Journal of Electron Spectroscopy and Related Phenomena, 2001
ABSTRACT The results of X-ray fluorescence measurements of advanced organic materials (organic se... more ABSTRACT The results of X-ray fluorescence measurements of advanced organic materials (organic semiconductors, superconductors and molecular magnets) are presented. The electronic structure and chemical bonding of these materials is discussed basing on comparison of X-ray emission spectra with spectra of reference samples and our MO LCAO calculations.
Journal of Biomedical Research & Environmental Sciences
Collagen and Polylactic Acid (PLA) as biomaterials in the tissue engineering have been investigat... more Collagen and Polylactic Acid (PLA) as biomaterials in the tissue engineering have been investigated for the structure and function in considerably large progress. From a viewpoint of its electronic structures in the subnano-meter range, we investigate the bonding nature for five models of the type I collagen, PLA models and the bimolecular interaction between the models by using Density Functional Theory (DFT) calculations with Frontier MO theory. In order to confirm the accuracy of the models, we compare the simulated IR and C1s X-ray photoelectron spectra with experimental results. Especially, the interaction between PLA and (AspHypGly)-collagen models was obtained as the chemical bond energy (1540 kJ/mol), and the results of PLA-other four collagen bimolecular models were given as intermolecular bond energies of 30 ∼ 81 kJ/mol. The intermolecular interaction is due to inter-H-bond of –OH---O=, -NH---O=, and –CH---O= functional groups, respectively, using MO calculations.
Kyoto University (京都大学)0048新制・課程博士工学博士甲第1385号工博第341号新制||工||254(附属図書館)UT51-48-J23京都大学大学院工学研究科燃料化学専... more Kyoto University (京都大学)0048新制・課程博士工学博士甲第1385号工博第341号新制||工||254(附属図書館)UT51-48-J23京都大学大学院工学研究科燃料化学専攻(主査)教授 米沢 貞次郎, 教授 福井 謙一, 教授 岡本 邦男学位規則第5条第1項該
A method using the H-2-NMR spectra was shown to be useful to study the solid state physics in dia... more A method using the H-2-NMR spectra was shown to be useful to study the solid state physics in diamagnetic and paramagnetic compounds and in crystals having a modulated structure. The spectra and T-1 of NMR in solids were measured for [M(H2O)(6)] [AB(6)] crystals to investigate the static and dynamic structure of H2O and [M(H2O)(6)](2+) as well as the dynamics of the electron spin in the paramagnetic M2+ ion. The physical properties of [M(H2O)(6)] [AB(6)] were found to be as follows: (1) The spin-lattice relaxations of the electron spin of M2+ in [M(H2O)(6)] [SiF6] (M2+ = Fe2+, Co2+, Ni2+) are dominated by the Orbach process, the Orbach process, and the Raman process, respectively. The spin-lattice relaxation of the electron spin Of Cu2+ in [Cu (H2O)(6)] [PtCl6] is caused by jumping between the Jahn-Teller configurations. (2) In [Cu(H2O)(6)] [PtCl6], H2O and [Cu(H2O)(6)](2+) undergo 180degrees flips and jumping between the different Jahn-Teller configurations, respectively. A weakeni...
The dynamics of [Zn(D2O)6]2+ in [Zn(D2O)6][SiF6] was investigated by 2H NMR one-dimensional spect... more The dynamics of [Zn(D2O)6]2+ in [Zn(D2O)6][SiF6] was investigated by 2H NMR one-dimensional spectra, two-dimensional exchange spectra and spin-lattice relaxation time (T1). The lineshapes of those spectra and T1 were dominated by the 180° flip of the water molecules and the reorientation of [Zn(D2O)6]2+ about the C3 axis. The variation of lineshape of the one-dimensional spectrum below room temperature can be explained by only the 180° flip of the water molecules. The spectrum at room temperature showed a typical shape due to the rapid 180° flip of water molecules. The change in lineshape of the one-dimensional 2H NMR spectrum is caused by the three-site jump of [Zn(D2O)6]2+ about its C3 axis above 333K. Information of the reorientation of [Zn(D2O)6]2+ below 333K could not be obtained from the one-dimensional spectrum and T1. In this temperature range, the two-dimensional exchange spectrum was effective for analysis of molecular motion. The effects of multiple motions, the 180° flip of the water molecules and the reorientation of [Zn(D2O)6]2+ about the C3 axis, on the lineshape of the two-dimensional exchange spectrum were studied using spectral simulation.
Novel potentials of photoemission electron spectroscopy have been recently enabled to be explored... more Novel potentials of photoemission electron spectroscopy have been recently enabled to be explored by an advent of upgraded relevant technology. The enhanced signal-to-noise ratio by an advancement of measurement technology has revived attention to the extrinsic loss beyond the sudden approximation of photoemission spectroscopy. The ultrashort laser pulses and their control by the state-of-the-art laser technology have given birth to the time-resolved photoemission spectroscopy. In this issue, we introduce some studies of the extrinsic loss and the time-resolved mode of the photoemission spectroscopy.
