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161.
Hiroshi Tanaka Toru Masuko Keisuke Homma Saburo Okajima 《Journal of polymer science. Part A, Polymer chemistry》1969,7(7):1997-2006
Polypropylene films of various isotacticities and crystallinities were stretched biaxially in one step in air at 140–152°C or polyaxially in poly(ethylene glycol) at 130–160°C, and the morphological changes were studied by electron microscopy (replica). In the initial stage of stretching, with vA = 1.4, the spherulites of one of the films used for the experiment were broken both from the centers and boundaries, and those of another film were broken mainly from the center. This difference in the deformation behavior seems to be characteristic of the film properties and independent of the method of stretching, although the factors involved are still unknown. On further stretching (vA = 22), well annealed spherulites were broken into many small blocklike fragments with unfolded fibrils running among them, particularly at the low stretching temperature (140°C), and fibrillation proceeded at the expense of the residual fragments. In the case of quenched or slightly crystallized material, the fragments were dendritic and divided into finer and finer fibrils on stretching. At elevated temperature, however, even for well annealed spherulites, the deformation behavior resembles that of the quenched material, and at a high degree of stretching the spherulites take on the fibrillar net structure in every case. In films containing a high amount of atactic fraction, radial, tangential, and boundary cracking occurred more easily, and broad fibrils were observed across the cracks. 相似文献
162.
We report the synthesis of open-ended MoS2 nanotubes and their application as the catalyst for methanation of carbon monoxide with hydrogen. Because the catalysis of the methanation reaction occurs at relatively low temperatures, such nanotubes may provide new solutions toward harnessing the environmental load caused by CO emission. 相似文献
163.
Tanaka T Murakami K Kanda A Patra D Yamamoto S Satoh N Kim SW Rahman SM Ohno H Iwata C 《The Journal of organic chemistry》2001,66(21):7107-7112
A total synthesis of (+/-)-stemodinone, a tetracyclic stemodane diterpene, from the known tricyclic methyl olefin 11 is described. The key steps involve an efficient ring-exchange reaction and palladium(0)-catalyzed lactone migration. The ring-exchange strategy for controlling the stereochemistry was based on an initial Diels-Alder reaction to form a new ring followed by cleavage of the original ring. Cleavage of the original ring of the Diels-Alder adduct 9 was achieved by an initial regio- and chemoselective Baeyer-Villiger oxidation followed by the Pd(0)-catalyzed lactone-migration reaction reported by us. 相似文献
164.
Pan PW Dickson RJ Gordon HL Rothstein SM Tanaka S 《The Journal of chemical physics》2005,122(3):34904
Functionally relevant motion of proteins has been associated with a number of atoms moving in a concerted fashion along so-called "collective coordinates." We present an approach to extract collective coordinates from conformations obtained from molecular dynamics simulations. The power of this technique for differentiating local structural fluctuations between classes of conformers obtained by clustering is illustrated by analyzing nanosecond-long trajectories for the response regulator protein Spo0F of Bacillus subtilis, generated both in vacuo and using an implicit-solvent representation. Conformational clustering is performed using automated histogram filtering of the inter-C(alpha) distances. Orthogonal (varimax) rotation of the vectors obtained by principal component analysis of these interresidue distances for the members of individual clusters is key to the interpretation of collective coordinates dominating each conformational class. The rotated loadings plots isolate significant variation in interresidue distances, and these are associated with entire mobile secondary structure elements. From this we infer concerted motions of these structural elements. For the Spo0F simulations employing an implicit-solvent representation, collective coordinates obtained in this fashion are consistent with the location of the protein's known active sites and experimentally determined mobile regions. 相似文献
165.
Kazuyoshi Tanaka Kazunari Yoshizawa Tokio Yamabe 《International journal of quantum chemistry》1991,40(3):305-314
We studied the midgap levels appearing in the photoexcited conductive polymers such as trans- and cis-polyacetylenes, poly(p-phenylene), polypyrrole, and polyacene based on the molecular orbital analysis. The midgap levels are constructed from the transformation of the highest occupied molecular orbital and the lowest unoccupied molecular orbital of the ground state. As the result of the localization of the wave functions associated with these midgap levels, large polarization is induced between adjacent carbon atoms. Based on the examination of the energy gap between the two midgap levels, the polymers with a nondegenerate ground state such as cis-polyacetylene, poly(p-phenylene), and polypyrrole would show no sizable photoconductivities. 相似文献
166.
Hiroshi Takeuchi Makoto Nakagawa Takayuki Saito Toru Egawa Kiyoshi Tanaka Shigehiro Konaka Toshiyuki Mitsuhashi 《International journal of quantum chemistry》1994,52(6):1339-1348
The energy spectra of free water molecules were measured at scattering angles 2θ ranging from 10.5° to 75.7°, using an angle-dispersive-type diffractometer and synchrotron radiation as an X-ray source. A silicon (111) monochrometer was used to obtain incident X-rays with the wavelengths of (1.543/n) Å (n = 1,3,4,5). Observed inelastic scattering peaks are clearly separated from eleastic ones at s values [s = (4π/λ) sin Å] larger than 8 Å?1. The increase of the separation with an increasing s value was consistent with the classical theory of the Compton shift. The total (elastic plus inelastic) intensities were obtained over a range of s = 0.74–5.0 Å?1. Experimental difference intensities Δσee and Δσne were obtained separately by combining the X-ray and high-energy electron scattering data. The experimental results are in reasonable agreement with the theoretical intensities calculated from SCF and CI molecular wave functions with a basis set of double-zeta plus polarization functions. © 1994 John Wiley & Sons, Inc. 相似文献
167.
