Yoshikawa; J Sakamoto; N Kanehisa; Y Kai; T Matsumura-Inoue; H Takashima; K Tsukahara

    The crystal structure of the title compound, [IrCl2(bqn)(2)]PF6, (bqn is 2,2'-biquinoline, C18H12N2), contains a monomeric [IrCl2(bqn)(2)](+) cation and a hexafluorophosphate anion. The iridium(III) ion is coordinated by four N atoms from two bqn ligands [mean Ir-N distance 2.065 (5) Angstrom] and two Cl atoms [Ir-Cl=2.342 (2) and 2.353 (2) Angstrom], forming a distorted octahedral environment. Each 2,2'-biquinoline ligand is planar, the mean deviations from the least-squares planes being 0.2431 (6) and 0.1665 (6) Angstrom., 2003年07月, ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 59 (7), M551 - M552, doi;web_of_science

    研究論文(学術雑誌)

  • Remarkably stereoselective photoinduced electron-transfer reaction between zinc myoglobin and optically active binaphthyl bisviologen

    H Takashima; M Tanaka; Y Hasegawa; K Tsukahara

    We have designed and synthesized new optically active bisviologens ([BNMV](4+)) containing a binaphthyl moiety to examine the stereoselective photoinduced electron-transfer (ET) reactions with zinc-substituted myoglobin (ZnMb) by flash photolysis. The photoexcited triplet state of ZnMb, (3)(ZnMb)*, was successfully quenched by [BNMV]4+ ions to form the radical pair of a ZnMb cation (ZnMb(.+)) and a reduced viologen ([BNMV](.3+)), followed by a thermal ET reaction to the ground state. The rate constants (k(q)) for the ET quenching at 25 degreesC were obtained as k(q)(R)-(2.9 +/- 0.2)x 10(7) M-1 s(-1) and k(q)(S)=(2.2 +/- 0.2) x 10(7) M-1 s(-1), respectively. The ratio of k(q)(R)/k(q)(S) = 1. 3 indicates that the (R)-isomer of the chiral viologen preferentially quenches (3)(ZnMb)*. On the other hand, the rate constants (k) for the thermal ET reaction from [BNMV](.3+) to ZnMb(-+) at 25 degreesC were k(R)=(1.2 +/- 0.1) x 10(8) M-1 s(-1) and k(S)= (0.47 +/- 0.03) x 10(8) M-1 s(-1), respectively, and the ratio remarkably increased to k(R)/k(S)=2.6. The activation parameters, DeltaH(not equal) and AS', were determined from the kinetic measurements at various temperatures (10-30 degreesC) to understand the ET mechanisms. In the quenching reaction, the energy differences of DeltaDeltaH(not equal)(R-S) and TDeltaDeltaS(not equal) (R-S) at 25 degreesC were calculated to be -3.9 +/- 1.6 and -3.3 +/- 0.2 kJ mol(-1), respectively, whereas DeltaDeltaH(not equal) (R-S)-7.7 +/- 1.9 kJ mol(-1) and TDeltaDeltaS(not equal) (R-S)-9.9 +/- 0.5kJ mol(-1) were found for the thermal ET reaction. Therefore, the thermal ET reaction to the ground state was proved to be dominated by the entropy term, and the large stereoselectivity may arise from the decrease in charge repulsion between donor and acceptor., 2003年05月, JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY, 8 (5), 499 - 506, doi;web_of_science

    研究論文(学術雑誌)

  • Microwave-Assisted Dehydration of Aqua Complexes

    Naokazu Yoshikawa; Hiroshi Takashima

    2002年12月, The Chemical Educator, 7, 354 - 355, doi

  • Supramolecular construction of covalently and noncovalently-linked photoinduced electron transfer systems in myoglobin scaffold

    H Takashima; YZ Hu; K Sano; S Shinkai; S Oishi; Hamachi, I

    Zinc Protoporphyrin IX-based compound 1 connected with ruthenium tris-bipyridine and beta -cyclodextrin and its reconstituted Myoglobin(Mb(1)) were newly synthesized to construct covalently and non-covalently linked electron transfer reactions using semisynthetic protein. In the presence of an electron acceptor such as anthraquinone, Mb(1) can bind it on the surface and form a self-assembled donor-sensitizer-acceptor triad. The final charge separated state via stepwise electron transfer was generated after photo-excitation of the ruthenium complex by laser flash photolysis., 2001年12月, ELECTROCHEMISTRY, 69 (12), 942 - 945, doi;web_of_science

    研究論文(学術雑誌)

  • Extremely slow intramolecular electron transfer in cytochrome c modified with a diethylenetriaminepentaacetatocobaltate(III) complex

    K Tsukahara; Y Kaida; N Iida; H Takashima; M Mizobe; R Arakawa

    2001年08月, JOURNAL OF INORGANIC BIOCHEMISTRY, 86 (1), 462 - 462, web_of_science

  • Direct comparison of electron transfer properties of two distinct semisynthetic triads with non-protein based triad: Unambiguous experimental evidences on protein matrix effects

