Theoretical study of NMR chemical shift induced by H/D isotope effect

The isotope effect induced by deuterium substituted species is observed in molecular properties, such as geometry, kinetics, and electronic state, of the molecules through nuclear-electron interaction. Theoretical considerations and experimental alignments have been studied by ab initio molecular orbital, density functional theory, and other empirical strategies. The Born-Oppenheimer approximation with nuclear vibrational wavefunction can treat isotope effect because nuclear mass effect account for the average istance of vibrational motion. In this study, we introduce Morse anharmonic oscillator model to calculate average internuclear distance of diatomic molecules having X-H bonding and X-D bonding. Morse parameters are determined by fitting to potential energy surface of molecular orbital and/or density functional calculations, and then the average distance are obtained as the expectation value of the analytical Morse vibrational wavefunction. Nuclear magnetic resonance shielding constants of the H/D isotopomer are calculated again on the average distance by using GIAO with B3LYP and CCSD calculation. © 2010 Wiley Periodicals, Inc.研究者情報D

能動的学習を促す授業の背景と動向: 概念整理と分類の試み、学生の主体性を促す反転授業「アクティブラーニング入門」実践報告

金沢大学国際基幹教育院高等教育開発・支援系教育企画会議FD研修会「能動的学習を促す授業設計と授業外支援」, 2014.11.4. 13:00-17:0

Theoretical studies of laser-induced multiphoton absorption processes on diatomic molecules

取得学位：博士(理学)，学位授与番号：博甲第859号，学位授与年月日：平成19年3月22

遠隔授業がつなぐ大学の学びのリ・デザイン ―デジタル・ペダゴジーへ

金沢大学国際基幹教育院高等教育開発・支援系大学教育リ・デザインに向けて、デジタル・ペダゴジーを反映させた今後の授業のあり方について紹介した。・大学教育の遠隔授業化の知見共有、本学対応・LMSを用いた遠隔授業設計概論とパターン・遠隔授業とアクティブラーニング（事例）・緊急遠隔授業の５つの原則・「デジタル・ペダゴジー」（デジタル時代の教育学）へ第23回関西大学FDフォーラム「遠隔授業のデザインを考える-人の縁を描く授業-」関西大学教育開発支援センター(主催), 2020年6月13日(開催

Theoretical studies on electronic structure and properties of type I copper center in copper proteins

We present a cluster model representing type I copper (T1Cu) center of copperprotein, which corrsponds to Multicopper Oxidases, Azurin, Stelacyanin and so on. Theelectronic structure and physical properties such as molecular orbital, atomic partial charge,partial spin densities, ionization energy (IP) of reduced T1Cu, electron affinity (EA) of oxidizedT1Cu, the bond and the angle constants etc. are calculated by using two typicalDensity Functional Theory (DFT) functionals, which are B3LYP and M06, with 6-31G(d)basis set. We find the dependency of several properties such as atomic partial charge, partialspin densities, IP, and EA on the DFT functionals. We also find that the DFT functionals givea better contribution to bond constants, especially in case of the interaction between copperand the axial ligand. We calculate the maximum absorption wavelength of T1Cu center andfind relatively a good agreement with experimental data

Solvent effects on electronic structure of active site of azurin by polarizable continuum model

We present a cluster model for the active site of oxidized azurin, and investigate the electronic structure of the active site of oxidized azurin by using density functional calculations with polarizable continuum model. The singly occupied molecular orbital and spin density in the model widely distribute around the Cu 3dx2-y2 and S(Cys112) 3p orbitals. The dependency of electronic properties such as partial charge density and spin density on the dielectric constant is discussed. We find that partial spin density and charge density on the copper ion become larger, when the dielectric constant increases. © 2005 Elsevier Ltd. All rights reserved.Embargo Period 24 month

Theoretical study of a π-stacking interaction in carbonic anhydrase

Human carbonic anhydrase II (HCA II) catalyses the reversible hydration of CO2. In this enzyme, the imidazole ring of histidine at position 64 (His64) functions to transfer the productive proton from the zinc-bound water to the buffer molecule in bulk-water. X-ray data of HCA II show that His64 has two types of side chain orientations, ”in” and ”out”, representing the direction of the imidazole ring toward and away from the active site, respectively. Maupin et al. reported that the imidazole of His64 can be rotated in a model system of the active site to clarify the proton transfer of catalytic mechanism. However, the indole ring of tryptophan at position 5 (Trp5) that is located near the ”out” of the imidazole ring of His64 was not considered in the model system. In this study, in order to estimate detailed rotational properties of His64, we constructed two His64-containing models with and without Trp5, and then simulate the constructed structures by using MP2 method and 6-311++G(d,p) basis sets. This allows us to tentatively determine the potential energies of the π-stacking interaction of the imidazole with the indole in relation to the side chain rotation of His64. The result indicates that the π-stacking interaction causes an increase of the energy barrier between ”in” and ”out” conformations, implying that the rotational motion of His64 is not relevant to explain the proton transfer during catalysis. Alternatively, a steady position of His64 would be needed in the proton transfer in catalytic mechanism of HCA II

特定ラーニングスペースの独自学習環境アセスメント分析

金沢大学 国際基幹教育院高等教育開発・支援