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Polarized Electronic Spectra of Organic/Inorganic Hybrid Materials of Chiral Schiff Base Ni（ll） or Cu（ll） Complexes and Disperse Red 1 or Azobenzene in PMMA Films

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Journal of Chemistry and Chemical Engineering 2011年第5期5卷 443-450页

作者： takashiro akitsu Yukie Miura Department of Chemistry Faculty of Science Tokyo University of Science Tokyo 162-8601 Japan

We have prepared new chiral Schiff base complexes, and copper（Ⅱ）（2） to investigate steric effect of ligands for 1 and bis（N-R-l-phenylethyl-5- methoxysalicydenaminato） nickel（Ⅱ）（1） 2 and known bis（N-R-l-phenylethyl-3,5-dichlorosalicydenaminato） nickel（Ⅱ）（3） and copper（Ⅱ）（4）. By using two kinds of photochromic dyes, disperse red 1 （DRI） and azobenzene （AZ）, we investigated the efficiency of increasing optical anisotropy of organic/inorganic hybrid materials of 1 through 4＋AZ or DRI＋PMMA in polymethylmethacrylate （PMMA） cast films by Weigert effect （and compared with cis-trans isomerization by alternate UV and visible light for 3 and 4 to previous study）. Gradual increase of optical anisotropy was observed for all the hybrid materials regardless of flexibility of Schiff base complexes, and the degree of dichroism and weak intermolecular interactions were discussed based on polarized absorption electronic spectra.

关键词： Photochromism chirality polarized light metal complexes Schiff base.

Anthraquinone Derivative Chiral Schiff Base Copper（Ⅱ） Complexes for Enzyme Type Bio-Fuel Cell Mediators

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Journal of Electrical Engineering 2016年第4期4卷 189-195页

作者： Yuto Takeuchi takashiro akitsu Department of Chemistry Faculty of Science Tokyo University of Science Tokyo 162-8601 Japan

Electrochemically, laccase, a family of multi-copper oxidase, has specificity for performing not only one-electron oxidation of phenolic-related compounds but also four-electron reduction of oxygen, which is expected to be a cathode of biofuel ceils. We have prepared three amino-acid derivatives （for enhancing affinity to laccase） and one control （just for determining redox behavior of ligands and Cu（II/I）） copper（lI） complexes 0-3 having phenolic-related ligands involving anthraquinone moiety. Enhancing current density of electron transfer between the cathode （composed of electron conducting materials such as Nation and carbon nanotube） and laccase could be observed for all 1-3 acting as good mediators according to （spectro）electrochemical results.

关键词： Biofuel cells oxygen reduction Schiffbase Cu(II) complex anthraquinone.

Viscosity Dependence of Solid-State CD Peaks of Chiral Schiff Base Ni（ll） and Cu（ll） Complexes in PMMA Soft Mater Matrices

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Journal of Chemistry and Chemical Engineering 2013年第6期7卷 487-494页

作者： Yu Okamoto takashiro akitsu Department of Chemistry Faculty of Science Tokyo University of Science Tokyo 162-8601 Japan

Two new chiral Schiff base acacen-derivative nickel（II） and copper（II） complexes have been prepared and characterized with IR, electronic, and CD spectra and X-ray crystallography. So-called artifact peaks of solid-state CD spectra due to restricted to rotate freely of molecules appeared at about 334 and 460 nm for nickel（II） and copper（II） complexes. Changes of intensity of the peaks have been investigated in different matrices such as solid-state （microcrystals or KBr pellets）, PMMA cast films and acetone solutions of various concentrations and pure acetone solutions. Although restricted orientation of molecules in rigid matrices leads to increase the peak intensity toward negative and positive optical rotation for nickel（II） and copper（II） complexes, respectively, the degree of increasing intensity depends on not concentration but viscosity of polymer solutions. Therefore, the artifact CD peaks of solid-state can act as an indicator of environmental viscosity of soft mater matrices.

关键词： Chirality solid-state circular dichroism soft mater Schiffbase nickel(II) copper(II).

Computational Study on UV-Vis and CD Spectra of Chiral Schiff Base Ni（ll）, Cu（ll） and Zn（ll） Complexes for Discussion of Induced CD

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Journal of Chemistry and Chemical Engineering 2012年第11期6卷 957-961页

作者： Chigusa Kominato takashiro akitsu Department of Chemistry Faculty of Science Tokyo University of Science Tokyo 162-8601 Japan

Simulated UV-vis and CD （circular dichroism） spectra were obtained for several chiral Schiff base Ni（II）, Cu（II） and Zn（II） complexes by TD-DFT （time dependent-density functional theory）and Z1NDO calculations. Dipole moments for them were also evaluated by ZINDO calculations and revealed that Cu（II） complexes exhibited the largest values than the analogous Ni（II） and Zn（II） complexes. Although these complexes possessed large dipole moments, induced CD by these complexes were observed a Cu（II）-containing metallodendrimer nor Cu-nanoclusters prepared in a PAMAM （polyamidoamine） dendrimer experimentally nevertheless of other related chiral Schiff base Ni（II）, Cu（II）, and Zn（II） complexes. The present results suggested that steric factors of ligands were more important than electronic factors for emerging induced CD bands by supramolecular interactions.

