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11.
Katsuma Hiraki Takeo Inoue Hidefumi Hirai 《Journal of polymer science. Part A, Polymer chemistry》1970,8(9):2543-2554
ESR spectra of homogeneous catalyst derived from tris(acetylacetonato)titanium(III) and triethylaluminum were observed at several temperatures from ?78°C, to +25°C, at molar ratios of aluminum to titanium of 1–108. At ?78°C, this catalyst yields a violet complex which shows an ESR signal with a g value of 1.959 and is associated with the first intermediate. At ?40°C to ?30°C, this signal decreases, and two signals with g values of 1.947 and 1.960 are observed. The latter two signals diminish at ?5°C to +10°C, while two kinds of new signals with g values of 1.965 and 1.969 appear overlapping each other. The structures of the species corresponding to these five signals are discussed on the basis of the ESR spectra, the intensity change, and the unpaired spin distribution. A new signal with a g value of 1.978 is found in the presence of butadiene at 25°C at Al/Ti > 8 and is assigned to a growing end of polybutadiene with this catalyst. The polymer yield increases remarkedly at Al/Ti molar ratios greater than 10. The microstructure of the resulting polymer consists almost completely of 1,2 units. The structure of the growing end is proposed to be a titanium (III) species containing two 1-substituted allyl groups, by comparison with the structure ascribed to the growing end of polybutadiene with n-butyl titanate-triethylaluminum catalyst. 相似文献
12.
Emission profiles of several organic sulfur compounds are investigated by modified molecular emission cavity analysis (MECA). Thiourea, 1,3-diethylthiourea, S-methyl- cysteine and taurine are pyrolyzed in a hydrogen stream and the pyrolytic products are determined by gas chromatography. The S2 emission mechanism is discussed on the basis of emission profiles and the composition of the pyrolytic products. Although some compounds give multipeaked responses, the splitting disappears when a worn surface cavity is used or oxalic acid is added to the sulfur compound in the cavity. When the emission profile from thiourea is compared with that from 1,3-diethylthiourea, it is clear that the multipeaked response is due to quenching by degradation products of the latter compound. The main product of pyrolysis is hydrogen sulfide. The emission intensity is related to the yield of hydrogen sulfide in pyrolysis. As methylmercaptan was not detected in the pyrolysis products, it is suggested that the quenching by the organic fragments results from their hydrogen consumption rather than their reaction with sulfur species. The S2 emission from sulfur-containing compounds is rapidly complete in the presence of oxalic acid, and it is suggested that such compounds are subject to reductive breakdown in the cavity. 相似文献
13.
用改进的介电松弛谱仪(精度2‰)测定了VDF/TrFE(7/27、65/35、52/48mol%)共聚物溶液成膜、液氮淬火、熔融慢冷和热处理试样在-120—130℃、10-2一104Hz范围的复数介电常数.介电松弛研究结果显示低结晶度的淬火试样较高结晶度的熔融慢冷和热处理试样的Tc高.结晶度上升,居里点处的介电常数增大.室温以下的介电频率谱分别由代表非晶区分子运动的β松弛(低频部)和局域运动的γ松弛(高频部)叠合而成.随结晶度提高,β松弛峰减小,γ松弛峰增大;非晶松弛强度减弱.晶区松弛强度增强. 相似文献
14.
Intramolecular alkene-carbonyl coupling reaction of N-benzyl-N-(o-alkenylaryl)carbamate derivative derived from o-aminostyrene, o-(aminomethyl)styrene and o-aminoallylbenzene smoothly proceeded by treating with zirconocene-butene complex to give the corresponding lactam derivative. 相似文献
15.