ABSTRACT We present a theory of proton transfer reactions which incorporate the modulation of the... more ABSTRACT We present a theory of proton transfer reactions which incorporate the modulation of the proton's potential surface by intermolecular vibrations and the effect of coupling to solvent degree of freedom. The proton tunnels between states corresponding to it being localized in the wells of a double minimum potential. The resulting tunnel splitting depends on the intermolecular separation. The solvent response to the proton's charge is modeled as that of a continuous distribution of harmonic oscillators and the intermolecular stretching mode is also damped because of the interaction with solvent degree of freedom. The transition rate is given by the Fermi Gorlden Rule expression.
ABSTRACT Ag-109 NMR signals in AgCu1-xI crystals were shifted to a low field relative to that in ... more ABSTRACT Ag-109 NMR signals in AgCu1-xI crystals were shifted to a low field relative to that in solid AgI with decreasing the unit cell constant analogously to Cu-63 MAS NMR signals reported in a previous study. The observed chemical shieldings were analysed using the results of Ag and Cu NMR shielding calculations of tetrahedral (T-d) MI43- (M = Ag, Cu) complex ions with the ab initio GAUSSIAN 94 program using a double-zeta basis set for the Ag, Cu, and I atoms. Since the shift is explained dominantly by the paramagnetic shielding term, which depends on the d-hole and p-electron densities in Ag or Cu atoms for the MI43- complex ions, the observed Ag-109 shift moved to a low field with decreasing the lattice constant, corresponding to an increase in the d-hole and p-electron densities for AgI43- (RAg-I = 2.68, 2.73, 2.77 Angstrom) relative to the AgI43- (RAg-I = 2.81 Angstrom) ion.
The X-ray photoelectron spectra of eight polymers [(CH2CH2) n,(CH2CH2NH) n,(CH2O) n,(CH2CH2S) n,(... more The X-ray photoelectron spectra of eight polymers [(CH2CH2) n,(CH2CH2NH) n,(CH2O) n,(CH2CH2S) n,(CH2CHX) n, and (CH2CX2) n (X= F, Cl)] were analyzed by the deMon density-functional method using the model oligomers. Calculated AIK α valence ...
Journal of Electron Spectroscopy and Related Phenomena, 2001
ABSTRACT The results of X-ray fluorescence measurements of advanced organic materials (organic se... more ABSTRACT The results of X-ray fluorescence measurements of advanced organic materials (organic semiconductors, superconductors and molecular magnets) are presented. The electronic structure and chemical bonding of these materials is discussed basing on comparison of X-ray emission spectra with spectra of reference samples and our MO LCAO calculations.
Journal of Biomedical Research & Environmental Sciences
Collagen and Polylactic Acid (PLA) as biomaterials in the tissue engineering have been investigat... more Collagen and Polylactic Acid (PLA) as biomaterials in the tissue engineering have been investigated for the structure and function in considerably large progress. From a viewpoint of its electronic structures in the subnano-meter range, we investigate the bonding nature for five models of the type I collagen, PLA models and the bimolecular interaction between the models by using Density Functional Theory (DFT) calculations with Frontier MO theory. In order to confirm the accuracy of the models, we compare the simulated IR and C1s X-ray photoelectron spectra with experimental results. Especially, the interaction between PLA and (AspHypGly)-collagen models was obtained as the chemical bond energy (1540 kJ/mol), and the results of PLA-other four collagen bimolecular models were given as intermolecular bond energies of 30 ∼ 81 kJ/mol. The intermolecular interaction is due to inter-H-bond of –OH---O=, -NH---O=, and –CH---O= functional groups, respectively, using MO calculations.
Kyoto University (京都大学)0048新制・課程博士工学博士甲第1385号工博第341号新制||工||254(附属図書館)UT51-48-J23京都大学大学院工学研究科燃料化学専... more Kyoto University (京都大学)0048新制・課程博士工学博士甲第1385号工博第341号新制||工||254(附属図書館)UT51-48-J23京都大学大学院工学研究科燃料化学専攻(主査)教授 米沢 貞次郎, 教授 福井 謙一, 教授 岡本 邦男学位規則第5条第1項該
A method using the H-2-NMR spectra was shown to be useful to study the solid state physics in dia... more A method using the H-2-NMR spectra was shown to be useful to study the solid state physics in diamagnetic and paramagnetic compounds and in crystals having a modulated structure. The spectra and T-1 of NMR in solids were measured for [M(H2O)(6)] [AB(6)] crystals to investigate the static and dynamic structure of H2O and [M(H2O)(6)](2+) as well as the dynamics of the electron spin in the paramagnetic M2+ ion. The physical properties of [M(H2O)(6)] [AB(6)] were found to be as follows: (1) The spin-lattice relaxations of the electron spin of M2+ in [M(H2O)(6)] [SiF6] (M2+ = Fe2+, Co2+, Ni2+) are dominated by the Orbach process, the Orbach process, and the Raman process, respectively. The spin-lattice relaxation of the electron spin Of Cu2+ in [Cu (H2O)(6)] [PtCl6] is caused by jumping between the Jahn-Teller configurations. (2) In [Cu(H2O)(6)] [PtCl6], H2O and [Cu(H2O)(6)](2+) undergo 180degrees flips and jumping between the different Jahn-Teller configurations, respectively. A weakeni...