关键词：锌(Ⅱ)配合物 Schiff碱 CD光谱镍(Ⅱ) 铜(Ⅱ) UV-Vis 手性计算

Anisotropic Lattice Strain of Composite Materials of LiMnO2 and H/D-Substituted Chiral Cyanide-Bridged Ni（Ⅱ）-Fe（Ⅲ） Coordination Polymers

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Journal of Chemistry and Chemical Engineering 2014年第6期8卷 557-563页

作者： Masaki Kobayashi takashiro akitsu Department of Chemistry Faculty of Science Tokyo University of Science Tokyo 162-8601 Japan

Composite materials composed of LiMnO2, a typical electrode material for lithium ion battery, and a chiral cyanide-bridged Ni（Ⅱ）-Fe（Ⅲ） coordination polymer [NiL2][Fe（CN）6]·4H2O （Ni-Fe, H-form）（L = （1R,2R）-（-）-1,2-cyclohexane-diamine） or its deuterium isomer, [NiL2][Fe（CN）6]·4D2O （Ni-Fe, D-form） have been prepared by the various ratios （w/w） of Ni-Fe：LiMnO2 = 10：0 （pure Ni-Fe）, 9：1, 8：2, 7：3, 6：4, 5：5, 4：6, 3：7, 2：8, 1：9 and 0：10 （pure LiMnO2）. Gradual shift of IR （infrared） spectra by changing the ratios and losing difference between H-form and D-form of Ni-Fe due to isotope effects revealed adsorption of Ni-Fe onto LiMnO2 to form composite materials. Formation of composite materials of Ni-Fe and LiMnO2 could be also proved losing ferromagnetic behavior of LiMnO2 on increasing of the ratios of Ni-Fe in each composite. In contrast to smoothly positive thermal expansion of pure LiMnO2 along the crystallographic b axis, variable temperature powder XRD （X-ray diffraction） patterns at 100-300 K of the composite materials exhibited thermally-accessible lattice distortion along the b axis with different ratios. It is also proved deviation of ideal linear correlation of an evaluation function, In K = a/T ＋ b （where, K = （d（T） - d（0））/d（T）, d（T） denotes nλ/（sin 2θ） at T （K））.

关键词： TD-DFT (time-depcndent density functional theory) LiMnO2 coordination polymers composites XRD anisotropy.

Novel Thermally-Accessible Structural Changes of Chiral and Some Related Cu（ll） Complexes

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Journal of Chemistry and Chemical Engineering 2014年第10期8卷 929-941页

作者： Satoshi Ehara takashiro akitsu Department of Chemistry Faculty of Science Tokyo University of Science Tokyo 162-8601 Japan

A mononuclear chiral copper（ll） complex, [Cu（RRchxn）2（C（CN）3）2]＇H20 （RRchxn = （1R, 2R）-diaminocyclohexane）（RRchxnH）, and its deuterated compound, [Cu（RRchxn）2（C（CN）3）z].D20 （RRchxnD）, and their isomers, [Cu（trchxn）2（C（CN）3）2]＇H20 （trchxn = trans-l,2-diaminocyclohexane）（trchxnH） and [Cu（trchxn）2（C（CN）3）2]＇D20 （trchxnD） have been prepared and characterized by means of 1R （infrared）, electronic, and CD （circular dichroism） spectra, magnetic susceptibility, and variable-temperature X-ray crystallography as single crystals or powder. Interestingly, depending on grain size of samples, RRchxnH exhibits the monoclinic form and the orthorhombic form, which are distinguished by systematic absence and powder XRD （X-ray diffraction） patterns clearly. Although single crystals did not exhibit phase transition, powder XRD patterns of RRchxnH and weakly hydrogen bonded RRchxnD emerged low-temperature phase of monoclinic in the orthorhombic patterns only around 200-220 K. However, as a control, powder XRD patterns of both trchxnH and trchxnD did not exhibit such phase transition clearly.

关键词： Copper(lI) complexes crystal structures temperature-dependence XRD chirality.

Improvement of Pretreatment for Environmental Analysis of Cr （VI） Ion for Sediment Soil in Tama River

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Journal of Chemistry and Chemical Engineering 2011年第3期5卷 207-210页

作者： Haruna Furukawa takashiro akitsu Department of Chemistry Faculty of Science Tokyo University of Science 1-3Kagurzaka Shinjuku-ku Tokyo 162-8601 Japan

Compounds containing Cr （VI） ion are widely used for chemical industry, paints, dyes, and other applications. Because of commonly known toxicity of Cr （VI） ion, Cr （VI） is one of the important check items for quality of water in natural river or industrial waste water. Although the only method for selective detection for Cr （VI） ion is diphenylcarbazide, of which pretreatment spends long time according to the regulat^ons by the Ministry of Environment, Japan. Herein we develop a new and simple pretreatment for the job site and suitable for education and attempt to apply for analysis of the soil in Tama River actually.

关键词： Environmental analytical chemistry chromium (VI) ion diphenylcarbazide UV-visible spectroscopy Tama River.

Inorganic Crystalline Materials from Oil Paintings in the 19th Century

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材料科学与工程（中英文A版） 2011年第1X期1卷 23-28页

作者： takashiro akitsu Nobuyuki Nakamura Harumi Itoh Department of Chemistry Faculty of Science Tokyo University of Science 1-3Kagurzaka Shinjuku-ku Tokyo 162-8601 Japan Yamaryo Art Conservation Studio 5-6-18 Kyounancho Musashino Tokyo 180-0023 Japan

Separate Observation with Polarized Electronic and IR Spectra of Hybrid Materials of Chiral Mn（Ⅱ） Complexes

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材料科学与工程（中英文A版） 2011年第4X期1卷 518-525页

作者： takashiro akitsu Rieko Tanaka Atsuo Yamazaki Department of Chemistry Faculty of Science Tokyo University of Science 1-3 Kagurazaka Shinjuku-ku Tokyo 162-8601 Japan