Joaquim I. GOES Nobuhiko Handa Satoru Taguchi Takeo Hama 《Photochemistry and photobiology》1995,62(4):703-710
Abstract— The impact of ultraviolet-B radiation (UVBR) on the biosynthesis and the composition of intracellular dissolved free and combined amino acids was examined in nitrate-replete and nitrate-deficient cultures of Tetraselmis sp. Several similarities were observed in the response of Tetraselmis sp. to nitrogen deficiency and exposure to UVBR, in support of a view that UVBR affects amino acid synthesis in phytoplankton via its inhibitory effects on nitrogen assimilation into the cells. At levels that still permitted the uptake of carbon into the cells, both nitrogen deficiency and UVBR exposure resulted in a reduction in the overall rates of carbon incorporated into amino acids, an increase in the absolute concentrations of amino acids within the intracellular dissolved free amino acid (INDFAA) pool and a decrease in the total cellular amino acid (TCAA) pool. An examination of the patterns of carbon assimilation into individual amino acids in cells exposed to UVBR revealed similarities with the patterns in cells subject to nitrogen deficiency. The most conspicuous changes from the controls included an increased incorporation of 13 C into glutamic' acid (glutamic acid + glutamine) and aspartic acid and a marked reduction into alanine and valine. Changes in the concentrations of amino acids within the INDFAA and TCAA pools were also similar in nitrate-deficient and UVBR-exposed cells and resembled the carbon assimilation patterns. These results strongly suggest that UVBR-induced changes in the biosynthesis and composition of amino acids are probably via its suppression of nitrogen assimilation into the cells. 相似文献
16.
Doi H Sakai T Iguchi M Yamada K Tomioka K 《Journal of the American Chemical Society》2003,125(10):2886-2887
The external chiral ligand-controlled asymmetric conjugate addition reaction of lithium amides with alpha,beta-unsaturated esters provided beta-amino esters in high yields and high enantioselectivities. 相似文献
17.
Analysis of the interaction between human plasma fibronectin and gelatin by affinity electrophoresis
The interaction between human plasma fibronectin and gelatin was analyzed by affinity electrophoresis, in which the fibronectin was subjected to electrophoresis in a 4% polyacrylamide gel in the presence and absence of gelatin, as an affinity ligand, and the fibronectin band was stained by an immunoblotting method. The apparent dissociation constants (Kd) of fibronectin for gelatin were calculated from affinity plots based on the original affinity equation at different pHs, urea concentrations, and temperatures. The fibronectin exhibited much lower affinity in the presence of urea. The Kds at 37 degrees C were 1.49 X 10(-7) M, 2.50 X 10(-6) M, and 3.58 X 10(-6) M with 2 M, 3 M, and 4 M urea, respectively. The van't Hoff plots of Kd values against absolute temperature (T) showed that the value of log Kd decreased in proportion to the increase in the value of 1/T within the range of 15-50 degrees C. The standard enthalpy, the standard free energy change at 37 degrees C, and the entropy change at 37 degrees C for association were calculated to be -124.7 kJ/mol, -33.23 kJ/mol, and -295.1 J/mol/deg, respectively. These results suggest that a hydrophilic interaction, such as hydrogen bond or van der Waals interaction, plays an important role in the binding of plasma fibronectin to gelatin. 相似文献
18.
Takeo Miyazawa Takeshi Endo Makoto Okawara 《Journal of polymer science. Part A, Polymer chemistry》1985,23(5):1527-1535
Some hindered amine polymers containing 2,2,6,6-tetramethylpiperidine structure were synthesized. A new monomer, 4-O-vinylbenzyl-2,2,6,6-tetramethylpiperidine, was homopolymerized and copolymerized with some vinyl monomers in the presence of AIBN as an initiator. The obtained amine polymers were oxidized with hydrogen peroxide to obtain the polymers having nitroxyl radical moiety. 相似文献
19.
Contrary to the precedents, 1,3-anti stereoselection was found in the intramolecular Michael addition of ethyl ,5-carbamoyloxy-4-trialkylsilyloxy-2-hexenoate to culminate in a synthesis of N-benzoyl-,-daunosomine. The antiperiplanar effect due to the group at 4-position was revealed to play a major role in the stereoselection in this type of reactions. N-benzoyl-,-3-epidaunosamine was also synthesized by 1,2-syn asymmetric induction. 相似文献
20.
Takeo Fujino Hiroaki Tagawa Takeo Adachi Hiroshi Hashitani 《Analytica chimica acta》1978,98(2):373-383
A simple gravimetric determination of oxygen in uranium oxides and ternary uranium oxides is described. In alkaline earth uranates which are formed by heating in air at 800–1100°C, uranium is in the hexavalent state over certain continuous ranges of alkaline earth-to-uranium ratios. Thus, if an alkaline earth uranate or a compound containing an alkaline earth element, e.g. MgO, is mixed with the oxide sample and heated in air under suitable conditions, oxygen can be determined from the weight change before and after the reaction. The standard deviation of the O:U ratio for a UO2+x test sample is ±0.0008–0.001, if a correction is applied for atmospheric moisture absorbed during mixing. 相似文献