    YZ Hu; H Takashima; S Tsukiji; S Shinkai; T Nagamune; S Oishi; Hamachi, I

    In order to understand the roles of protein matrix in electron transfer processes (ET) within biological systems, a heme-based donor (Zn-heme: ZnPP)-sensitizer (Ru2+(bpy)(3))-acceptor (cyclic viologen: BXV4+) triad 1 was used as a probe molecule. Two semisynthetic systems, Cyt-b(562)(1) and Mb(1), in which the triad is incorporated into cytochrome b(562) (Cyt-b(562)) or into myoglobin (Mb), were constructed by cofactor reconstitution. These two semisynthetic proteins were compared with the triad itself (i.e., without the protein matrix) using absorption spectroscopy, steady state emission and excitation studies, laser flash photolysis experiments, and molecular modeling. Photoexcitation of the ZnPP moiety of Cyt-b(562)(1) or Mb(1) leads to a direct ET from the triplet state of ZnPP state ((ZnPP)-Zn-3) to BXV4+ to generate a final charge-separated (CS) state, Cyt-b(562)(Zn+)-Ru2+-BXV3+. or Mb(Zn+)-Ru2+-BXV3+.. On the other hand, direct ET from the excited ZnPP moiety to the BXV4+ moiety is also involved in 1 in the absence of the protein matrix, but the excited state of ZnPP involved is not (ZnPP)-Zn-3, but the singlet excited state ((ZnPP)-Zn-1) in this pathway. When the Ru2+(bpy)(3) moiety of Cyt-b(562)(1) or Mb(1) is excited, a stepwise ET relay occurs with the ion-pair, Cyt-b(562)(Zn)Ru3+-BXV3+. or Mb(Zn)-Ru3+-BXV3+. as an intermediate, leading to the same final CS state as that generated in the direct ET pathway. The lifetimes of the corresponding final CS states were determined to be 300 ns for 1 in the absence of the protein matrix, 600-900 ns for Cyt-b(562)(1) and 1.1-18 mu s for Mb(1), the values of which are greatly affected by the protein matrix. Molecular modeling study of the three systems consistently explained the differences of their photophysical behavior., 2000年06月, CHEMISTRY-A EUROPEAN JOURNAL, 6 (11), 1907 - 1916, doi;web_of_science

    研究論文(学術雑誌)

  • Cyclodextrin-appended myoglobin as a tool for construction of a donor-sensitizer-acceptor triad on a protein surface

    Hamachi, I; H Takashima; YZ Hu; S Shinkai; S Oishi

    A protein-based and noncovalently-linked donor-sensitizer-acceptor triad has been prepared by self-assembly via mechanical linkages and hydrophobic interactions, and its photoinduced electron transfer properties have been studied., 2000年, CHEMICAL COMMUNICATIONS, (13), 1127 - 1128, doi;web_of_science

    研究論文(学術雑誌)

  • 生体分子インターフェースとしてのデンドリマー:非対称性ルテニウム錯体によるシトクロムcの光還元

    浜地 格; 高島 弘

    2000年, Otsuka Commune, 2-3

  • Electron transfer from Zn-protoporphyrin IX to ruthenium ammine attached at His63 of reconstituted cytochrome b562

    Hamachi, I; H Takashima; S Tsukiji; S Shinkai; T Nagamune; S Oishi

    Site-specific modification of Cytochrome b562 With ruthenium ammine (RuA5) at 63-His was successfully carried out. Electron transfer rate from ZnPP in the heme crevice to Ru(III)A5 coordinated to 63-His on the protein surface was determined by the laser flash photolysis., 1999年07月, CHEMISTRY LETTERS, 28 (7), 551 - 552, doi;web_of_science

    研究論文(学術雑誌)

  • Chiral recognition of phenylacetic acid derivatives by aminated cyclodextrins

    T Kitae; H Takashima; K Kano

    Chiral recognition of mandelic acid (1), acetylmandelic acid (2), 1-methoxyphenyl acetic acid (3), phenylsuccinic acid (4), 2-phenylpropanoic acid (5) and ibuprofen (6) in their anionic forms by protonated 6(A)-amino-6(A)-deoxy-beta-cyclodextrin (mono-NH3+-beta-CD) and 6(A),6(D)-diamino-6(A),6(D)-dideoxy-beta-cyclodextrin (di-NH3+-beta-CD) has been studied by means of capillary zone electrophoresis (CZE) and H-1 NMR spectroscopy. Both methods show the preferable guests for mono-NH3+-beta-CD to be the (R)-enantiomers of 1, 3 and 5 and the (S)-enantiomers of 2, 4 and 6. Cooperative work of Coulomb interactions and inclusion is essential for chiral recognition of these anionic guests., 1999年03月, JOURNAL OF INCLUSION PHENOMENA AND MACROCYCLIC CHEMISTRY, 33 (3), 345 - 359, doi;web_of_science

    研究論文(学術雑誌)

  • Chiral recognition of phenylacetic acid derivatives by aminated cyclodextrins

    Takashi Kitae; Hiroshi Takashima; Koji Kano

    Chiral recognition of mandelic acid (1), acetylmandelic acid (2), 1-methoxyphenylacetic acid (3), phenylsuccinic acid (4), 2-phenylpropanoic acid (5) and ibuprofen (6) in their anionic forms by protonated 6A-amino-6A-deoxy-β-cyclodextrin (mono-NH+ 3-β-CD) and 6A,6D-diamino-6A,6D-dideoxy-β-cyclodextrin (di-NH+ 3-β-CD) has been studied by means of capillary zone electrophoresis (CZE) and 1H NMR spectroscopy. Both methods show the preferable guests for mono-NH+ 3-β-CD to be the (R)-enantiomers of 1, 3 and 5 and the (S)-enantiomers of 2, 4 and 6. Cooperative work of Coulomb interactions and inclusion is essential for chiral recognition of these anionic guests., 1999年, Journal of Inclusion Phenomena, 33 (3), 345 - 359, doi