The dynamics of [Zn(D2O)6]2+ in [Zn(D2O)6][SiF6] was investigated by 2H NMR one-dimensional spect... more The dynamics of [Zn(D2O)6]2+ in [Zn(D2O)6][SiF6] was investigated by 2H NMR one-dimensional spectra, two-dimensional exchange spectra and spin-lattice relaxation time (T1). The lineshapes of those spectra and T1 were dominated by the 180° flip of the water molecules and the reorientation of [Zn(D2O)6]2+ about the C3 axis. The variation of lineshape of the one-dimensional spectrum below room temperature can be explained by only the 180° flip of the water molecules. The spectrum at room temperature showed a typical shape due to the rapid 180° flip of water molecules. The change in lineshape of the one-dimensional 2H NMR spectrum is caused by the three-site jump of [Zn(D2O)6]2+ about its C3 axis above 333K. Information of the reorientation of [Zn(D2O)6]2+ below 333K could not be obtained from the one-dimensional spectrum and T1. In this temperature range, the two-dimensional exchange spectrum was effective for analysis of molecular motion. The effects of multiple motions, the 180° flip of the water molecules and the reorientation of [Zn(D2O)6]2+ about the C3 axis, on the lineshape of the two-dimensional exchange spectrum were studied using spectral simulation.
Novel potentials of photoemission electron spectroscopy have been recently enabled to be explored... more Novel potentials of photoemission electron spectroscopy have been recently enabled to be explored by an advent of upgraded relevant technology. The enhanced signal-to-noise ratio by an advancement of measurement technology has revived attention to the extrinsic loss beyond the sudden approximation of photoemission spectroscopy. The ultrashort laser pulses and their control by the state-of-the-art laser technology have given birth to the time-resolved photoemission spectroscopy. In this issue, we introduce some studies of the extrinsic loss and the time-resolved mode of the photoemission spectroscopy.
ABSTRACT We present a theory of proton transfer reactions which incorporate the modulation of the... more ABSTRACT We present a theory of proton transfer reactions which incorporate the modulation of the proton's potential surface by intermolecular vibrations and the effect of coupling to solvent degree of freedom. The proton tunnels between states corresponding to it being localized in the wells of a double minimum potential. The resulting tunnel splitting depends on the intermolecular separation. The solvent response to the proton's charge is modeled as that of a continuous distribution of harmonic oscillators and the intermolecular stretching mode is also damped because of the interaction with solvent degree of freedom. The transition rate is given by the Fermi Gorlden Rule expression.
ABSTRACT Ag-109 NMR signals in AgCu1-xI crystals were shifted to a low field relative to that in ... more ABSTRACT Ag-109 NMR signals in AgCu1-xI crystals were shifted to a low field relative to that in solid AgI with decreasing the unit cell constant analogously to Cu-63 MAS NMR signals reported in a previous study. The observed chemical shieldings were analysed using the results of Ag and Cu NMR shielding calculations of tetrahedral (T-d) MI43- (M = Ag, Cu) complex ions with the ab initio GAUSSIAN 94 program using a double-zeta basis set for the Ag, Cu, and I atoms. Since the shift is explained dominantly by the paramagnetic shielding term, which depends on the d-hole and p-electron densities in Ag or Cu atoms for the MI43- complex ions, the observed Ag-109 shift moved to a low field with decreasing the lattice constant, corresponding to an increase in the d-hole and p-electron densities for AgI43- (RAg-I = 2.68, 2.73, 2.77 Angstrom) relative to the AgI43- (RAg-I = 2.81 Angstrom) ion.
The X-ray photoelectron spectra of eight polymers [(CH2CH2) n,(CH2CH2NH) n,(CH2O) n,(CH2CH2S) n,(... more The X-ray photoelectron spectra of eight polymers [(CH2CH2) n,(CH2CH2NH) n,(CH2O) n,(CH2CH2S) n,(CH2CHX) n, and (CH2CX2) n (X= F, Cl)] were analyzed by the deMon density-functional method using the model oligomers. Calculated AIK α valence ...
Uploads
Papers by Kazunaka ENDO