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551.
Styrene (St) and methyl methacrylate (MMA) were polymerized by azobisisobutyronitrile at 50°C. in the presence of silanes such as tetramethylsilane, trimethylcholorosilane, dimethyldichlorosilane, methyltrichlorosilane, and tetrachlorosilane. The polymerization rates of both St and MMA in the presence of silanes were nearly equal to those in the absence of silanes. On the other hand, the molecular weights decreased gradually as the concentration of chlorosilane increased. The chain transfer constants of all the silanes in the polymerization of St and MMA at 50°C. were calculated by Mayo's equation. The chain transfer constants of Me4Si, Me3SiCl, Me2SiCl, MeSiCl3, and SiCl4 were 0.31 × 10?3, 1.25 × 10?3, 1.78 × 10?3, 1.92 × 10?3, and 2.0 × 10?3, for St and 0.13 × 10?3, 0.22 × 10?3, 0.245 × 10?3, 0.27 × 10?3, and 0.30 × 10?3, for MMA, respectively. From these results, it was found that the Si? Cl bond was radically cleaved. The Qtr values of the silanes, in the same order as above, were found to be 1.03 × 10?4, 2.33 × 10?4, 2.83 × 10?4, 3.10 × 10?4, and 3.35 × 10?4, respectively and the etr values were +0.58, +1.30, +1.50, +1.48, and +1.43, respectively. 相似文献
552.
Y. Kumashiro T. Enomoto K. Sato Y. Abe K. Hirata T. Yokoyama 《Journal of solid state chemistry》2004,177(2):529-532
The electrical properties of n-BP films newly prepared by thermal CVD in the B2H6-PH3-H2 system were improved by a deuterium lamp excitation. High-temperature electrical conductivity and thermoelectric power of amorphous boron and polycrystalline boron phosphide films grown on silica glass were measured to evaluate the thermoelectric figure-of-merit (Z). In particular, the Z-value for photo-thermal BP films was higher (10−4/K) than that of boron films, indicating that they are promising for high-temperature thermoelectric materials. 相似文献
553.
Masaru Enomoto 《Tetrahedron》2006,62(6):1102-1109
Based on the previously revised stereochemistries for communiols A-C, the ent-8-epi- and ent-6-epi-stereoisomers of the original structures proposed for communiols D and H, respectively, were synthesized as highly probable candidates for their genuine structures by using the Sharpless asymmetric dihydroxylation as the source of chirality. Complete accord in spectral properties between each synthetic candidate and the corresponding natural material as well as the fact that communiols A-D and H were all isolated from the same fungal source, led us to the conclusion that the stereochemistries of communiols D and H should also be revised to their (3S,5S,7R,8S,11R)- and (5S,7R,8S)-forms, respectively. 相似文献
554.
Beryllium (ca. 10?2?10?4 M) is determined by adding excess of 1,2-phenylenediamine-N,N,N′, N′-tetraacetic acid (PhDTA, H4L) and back-titrating with copper(II); arsenazo-I serves as indicator. Formation constants of BeL and BeHL were determined by potentiometry: log KBeL=6.48±0.02 and log KHBeHL=3.48±0.03 (25°C, I=1 M in NaClO4). Expressions for the titration curve are given together with theoretical errors. 相似文献
555.
Copolymerization of methacrylic acid alkali metal salts (MAAM; M = Li, Na, K, Rb or Cs) and oligo(oxyethylene) methacrylate (MEO) was carried out in bulk or in poly(oligo(oxyethylene) methacrylate) (PMEO) at 60°C. The copolymers of MAAM and MEO which were obtained by bulk polymerization showed a cation conductivity of around 1 × 10?7 S/cm at room temperature. On the other hand, the copolymers obtained by radical polymerization in PMEO, showed a higher cation conductivity (10?6–10?5 S/cm). Furthermore, higher cation conductivity was observed for the copolymer systems containing alkali metal cations with a larger ion radius. This tendency was explained by the strength of the bond between alkali metal cation and ether oxygens. The degree of dissociation had little effect on this difference in the conductivity. The effective dissociation of methacrylic salts was enhanced in the copolymer compared to the homopolymer because of the suppression of the adjacent dissociative carboxylic acid groups. Arrhenius plots for ionic conductivity show the migration of ions along with the segmental motion of the polymer matrix. 相似文献
556.