    研究論文(学術雑誌)

  • Ru(bpy)(3)-based artificial receptors toward a protein surface: selective binding and efficient photoreduction of cytochrome C

    H Takashima; S Shinkai; Hamachi, I

    The binding properties of a series of Ru(bpy)(3) complexes to cytochrome c are described; these compounds act as selective cytochrome c receptors and one derivatie is shown to be a photodriven modulator of the cytochrome c redox state., 1999年, CHEMICAL COMMUNICATIONS, (23), 2345 - 2346, doi;web_of_science

    研究論文(学術雑誌)

  • Entropy-dominating strong binding of carboxylate anions to protonated aminocyclodextrin

    K Kano; T Kitae; H Takashima; Y Shimofuri

    Protonated heptakis(6-amino-6-deoxy)-beta-cyclodextrin complexes with p-methylbenzoate and N-acetylrryptophan anions more strongly than a monoamino-beta-cyclodextrin cation. Such a strong association is dominated by large and positive entropy changes for complexation which might be due to extensive dehydration from both host and guest upon complexation., 1997年, CHEMISTRY LETTERS, 26 (9), 899 - 900, doi;web_of_science

    研究論文(学術雑誌)

  • Use of Electrostatic Interaction for Chiral Recognition. Enantioselective Complexation of Anionic Bindphtyls with Protonated Amino-β-Cyclodextrin

    Koji Kano; Takashi Kitae; Hiroshi Takashima

    The studies using NMR and capillary zone electrophoresis clearly reveal that protonated 6(A)-amino-6(A)-deoxy-beta-cyclodextrin recognizes the chirality of anionic binaphthyl derivatives such as 1,1'-binaphthyl-2,2'-diyl phosphate and 1,1'-binaphthyl-2,2'-dicarboxylate through electrostatic interaction between the host and the guest and simultaneous inclusion., 1996年, Journal of Inclusion Phenomena, 25 (1-3), 243 - 248, doi;web_of_science

    研究論文(学術雑誌)

  • シクロデキストリン/ポリ塩化ビニルキャストフィルムの作製とその不斉認識能

    加納航治; 高島 弘; 谷内靖子

    The poly(vinylchloride) (PVC) thin films embedding amphiphilic cyclodextrins at the one sides of the films have been prepared by spreading the solutions of the mixtures of PVC and cyclodextrin derivatives in THF-toluene on water. The XPS analyses indicate that the hydrophilic cyclodextrin head groups are arranged at the surfaces of the polymer films. The chiral recognition of such cyclodextrin films has been studied by dipping the films in the aqueous solutions of (R)- and (S)-1,1'-binaphthyl-2,2'-diylphosphates (BNP) and analyzing the films by means of XPS spectroscopy. The (S)-BNP is preferentially bound to the cyclodextrin-embedding PVC films, which is in agreement with the results obtained for the homogeneous aqueous system as well as those for the cyclodextrin monolayer and LB membranes. The enantiomer selectivity of the film is altered by the dipping time. The XPS and FT-IR measurements indicate that the 2-naphthoate anion in water is bound to the cyclodextrin film in its salt form. Deducing from this result, the BNP anion in water seems to be transferred to the cyclodextrin film in its salt form. It is assumed that the chiral recognition is achieved by the enantioselective inclusion of BNP into the cyclodextrin cavity at the surface of the PVC film., 1996年, 高分子論文集, 53 (9), 542 - 547, doi;web_of_science

    研究論文(学術雑誌)

  • Structures, DFT calculations and emission properties of protonated adenine, cytosine and guanine bases

    Naokazu Yoshikawa; Shoko Yamazaki; Kana Kimori; Yuna Kakimoto; Kanako Mito; Shiori Eguchi; Risa Yokoyama; Nobuko Kanehisa; Norimitsu Tohnai; Eiji Nakata; Hiroshi Takashima

    2020年12月, Trends in Photochemistry & Photobiology, 19, 1 - 16

    研究論文(学術雑誌)

  • Photophysical and elecron-transfer reaction properties of tris(2,2’-bipyridine)ruthenium(II)-based inhibitors that covalently bound to the active site of chymotrypsin

    Hiroko Kimura; Natsuko Nagasato; Natsumi Kato; Mei Kojima; Chisato Enomoto; Eiji Nakata; Hiroshi Takashima

    2021年03月, Journal of Photochemistry and Photobiology, 6, 100027, doi;rm:research_project_id;rm:research_project_id

    研究論文(学術雑誌)

  • Emission properties of 1,10-phenanthroline derivatives induced by protonation of a nitrogen atom

    Naokazu Yoshikawa; Shoko Yamazaki; Yuna Kakimoto; Shiori Eguchi; Risa Yokoyama; Nobuko Kanehisa; Norimitsu Tohnai; Eiji Nakata; Hiroshi Takashima