Summary For the quantitative analyses of evolved CO2and H2O during the thermal decomposition of solids, calibration curves, i.e. the amounts of evolved gases vs. the corresponding
peak areas of mass chromatograms measured by TG-MS, were plotted as referenced by the reaction stoichiometry of the thermal
decomposition of sodium hydrogencarbonate NaHCO3. The accuracy and reliability of the quantitative analyses of the evolved CO2and H2O based on the calibration curves were evaluated by applying the calibration curves to the mass chromatograms for the thermal
decompositions of copper(II) and zinc carbonate hydroxides. It was indicated from the observed ratio of evolved CO2and H2O that the compositions of copper(II) and zinc carbonate hydroxides examined in this study correspond to mineral malachite,
Cu2CO3(OH)2, and hydrozincate, Zn5(CO3)2(OH)6, respectively. Reliability of the present analytical procedure was confirmed by the fairly good agreement of the mass fraction
of the evolved gases calculated from the analytical values with the total mass-loss during the thermal decompositions measured
by TG. 相似文献
168.
Joonho Lee Wataru Shimoda Toshihiro Tanaka 《Monatshefte für Chemie / Chemical Monthly》2005,40(10):1829-1834
Temperature dependence of the surface tension of liquid Sn–Ag and Sn–Cu base lead-free solder alloys and oxygen partial pressure
dependence of liquid Sn–Ag alloy were evaluated using the experimental data obtained, respectively, by the constrained drop
method and the sessile drop method in the previous studies [1, 2]. The temperature dependences of the surface tension have
maximum positive values when the mol fraction of Ag and Cu is about 0.7, while those for pure liquid Sn, Ag, and Cu have negative
values. The calculated values based on Butler’s equations were found to be in reasonable agreement with those of the experimental data. The oxygen partial pressure dependences
of the surface tension of liquid Sn–Ag alloys at 1253 K have a minimum value when the mol fraction of Ag is about 0.9 and
the oxygen partial pressure is less than about 10−13 atm. From this, it is considered that the oxygen adsorption increased by adding Ag to Sn when the mol fraction of Ag is less
than 0.9. 相似文献
169.
A new ion chromatographic (IC) system, which uses zwitterionic (e.g., Zwittergent 3-14) micelles as both stationary and mobile phases, highly useful for the analysis of inorganic anions in biological samples, was developed. The zwitterionic micellar stationary phase (which is obtained by immobilizing the zwitterionic surfactant on surfaces of the reversed-phase ODS) showed high ability to confine the elution bands of the large amount of SO4(2-) and Cl- to narrow zones. As a result, a base-line separation of NO2-, Br- and NO3- from SO4(2-) and Cl- is always achieved. The zwitterionic micellar mobile phase, (which is obtained by dissolving the zwitterionic surfactant with a suppressive electrolytic solution, e.g., aqueous NaHCO3 solution), on the other hand, showed high ability for rapid elution of proteins. The separation column is therefore always being cleaned up even after the protein-containing sample is directly injected. The zwitterionic micelles are also insensitive to conductivity detection, therefore either the suppressed or the non-suppressed conductivity detection method is applicable for detection of the analyte ions. Urine and serum were chosen as the model real samples and were analysed with direct sample injection; the results of successful determination of a number of inorganic anions (SO4(2-), Cl-, NO2-, Br- and NO3-) in both samples have demonstrated the usefulness of this new IC system. 相似文献
170.
Yoshio Tanaka Morishige Atsukawa Yukio Shimura Akira Okada Hideki Sakuraba Tokuji Sakata 《Journal of polymer science. Part A, Polymer chemistry》1975,13(5):1017-1028
A soluble and self-crosslinkable linear copolymer with pendant epoxy and pyridyl groups was obtained from glycidyl methacrylate (M1) and 2-vinylpyridine (M2) or 2-vinyl-5-ethylpyridine (M2) by the action of azobisisobutyronitrile. The monomer reactivity ratios were determined in tetrahydrofuran at 60°C: r1 = 0.510, r2 = 0.620 with 2-vinylpyridine and r1 = 0.57, r2 = 0.62 with 2-vinyl-5-ethylpyridine. These were consistent with the calculated values with the reported Q and e values for these monomers. The intrinsic viscosities of the copolymers with 2-vinylpyridine and with 2-vinyl-5-ethylpyridine were found to be 0.17–0.19 and 0.26–0.38, respectively, in tetrahydrofuran at 30°C; they were independent of the copolymer composition. The copolymers were amorphous, had no clear melting points, and became insoluble crosslinked polymers under heating without further addition of any curing agents. 相似文献