R. G. Weginwar B. Liu S. Ambe S. Enomoto H. Maeda F. Ambe 《Journal of Radioanalytical and Nuclear Chemistry》1996,210(1):119-127
The solvent extraction of Zr and Hf was studied using 444-trifluoro-1-(2-thienyl)-1,3-butanedione (TTA) from a multitracer solution containing carrier-free radioisotopes of Zr, Hf, and other elements. The multitracer was prepared from Au foil irradiated with high-energy heavy-ion beams. Effects of HCl and HNO3 concentrations and organic solvent on the extraction and coextraction of other radionuclides have been studied. It was found that decalin (decahydronaphthalene) was the best solvent among 14 solvents studied and the optimum aqueous phase was 2 mol·dm–3 HCl or HNO3. About 2–10% of Sr, Rb, Sc and Nb were coextracted with Zr and Hf. The reversed phase extraction of Zr and Hf was also developed by using ethylenediaminetetraacetic acid (EDTA) solution at pH range of 8.5–10. 相似文献
557.
Many alkali metal carboxylates when dissolved in poly(ethylene oxide) (PEO) oligomers, are phaseseparated by heating. These were revealed to be the crystals of the initially dissolved corresponding salts from the X-ray diffraction patterns. Some acetate salts achieve the lower limit of the lattice energy for phase separation of ordinary inorganic salts by heating in PEO oligomers. These carboxylate salts were therefore expected to show crystallization behavior in PEO oligomers by heating. The effects of cation size, alkyl chain length and molecular weight of PEO on the solubility are summarized. Negative temperature dependence of solubility of these acetate salts is seen in the PEO oligomers only when the salts have long alkyl chains. The salts containing larger cations needed a longer chain length of PEOs for crystallization by heating. These salts with longer alkyl chains showed positive temperautred dependence in lower molecular weight polyethers, but negative temperature dependence in solubility in PEO with molecular weights higher than 400. In PEO400, all the carboxylates with longer alkyl chains were phase separated by heating. 相似文献
558.
Fukuzawa K Kitaura K Uebayasi M Nakata K Kaminuma T Nakano T 《Journal of computational chemistry》2005,26(1):1-10
We have theoretically examined the relative binding affinities (RBA) of typical ligands, 17beta-estradiol (EST), 17alpha-estradiol (ESTA), genistein (GEN), raloxifene (RAL), 4-hydroxytamoxifen (OHT), tamoxifen (TAM), clomifene (CLO), 4-hydroxyclomifene (OHC), diethylstilbestrol (DES), bisphenol A (BISA), and bisphenol F (BISF), to the alpha-subtype of the human estrogen receptor ligand-binding domain (hERalpha LBD), by calculating their binding energies. The ab initio fragment molecular orbital (FMO) method, which we have recently proposed for the calculations of macromolecules such as proteins, was applied at the HF/STO-3G level. The receptor protein was primarily modeled by 50 amino acid residues surrounding the ligand. The number of atoms in these model complexes is about 850, including hydrogen atoms. For the complexes with EST, RAL, OHT, and DES, the binding energies were calculated again with the entire ERalphaLBD consisting of 241 residues or about 4000 atoms. No significant difference was found in the calculated binding energies between the model and the real protein complexes. This indicates that the binding between the protein and its ligands is well characterized by the model protein with the 50 residues. The calculated binding energies relative to EST were very well correlated with the experimental RBA (the correlation coefficient r=0.837) for the ligands studied in this work. We also found that the charge transfer between ER and ligands is significant on ER-ligand binding. To our knowledge, this is the first achievement of ab initio quantum mechanical calculations of large molecules such as the entire ERalphaLBD protein. 相似文献
559.
560.