    2021年05月, Journal of Molecular Structure, 1242, 130728, rm:research_project_id

    研究論文(学術雑誌)

MISC

  • 疎水性ピレン誘導体とγ‐CD複合体の水中での円偏光発光特性

    沢井美香; 高島弘; 恒石響; 味村優輝; 今井喜胤

    2019年05月18日, ホスト-ゲスト・超分子化学シンポジウム講演要旨集, 17th, 69, j_global

  • シクロデキストリンを用いた疎水性ピレン誘導体の水中での光特性

    高島弘; 沢井美香; 恒石響; 味村優輝; 今井喜胤

    2019年05月18日, ホスト-ゲスト・超分子化学シンポジウム講演要旨集, 17th, 26, j_global

  • サイエンス・オープンラボを通した化学(電池の歴史、化学発光)学習ー大学生による演示実験を動機付けにした高等学校授業開発研究ー

    高島 弘; 竹内孝江; 三方裕司; 浦 康之; 中島隆行; 松浦紀之

    2019年03月, 教育システム研究, (14), 103 - 111

  • サイエンス・オープンラボを通した化学(有機合成、酸化還元、界面活性剤)学習ー大学生による演示実験を動機付けにした高等学校授業開発研究ー

    三方裕司; 竹内孝江; 高島 弘; 松浦紀之; 長谷圭城

    2018年03月, 教育システム研究, (13), 429 - 436

  • キモトリプシンを用いた新奇な円偏光発光(CPL)システムの構築

    日比野可奈子; 高島弘; 原伸行; 今井喜胤

    2017年03月03日, 日本化学会春季年会講演予稿集(CD-ROM), 97th, ROMBUNNO.1PB‐122, j_global;url

  • 非環状オリゴ糖によるヘリシティーの認識

    高岡涼子; 高島弘; 加納航治; 山口雅彦; 大久保仁; 平間正博

    1997年03月, 日本化学会講演予稿集, 72nd (2), 686, j_global;url

講演・口頭発表等

  • 酵素活性部位に結合したトリスビピリジン型ルテニウム錯体の光誘起電子移動反応

    木守佳那; 中田栄司; 高島弘

    第14回有機π電子系シンポジウム, 2021年01月08日

  • Photoinduced electron-transfer reactions of metal complexes as photosensitizers bound to the active site of enzyme

    高島弘; 木守佳那; 中田栄司

    The 11th International Symposium of Advanced Energy Science\n~ Beyond the Decade of Zero Emission Energy ~, 2020年09月15日, rm:research_project_id

  • シクロデキストリンによるアントラセン誘導体の固体状態における包接と円偏光発光

    柿本悠奈; 高島弘; 味村優輝; 今井喜胤

    2020年web光化学討論会, 2020年09月11日, 2020年09月09日, 2020年09月09日

  • 疎水性ピレン誘導体/γ-CD複合体を用いた水中での円偏光発光(CPL)特性

    沢井 美香; 高島 弘; 味村 優輝; 今井 喜胤

    日本化学会第100春季年会, 2020年03月23日, false

  • チロシン残基を導入したトリスビピリジン型ルテニウム(II)錯体の光特性

    木守 佳那; 高島 弘; 中田 栄司

    日本化学会第100春季年会, 2020年03月22日, false

  • ターピリジンへのプロトンとアニオン付加による蛍光特性の変化とDFT計算

    吉川直和; 山崎祥子; 金久展子; 中田栄司; 加藤なつみ; 窪田曙; 沢井美香; 高島 弘

    日本結晶学会令和元年度年会および総会, 2019年11月, 日本結晶学会, false

  • Photoinduced electron-transfer reactions of metal complexes as photosensitizers bound to the active site of enzyme

    高島弘

    The 10th International Symposium of Advanced Energy Science\n~ Beyond the Decade of Zero Emission Energy ~, 2019年09月05日, 京都大学エネルギー理工研究所, 京都大学エネルギー理工研究所, false, rm:research_project_id

  • 酵素活性中心へ導入したトリスビピリジン型ルテニウム(II)錯体の光電子移動反応

    高島 弘; 加藤 なつみ; 中田 栄司

    錯体化学会第69回討論会, 2019年09月, 錯体化学会, 名古屋大学(名古屋市), false

  • 円偏光発光(CPL)特性を有するピレン-シクロデキストリン超分子発光体の創製

    味村 優輝; 本村友希; 沢井 美香; 靜間 基博; 北松瑞生; 高島 弘; 今井 喜胤

    第30回基礎有機化学討論会, 2019年09月, 基礎有機化学会, 大阪国際交流センター, false

  • Anion influence of emission properties and DFT calculations of diprotonated and triprotonated terpyridines

    高島弘

    31st Nano Congress for Future Advancements, 2019年08月, ConferenceSeries llc LTD, ロンドン, true

