|久枝 良雄（ひさえだ よしお）||データ更新日：2020.07.20|
教授 ／ 工学研究院 応用化学部門 生体機能化学講座
|1.||Guolin Zhang, Li Zhang, Dan Zhang, Qiuhua Wu, Yoshihiro Sasaki, Yoshio Hisaeda, Kazuma Yasuhara, Jun ichi Kikuchi, Xi Ming Song, Aerobic oxidation of thioglycol catalysed by metallophthalocyanine in an organic-inorganic hybrid vesicle “cerasome”, Inorganic Chemistry Communications, 10.1016/j.inoche.2020.107866, 115, 2020.05, [URL], A molecular assembly of a hydrophobized metallophthalocyanine derivative embedded in a cerasome, an organic–inorganic hybrid vesicle with a lipid bilayer and silica surface, was a potent catalyst for aerobic oxidation of thioglycol. The catalytic activity was higher than those in hexadecyl 2-hydroxy-3-chloropropyl phosphate vesicles, sodium dodecylsulfate micelles, ethanol, and benzene..|
|2.||Taro Koide, Takafumi Maeda, Tsukasa Abe, Yoshihito Shiota, Yoshio Yano, Toshikazu Ono, Kazunari Yoshizawa, Yoshio Hisaeda, Mechanistic Study on Ring-Contracting Skeletal Rearrangement from Porphycene to Isocorrole by Experimental and Theoretical Methods, European Journal of Organic Chemistry, 10.1002/ejoc.201901659, 2020, 12, 1811-1816, 2020.03, [URL], In this study, the ring contracting skeletal rearrangement reaction in one-pot under basic conditions from octaethylporphycene to two types of isocorroles, i.e., the meso-formyl and meso-free forms, was confirmed and the reaction mechanism was proposed by the comparative analyses of the experimental and theoretical studies. The electron accepting nature of the porphycene and imine-amine conversion of pyrrole rings make it possible to react with hydroxide ions and the following reaction to afford isocorroles. Based on this reaction, the valence of the compound as a ligand as well as the photochemical and electrochemical properties were dramatically changed..|
|3.||Keita Shichijo, Mamoru Fujitsuka, Yoshio Hisaeda, Hisashi Shimakoshi, Visible light-driven photocatalytic duet reaction catalyzed by the B12-rhodium-titanium oxide hybrid catalyst, Journal of Organometallic Chemistry, 10.1016/j.jorganchem.2019.121058, 907, 2020.02, [URL], The hybrid catalyst composed of the B12 complex and rhodium ion (Rh3+) modified titanium oxide was synthesized for the visible light-driven B12 inspired catalytic reaction. The hybrid catalyst contains 4.93 × 10−6 molg−1 of the B12 complex and 5.43 × 10−5 molg−1 of the Rh(III) ion on the surface of titanium oxide. Visible light irradiation (λ ≧ 420 nm) of the hybrid catalyst in the presence of triethylamine (Et3N) as a sacrificial reagent showed absorption at 390 nm, typical for the Co(I) state of the B12 complex monitored by diffuse reflectance UV–vis analysis, which imply that electron transfer from the titanium oxide to Co(III) center of the B12 complex occurred by the visible light irradiation. Benzotrichloride was converted to N,N-diethylbenzamide by the visible light irradiation catalyzed by the hybrid catalyst in air at room temperature. Both the conduction band electron and valence band hole of the catalyst were utilized for the reaction to form the amide product. The reaction mechanism of the duet reaction was proposed..|
|4.||Taro Koide, Zihan Zhou, Ning Xu, Yoshio Yano, Toshikazu Ono, Zhongli Luo, Hisashi Shimakoshi, Yoshio Hisaeda, Electrochemical properties and catalytic reactivity of cobalt complexes with redox-active meso -substituted porphycene ligands, Journal of Porphyrins and Phthalocyanines, 10.1142/S1088424619500780, 24, 1-3, 90-97, 2020.01, [URL], The cobalt complexes of meso-aryl substituted porphycenes were synthesized and characterized. The reduction potentials of the complexes were shifted to the positive side depending on the strength of the electron-withdrawing properties of the meso-substituents, while the optical properties, such as the absorption spectra of these complexes, were similar. This suggests that the energy levels of the molecular orbitals of the complexes were changed by the meso-substituents while the gaps of the orbitals were not significantly changed. The one-electron reduction of the complex did not afford the Co(I) species, but the ligand-reduced radical anion, which was characterized by electrospectrochemistry. The generated ligand-reduced species reacted with alkyl halides to form the Co(III)-alkyl complex. As a result, the reduction potential of the electrolytic reaction could be directly controlled by the substituents of the porphycene. The catalytic reaction with trichloromethylbenzene was also performed and it was found that the ratio of the obtained products was changed by the reduction potentials of the catalyst, i.e. the cobalt porphycenes..|
|5.||Toshikazu Ono, Hyuga Shinjo, Daiki Koga, Yoshio Hisaeda, Synthesis of a meso-Tetraalkylporphycene Bearing Reactive Sites
Toward Porphycene–Polydimethylsiloxane Hybrids with Enhanced Photophysical Properties, European Journal of Organic Chemistry, 10.1002/ejoc.201901497, 2019, 46, 7578-7583, 2019.12, [URL], meso-Tetraalkyl porphycenes exhibit unique optical properties with wide potential applications. The very fact that incorporation of porphycenes into polymeric materials is rare, make this approach a particularly attractive one. In this work, meso-tetrakis(3-butenyl)porphycene bearing four terminal olefin groups is prepared via two synthetic strategies: 1) the McMurry reaction using 5,5′-diacyl-2,2′-bipyrroles as precursors and 2) the oxidative coupling of dipyrroethenes. The newly obtained porphycene has been characterized by single X-ray crystallography. A porphycene–polydimethylsiloxane hybrid film is successfully prepared by a platinum-catalyzed hydrosilylation reaction. The hybrid film can be anchored with tweezers, showing a weak red emission with a quantum yield of 0.4 % at room temperature, whose intensity drastically increases reaching a quantum yield of 6.7 % in liquid nitrogen (77 K). This report represents the first example of porphycene-containing elastomeric films for potential application in various fields..