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61.
Takeshi Yamanobe Isao Ando Hazime Saitô Ryoko Tabeta Akira Shoji Takuo Ozaki 《Chemical physics》1985,99(2):259-264
An attempt was made to calculate 13C NMR chemical shifts of poly(β-benzyl L-aspartate) having the right-handed α-helix (αR-helix) and left-handed α-helix (αL-helix) forms by a tight-binding MO sum-over-states theory within the extended Hückel framework, in order to examine whether or not the conformation-dependent 13C chemical shifts previously determined by the cross polarization-magic angle spinning technique are reproduced by a change of electronic structure of the polymer. It is found that the relative displacements of the observed Cα, Cβ and carbonyl 13C chemical shifts between the αR- and αL-helices are reproduced qualitatively by the calculation. 相似文献
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65.
Masaru Matsuo Fumihiko Ozaki Yasuyuki Konno Tetsuya Ogita 《Journal of Polymer Science.Polymer Physics》1981,19(10):1531-1547
The deformation of liquid-crystalline spherulites of poly(γ-benzyl-L -glutamate) (PBLG) in an electric field was investigated by light scattering, polarized-light microscopy, and birefringence measurements. Under the polarizing microscope, the deformation was found to be dependent upon the field strength. The spherulites deformed perpendicular to the field. Above 75 V/cm in N,N-dimethylformamide or 120 V/cm in 1,1,2-trichloroethane, the deformed spherulites were transformed to rodlike textures. With increasing voltage, the rods gradually oriented parallel to the electric field. On the basis of the experimental results, models for affine deformation are proposed. With these models, light-scattering patterns are calculated. The calculated and experimental patterns agree semiquantitatively. 相似文献
66.
Endo O Furuta T Ozaki H Sonoyama M Mazaki Y 《The journal of physical chemistry. B》2006,110(26):13100-13106
The aggregation and reaction of 17,19-hexatriacontadiyne molecules are studied on a Au(111) surface. The molecular orientation and arrangement are elucidated by infrared reflection absorption spectroscopy (IRAS) and scanning tunneling microscopy (STM). A vapor-deposited monolayer and a multilayered film formed by adsorption from the solution provide IRA spectra with bands due to the antisymmetric and symmetric stretching of methylenes in the gauche conformation. After the adsorbed film is rinsed with the solvent, however, the spectrum loses the gauche bands and is characterized by the enhanced C-H(distal) and C-H(proximal) stretching bands, which means that all-trans molecules are laid flat. Only STM images for the rinsed film display columnar structures on the herringbones of the reconstructed Au(111) surface; the alkyl chain direction is found to be parallel to the Au atom row. The results indicate that an ordered monolayer is formed first at the liquid-solid interface, and then, disordered overlayers with the gauche conformation are grown but removed by a rinse. Upon exposure to UV light, thus obtained monomer columns are converted into oligomers with flexible backbones and an increased gauche population in the alkyl chains, which resemble red phase polydiacetylenes in LB films. 相似文献
67.
Fukuma H Nakashima K Ozaki Y Noda I 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,65(3-4):517-522
Generalized two-dimensional (2D) fluorescence correlation spectroscopy has been used to resolve the fluorescence spectra of two tryptophan (Trp) residues in alcohol dehydrogenase and lysozyme. In each protein, one Trp residue is buried in a hydrophobic domain of the protein matrix and the other Trp residue is located at a hydrophilic domain close to the protein-water interface. Fluorescence quenching by iodide ion, a hydrophilic quencher, was employed as a perturbation to induce the intensity change in the spectra. The Trp residue which is located at the hydrophilic domain is effectively quenched by the quencher, while the Trp residue located at the hydrophobic domain is protected from the quenching. Therefore, the fluorescence of these two Trp residues have a different sensitivity to the quenching, showing a different response to the concentration of the quencher. Fluorescence spectra of the two Trp residues in alcohol dehydrogenase, which are heavily overlapped in conventional one-dimensional spectra, have been successfully resolved by the 2D correlation technique. From the asynchronous correlation map, it was revealed that the quenching of Trp located at the hydrophobic part was brought about after that of Trp located at the hydrophilic part. In contrast, the fluorescence spectra of the two Trp residues could not be resolved after the alcohol dehydrogenase was denatured with guanidine hydrochloride. These results are consistent with the well-known structure of alcohol dehydrogenase. Furthermore, it was elucidated that the present 2D analysis is not interfered by Raman bands of the solvent, which sometimes bring difficulty into the conventional fluorescence analysis. Fluorescence spectra of the Trp residues in lysozyme could not be resolved by the 2D correlation technique. The differences between the two proteins are attributed to the fact that the Trp residue in the hydrophobic site of lysozyme is not sufficiently protected from the quenching. 相似文献
68.
Abstract In about the last 20 years, Raman spectroscopy has made phenomenal progress owing to technological innovations in lasers, detectors, and computers. Today, application of Raman spectroscopy spreads over large areas of science and technology. Medical science has also become one of the targets of Raman spectroscopy [1]; it has considerable promise as a diagnostic o r analytical tool in medicine since it is an excellent nondestructive structural probe for constituents of biological materials [2–6]. 相似文献
69.
For a prime number p and a finite set S of prime numbers congruent to 1 modulo p, we consider the Galois group of the maximal pro-p-extension unramified outside S over the ${\mathbb Z_p}$ -extension of the rational number field. In this paper, we give a family of S for which the Galois group is a metacyclic pro-p group with an application to Greenberg’s conjecture. 相似文献
70.
Experimental investigations on the ferroelectric liquid crystal, R-4′(1-butoxycarbonyl-1-ethoxy) phenyl 4-(4-octyloxy phenyl) benzoate (1BC1EPOPB) of large spontaneous polarization (P S(+) = 240?nC?cm?2), using dielectric and calorimetric techniques, are reported. The temperature range of 25.0–125.0°C has been chosen for dielectric measurements. Dielectric dispersion studies are carried out in the temperature range 45.0–75.0°C and in the frequency range 2?Hz to 2?MHz for the smectic A, smectic C* and smectic X phases. A new phase called ‘smectic X’ has been found around 56.3°C. The transition temperatures identified by the dielectric dispersion studies for different phases and those given by DSC techniques are in close agreement. 相似文献