  • 疎水性ピレン誘導体とγ-CD複合体の水中での円偏光発光特性

    沢井 美香; 高島 弘; 恒石 響; 味村 優輝; 今井 喜胤

    第17回ホストゲスト・超分子化学シンポジウム, 2019年05月, ホストゲスト・超分子化学研究会, 金沢歌劇座, false

  • シクロデキストリンを用いた疎水性ピレン誘導体の水中での光特性

    高島 弘; 沢井 美香; 恒石 響; 味村 優輝; 今井 喜胤

    第17回ホストゲスト・超分子化学シンポジウム, 2019年05月, ホストゲスト・超分子化学研究会, 金沢歌劇座, false

  • ピレン-シクロデキストリン超分子発光体における非古典的円偏光発光(CPL)特性制御

    味村 優輝; 今井 喜胤; 沢井 美香; 高島 弘

    第17回ホストゲスト・超分子化学シンポジウム, 2019年05月, ホストゲスト・超分子化学研究会, 金沢歌劇座, false

  • 疎水性ピレン誘導体とγ-CDを用いた水中での円偏光発光 (CPL)システムの構築

    沢井 美香; 高島 弘; 恒石 響; 味村 優輝; 今井 喜胤

    日本化学会第99春季年会, 2019年03月, 日本化学会, 甲南大学 岡本キャンパス, false

  • ポリピリジンのプロトン付加体の合成・X線結晶構造解析とDFT計算

    吉川直和; 山崎祥子; 加藤なつみ; 窪田曙; 沢井美香; 野田薫; 金久展子; 井上 豪; 高島 弘

    日本結晶学会2018年度年会および総会, 2018年11月, 東京工業大学 大岡山キャンパス, false

  • Photoinduced electron-transfer reactions of metal complexes as photosensitizers bound to the active site of enzyme

    高島弘

    The 9th International Symposium of Advanced Energy Science\n~ Interplay for Zero-Emission Energy ~, 2018年09月, 京都大学エネルギー理工研究所, 京都大学エネルギー理工研究所, false

  • Synthesis, x-ray crystal structure, emission property, and DFT calculation of monoprotonated polypyridine

    高島弘

    25th Nano Congress for Future Advancements, 2018年08月, ConferenceSeries llc LTD, アイルランド, true

  • 酵素活性中心に結合させたトリスビピリジン型ルテニウム(II)錯体の光誘起電子移動反応

    高島 弘; 加藤 なつみ

    錯体化学会第68回討論会, 2018年07月, 錯体化学会, 仙台国際センター(仙台市), false

  • 疎水性ピレン誘導体のシクロデキストリンによる水中でのエキシマーおよび円偏光蛍光

    高島 弘; 窪田曙; 沢井美香

    第16回ホストーゲスト・超分子化学シンポジウム, 2018年06月, 東京理科大学 野田キャンパス, false

  • 酵素活性阻害能をもつチロシン含有トリスビピリジン型ルテニウム(II)錯体の合成と光物理的性質

    加藤 なつみ; 高島 弘

    第45回生体分子科学討論会, 2018年06月, 第45回生体分子科学討論会実行委員会, 大阪市立大学 田中記念館, false

  • Synthesis of tris(2,2'-bipyridine)ruthenium(II) complex containing tyrosine molecules and its introduction into active site of chymotrypsin.

    高島弘

    IUPAC Analytical Chemistry Division Workshop, 2018年04月, Nara Women's University, true

  • ポリピリジン配位子を含むルテ二ウム(II)錯体の三重項状態と遷移状態の研究

    吉川直和; 加藤なつみ; 山崎祥子; 金久展子; 井上 豪; 高島 弘

    平成29年度 日本結晶学会年会および会員総会, 2017年11月, false

  • Photoinduced electron-transfer reactions of metal complexes as photosensitizers bound to the active site of enzyme

    高島弘

    The 8th International Symposium of Advanced Energy Science\n~ Interdisciplinary Approach to Zero-Emission Energy ~, 2017年09月, 京都大学エネルギー理工研究所, 京都大学エネルギー理工研究所, false

  • シクロデキストリンを用いたタンパク質活性中心への金属ポルフィリンの導入と光特性

    岡口咲希; 高島 弘

    錯体化学会第67回討論会, 2017年09月, 錯体化学会, 北海道大学, false

  • シクロデキストリンを用いた金属ポルフィリンのタンパク質活性中心への導入と光特性

    岡口咲希; 加藤なつみ; 高島 弘

    第15回ホストーゲスト・超分子化学シンポジウム, 2017年06月, 立命館大学びわこくさつキャンパス, false

  • シクロデキストリンを用いた酵素活性中心への金属ポルフィリンの導入と光特性

    高島 弘; 岡口咲希; 加藤なつみ

    第15回ホストーゲスト・超分子化学シンポジウム, 2017年06月, false

  • キモトリプシンを用いた新奇な円偏光発光(CPL)システムの構築

    日比野 可奈子; 高島 弘; 原 伸行; 今井 喜胤

    日本化学会第97春季年会, 2017年03月, 日本化学会, 慶応義塾大学 日吉キャンパス, false

  • キモトリプシン活性中心へ導入したポルフィリン亜鉛錯体の光物性

    岡口咲希; 高島 弘

    日本化学会第97春季年会, 2017年03月, 日本化学会, 慶応義塾大学 日吉キャンパス, false

  • シクロデキストリンを用いた疎水性ポルフィリンのタンパク質への導入

    長田 怜香; 高島 弘

    日本化学会第97春季年会, 2017年03月, 日本化学会, 慶応義塾大学 日吉キャンパス, false

  • キモトリプシン(CHT)を用いる新奇な円偏光発光(CPL)システムの構築

    原伸行; 日比野可奈子; 高島弘; 今井喜胤

    日本油化学会第55年会, 2016年09月, 奈良女子大学, false

  • キモトリプシン活性中心へ導入した亜鉛ポルフィリンの光特性

    岡口咲希; 高島 弘

    錯体化学会第66回討論会, 2016年09月, 錯体化学会, 福岡大学七隈キャンパス(〒814-0180 福岡市城南区七隈八丁目19-1), false

  • 混合配位子を含むルテ二ウム(II)錯体の励起三重項状態の研究とDFT計算

    吉川直和; 木村紘子; 山邊信一; 金久展子; 井上 豪; 高島 弘

    第28回配位化合物の光化学討論会, 2016年08月, 複合系の光機能研究会, 京都工芸繊維大学(606-8585 京都府京都市左京区松ヶ崎橋上町), false

  • キモトリプシン活性中心に結合したトリスビピリジン型ルテニウム(II)錯体の光誘起電子移動反応

    木村紘子; 高島 弘

    第28回配位化合物の光化学討論会, 2016年08月, 複合系の光機能研究会, 京都工芸繊維大学(606-8585 京都府京都市左京区松ヶ崎橋上町), false

  • キ?モ?ト?リ?プ?シ?ン?活?性?中?心?へ?導?入?し?た?ト?リ?ス?ビ?ピ?リ?ジ?ン?型?ル?テ?ニ?ウ?ム?(?I?I?)?錯?体?の?光?誘?起?電?子?移?動?反?応

    木村紘子; 高島 弘

    第14回ホスト・ゲスト化学シンポジウム, 2016年06月, ホスト-ゲスト・超分子化学研究会, 高知城ホール (〒780-0850高知県高知市丸ノ内二丁目1番10号), false

  • キモトリプシン活性阻害剤を導入した亜鉛ポルフィリンの合成と特性

    岡口咲希; 高島 弘

    第14回ホスト・ゲスト化学シンポジウム, 2016年06月, ホスト-ゲスト・超分子化学研究会, 高知城ホール (〒780-0850高知県高知市丸ノ内二丁目1番10号), false

  • キモトリプシン活性中心に結合させたトリスビピリジン型ルテニウム(II)錯体の光誘起電子移動反応

    木村紘子; 高島 弘

    日本化学会第96春季年会, 2016年03月, 日本化学会, 同志社大学 京田辺キャンパス, false

  • キモトリプシン活性中心に結合したトリスビピリジン型ルテニウム(II)錯体の光物理的性質および光誘起電子移動反応

    木村紘子; 高島 弘

    日本化学会秋季事業 第5回 CSJ化学フェスタ2015, 2015年10月, 東京都江戸川区 タワーホール船堀, false

  • テトラピリジルピラジンのプロトン付加体の発光特性とDFT計算

    吉川直和; 山邊信一; 金久展子; 井上 豪; 高島 弘

    2015年 光化学討論会, 2015年09月, 大阪市立大学 杉本キャンパス(大阪市住吉区), false

  • キモトリプシン修飾部位を複数導入したトリスビピリジン型ルテニウム(II)錯体の合成と光物理的性質

    木村紘子; 高島 弘

    錯体化学会第65回討論会, 2015年09月, 奈良女子大学, false

  • カルボニックアンヒドラーゼ活性阻害部位を導入した種々のトリスビピリジン型ルテニウム(II)錯体の光誘起電子移動反応

    諏訪美生子; 高島 弘

    日本化学会第95春季年会, 2015年03月, 日本大学理工学部 船橋キャンパス, false

  • トリスビピリジン型ルテニウム(II)錯体を活性中心へ導入したキモトリプシンの光誘起電子移動反応

    永里夏子; 高島 弘

    日本化学会第95春季年会, 2015年03月, 日本大学理工学部 船橋キャンパス, false

  • キモトリプシン活性中心へ導入したトリスビピリジン型ルテニウム(II)錯体の光誘起電子移動反応

    永里夏子; 高島 弘

    日本化学会秋季事業 第4回 CSJ化学フェスタ2014, 2014年10月, 日本化学会, 東京都江戸川区 タワーホール船堀, false

  • カルボニックアンヒドラーゼ活性阻害部位を複数導入したトリスビピリジン型ルテニウム(II)錯体の光誘起電子移動反応

    諏訪 美生子; 高島 弘

    錯体化学会第64回討論会, 2014年09月, 中央大学理工学部 後楽園キャンパス, false

  • キモトリプシン活性中心へ導入したトリスビピリジン型ルテニウム(II)錯体の光誘起電子移動反応

    永里 夏子; 高島 弘

    錯体化学会第64回討論会, 2014年09月, 中央大学理工学部 後楽園キャンパス, false

  • トリスビピリジン型ルテニウム(II)錯体のキモトリプシンへの導入と光特性

    永里夏子; 高島 弘

    錯体化学会第63回討論会, 2013年11月, 琉球大学 千原キャンパス, false

  • PHOTOINDUCED ELECTRON TRANSFER REACTIONS OF WATER SOLUBLE QUANTUM DOT COORDINATED BY CYTOCHROME C

    高島弘

    New Trends of Nano- or Bio-materials Design in Supramolecular Chemistry, 2013年09月, 九州大学医学部キャンパス, true

  • DFT計算と発光エネルギーによるポリピリジン配位子を含むルテ二ウム(II)錯体の励起三重項状態の研究

    吉川直和; 山邊信一; 榊 茂好; 金久展子; 井上 豪; 高島 弘

    第25回配位化合物の光化学討論会, 2013年08月, 佐賀県唐津市 唐津ロイヤルホテル, false

  • 水溶性CdSe/ZnS(コア/シェル型)量子ドットを利用したシトクロムcの光還元反応

    早藤未帆; 高島 弘; 塚原敬一

    日本化学会第93春季年会, 2013年03月, 立命館大学びわこ・くさつキャンパス

  • 銅置換カルボニックアンヒドラーゼの調整と非対称トリスビピリジン型ルテニウム(II)錯体との相互作用

    今村 菜留未; 高島 弘; 塚原 敬一

    錯体化学会第62回討論会, 2012年09月, 富山大学五福キャンパス, false

  • 亜硝酸還元酵素活性中心モデル銅(II)錯体を結合した亜鉛ミオグロビンの調製と光特性

    山崎 菜々実; 高島 弘; 塚原 敬一

    錯体化学会第62回討論会, 2012年09月, 富山大学五福キャンパス, false

  • DFT計算によるターピリジンとアニオン配位子を含むイリジウム(III)錯体の三重項状態の研究

    吉川直和; 山辺信一; 榊 茂好; 金久展子; 井上豪; 高島弘; 塚原敬一

    第24回配位化合物の光化学討論会, 2012年08月, 東京大学 駒場リサーチキャンパス

  • 金属蛋白質表面での相互作用を利用した光誘起電子・エネルギー移動反応

    高島 弘

    錯体化学若手の会 近畿地区勉強会, 2012年06月, 錯体化学若手の会, 京都大学吉田キャンパス, false

  • トリスビピリジン型ルテニウム(II)錯体にビオローゲンを結合させたカルボニックアンヒドラーゼ活性阻害剤の合成と光特性

    辻野歩由美; 高島 弘; 塚原敬一

    日本化学会第92春季年会, 2012年03月, false

  • 亜硝酸還元酵素活性中心モデル銅錯体を結合した亜鉛ポルフィリンの合成と光特性

    山﨑菜々実; 高島 弘; 塚原敬一

    日本化学会第92春季年会, 2012年03月

  • カルボニックアンヒドラーゼ活性阻害部位を複数導入したトリスビピリジン型ルテニウム(II)錯体の酵素活性阻害能

    今村菜留未; 高島 弘; 塚原敬一

    日本化学会第92春季年会, 2012年03月, false

  • 酵素活性中心に導入した光増感金属錯体の 光誘起電子移動反応

    高島弘; 木守佳那; 柿本悠奈; 中田栄司

    京都大学エネルギー理工学研究所ゼロエミッションエネルギー研究拠点共同利用・共同研究成果報告会, 2021年03月09日, 2021年03月09日, 2021年03月09日, rm:research_project_id

  • トリプシン活性中心へ導入したトリスビピリジン型ルテニウム(II)錯体の光誘起電子移動反応

    高島弘; 中田栄司

    第32回配位化合物の光化学討論会, 2021年08月09日, 2021年08月09日, 2021年08月09日, rm:research_project_id

  • Photoinduced electron-transfer reactions of metal complexes as photosensitizers bound to the active site of enzyme

    高島弘; 柿本悠奈; 江口詩織; 横山理沙; 中田栄司

    The 12th International Symposium of Advanced Energy Science\n~ Beyond the Decade of Zero Emission Energy ~, 2021年09月07日, 2021年09月07日, 2021年09月07日, rm:research_project_id

  • アントラセン誘導体のシクロデキストリンによる固体状態での包接とその光学特性

    柿本 悠奈; 今井 喜胤; 中田 栄司; 高島 弘

    2021年光化学討論会, 2021年09月, 2021年09月14日, 2021年09月14日

  • キモトリプシン活性中心へのピレン分子の導入とその光特性

    横山理沙; 今井 喜胤; 中田 栄司; 高島 弘

    第31回基礎有機化学討論会, 2021年09月, 2021年09月21日, 2021年09月21日

  • 水中における疎水性ピレン誘導体/γ-シクロデキストリン錯体の円偏光発光特性

    江口詩織; 今井 喜胤; 中田 栄司; 高島 弘

    第31回基礎有機化学討論会, 2021年09月, 2021年09月21日, 2021年09月21日

担当経験のある科目(授業)

  • 卒業研究III (奈良女子大学)

  • 化学生物環境学特別研究IV (奈良女子大学)

  • 化学生物環境学特別研究III (奈良女子大学)

  • 生物無機化学セミナーB-II (奈良女子大学)

  • 卒業研究IV (奈良女子大学)

  • 課題研究II (奈良女子大学)

  • 化学生物環境学特別研究II (奈良女子大学)

  • 卒業研究II (奈良女子大学)

  • 課題研究I (奈良女子大学)

  • 化学のための研究倫理 (奈良女子大学)

  • 化学生物環境学特別研究I (奈良女子大学)

  • 生物無機化学セミナーB-I (奈良女子大学)

  • 卒業研究I (奈良女子大学)

  • 化学セミナー4 (奈良女子大学)

  • 化学セミナー3 (奈良女子大学)

  • 卒業研究4 (奈良女子大学)

  • 卒業研究3 (奈良女子大学)

  • 化学実験ⅠI (奈良女子大学)

  • 化学キャリアセミナーII (奈良女子大学)

  • パサージュ17B (奈良女子大学)

  • 化学基礎実験2 (奈良女子大学)

  • 基礎無機化学通論Ⅱ (奈良女子大学)

  • 化学基礎実験3 (奈良女子大学)

  • 無機化学通論Ⅱ (奈良女子大学)

  • プロジェクト演習(C) (奈良女子大学)

  • 化学実験Ⅰ (奈良女子大学)

  • 無機生体関連化学セミナーⅡ (奈良女子大学)

  • 基礎化学Ⅰ (奈良女子大学)

  • 無機化学通論II (奈良女子大学)

  • 無機化学外国語特論II (奈良女子大学)

  • サイエンス・オープンラボII(C) (奈良女子大学)

  • サイエンス・オープンラボI(C) (奈良女子大学)

  • 化学セミナー4 (奈良女子大学)

  • 化学実験I (奈良女子大学)

  • 奈良女子大学の化学 (奈良女子大学)

  • 化学セミナー3 (奈良女子大学)

  • 可視化リテラシー (奈良女子大学)

  • 機能化学概論 (奈良女子大学)

  • 化学特別研究IV (奈良女子大学)

  • 化学特別研究II (奈良女子大学)

  • プロジェクト演習(C) (奈良女子大学)

  • 化学セミナー2 (奈良女子大学)

  • 化学特別研究III (奈良女子大学)

  • 化学特別研究I (奈良女子大学)

  • 化学セミナー1 (奈良女子大学)

  • 基礎無機化学通論I (奈良女子大学)

  • 基礎化学I (奈良女子大学)

  • 化学特別講義 (奈良女子大学)

  • 基礎物理化学通論I (奈良女子大学)

  • 金属蛋白質設計論演習 (奈良女子大学)

  • 金属蛋白質設計論 (奈良女子大学)

  • 無機化学外国語特論I (奈良女子大学)

  • サイエンス・オープンラボII (奈良女子大学)

  • サイエンス・オープンラボI (奈良女子大学)

  • 機器分析法2 (奈良女子大学)

  • 機器分析法1 (奈良女子大学)

  • 基礎化学2 (奈良女子大学)

  • 化学専門実験3 (奈良女子大学)

  • 生体分子電子移動論 (奈良女子大学)

  • 無機生体関連化学セミナーII (奈良女子大学)

  • 光機能分子化学 (奈良女子大学)

  • 卒業研究4 (奈良女子大学)

  • 卒業研究3 (奈良女子大学)

  • 化学実験II (奈良女子大学)

  • 化学実験IB (奈良女子大学)

  • 化学実験IA (奈良女子大学)

  • 化学特別講義III (奈良女子大学)

  • サイエンス・オープンラボ (奈良女子大学)

  • 化学のための物理演習 (奈良女子大学)

  • 化学実験1B (奈良女子大学)

  • 卒業研究2 (奈良女子大学)

  • 化学基礎実験3 (奈良女子大学)

  • 化学基礎実験1 (奈良女子大学)

  • 基礎化学演習 (奈良女子大学)

  • 化学実験2 (奈良女子大学)

  • 化学実験1A (奈良女子大学)

  • 卒業研究1 (奈良女子大学)

  • 化学セミナー (奈良女子大学)

  • 化学特別講義I (奈良女子大学)

  • 化学基礎実験2 (奈良女子大学)

所属学協会

  • 光化学協会

  • 錯体化学若手の会

  • 複合系の光機能研究会

  • 日本化学会生体機能関連化学部会

  • 錯体化学会

  • 日本化学会

  • ホスト-ゲスト・超分子化学研究会

Works(作品等)

  • 酵素活性中心に導入した光増感金属錯体の光誘起電子移動反応

    2017年04月 - 2021年03月, rm:research_project_id

  • 金属錯体-酵素複合体のMALDI-TOF-MS質量分析

    2016年10月

  • タンパク質を用いる円偏光発光システムの構築

    2016年04月

  • 金属錯体-酵素複合体のMALDI-TOF-MS質量分析

    2015年04月 - 2015年04月

  • 再構成ヘムタンパク質の新規光触媒機能発現に関する研究

    2008年04月 - 2014年03月

  • 発光性金属錯体および配位子のDFT計算

    2013年04月

  • 発光性金属錯体および配位子のDFT計算

    2006年 - 2013年

  • 金属蛋白質複合体の結晶化および構造解析

    2009年10月 - 2011年03月

  • 光学活性有機電子キャリアーの合成と機能評価

    2006年06月 - 2009年12月

  • 化学修飾金属蛋白質の光電子移動を利用した蛍光生CO2センサ素子の開発

    2008年07月 - 2009年03月

  • 化学修飾ヘムタンパク質の光ダイナミックスに関する研究

    2006年12月 - 2007年03月

  • 超高速時間分解測定を用いた化学修飾タンパク質の光誘起電子移動反応解析

    2004年04月 - 2006年12月

  • 金属配位化合物・酸化還元有機化合物のX線結晶構造解析

    2003年04月



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