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151.
Yuh-Wern Wu 《中国化学会会志》1996,43(6):507-509
The relative rates for the addition reactions of tert-butyl radical to 2-substituted ally chlorides I have een determined. The correlation of log k/k0, vs. σm gives a ρ mvalue of 3.59 with correlation coefficient of 0.930. When the substituent CH2Cl is excluded, correlation coefficient raises to 0.990 and ρ value becomes 3.39. The large p value and the deviation of relative rate of substituent CH2C1 are discussed. 相似文献
152.
153.
V. B. Vol'eva T. I. Prokofeva A. I. Prokofev I. S. Belostotskaya N. L. Komissarova V. V. Ershov 《Russian Chemical Bulletin》1995,44(9):1720-1724
The interaction of 3,6-di-tert-butyl-ortho-benzoquinone (1) and 3,5-di-tert-butyl-ortho-benzoquinone (2) with NH3 in water—alcohol medium and with (NH4)2CO3 in a solid phase has been studied. Redox processes with participation of a nucleophile of the medium take place for1, while2 reacts with NH3 at the carbonyl group with transformation of the quinone imide. The mechanism of redox transformation of1 has been proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1789–1793, September, 1995.This work was carried out with financial support from the Russian Foundation for Basic Research (Project No. 94-03-08653). 相似文献
154.
流动注射邻菲啰啉化学发光体系测定羟自由基 总被引:3,自引:0,他引:3
利用Vitc-CuSO4-H2O2产生的羟自由基,建立流动注射邻菲口罗啉化学发光体系测定羟自由基的产生及物质对羟自由基的清除能力。体系中各种物质浓度的最佳组合是:邻菲口罗啉1.0×10-3mol/L(pH 8.2硼砂-硼酸缓冲液配制、内含CTMAB浓度为5.0×10-3mol/L)、Cu2+1.5×10-3mol/L、H2O2体积分数0.6%、抗坏血酸1.5×10-3mol/L。硫脲清除羟自由基的量效关系Y=25.0009ln(x)+65.3120,r=0.9988,IC50=0.542 mmol/L。龙井茶水提液对羟自由基具有较强的清除作用。 相似文献
155.
在CCSD(T)/6-311G(d,f)//MP2/6-311G(d,f) ZPE水平下,计算得到含有8个异构体和11个过渡态的HSCCS自由基体系势能面,讨论了异构体的结构与稳定性及异构体之间的异构化过程.结果表明异构体m1的能量最低,除m1以外,异构体m2和m3的能量也比较低,在MP2水平上,过渡态TS1的能量比异构体m2仅高3.9kJ/mol,而在CCSD(T)水平上,TS1的能量比m2低14.6 kJ/mol,这说明异构体m2可以迅速转化为能量更低的m1.异构体m3的能量比异构体m1高49.99 kJ/mol,可以推断,在合适的实验条件下可以观测到异构体m1. 相似文献
156.
Manabu Tanaka Kaoru Hatta Tomohiko Edura Ken Tsutsui Yasuo Wada Hiroyuki Nishide 《先进技术聚合物》2007,18(11):925-931
The electric conductivity of π‐conjugated and radical‐bearing polymers, i.e., polythiophenes bearing pendant galvinoxyl and phenoxyl radical groups, was measured using a microcomb‐shaped electrode. The electric conductivity was found to be enhanced by the radical content in the polymer. The infrared (IR) and Raman spectroscopies suggested a structural change from an aromatic form to a quinoid one in the polythiophene backbone by the phenoxyl radical generation. The effect of the pendant galvinoxyl radical's unpaired electron on the electric conductivity of the polythiophene was discussed by comparing the conductivity of a radical‐bearing polystyrene and a polythiophene mixed with low‐molecular radical molecules. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
157.
以支撑磷脂双层膜(supported bilayer lipid membrane, s-BLM)作为生物膜模型, 利用Fenton体系产生羟自由基(hydroxyl free radical, •OH), 采用循环伏安法研究了s-BLM与•OH之间的相互作用. 结果表明: •OH通过与磷脂发生化学反应, 诱发s-BLM上形成孔洞或缺陷, 这种作用对时间、FeSO4和H2O2的浓度具有依赖性, 且不可恢复. 具有还原性基团的抗氧化剂维生素C, 还原型谷胱甘肽和L-半胱氨酸, 通过与•OH发生氧化还原反应, 可抑制•OH与s-BLM的相互作用, 降低•OH对s-BLM结构的破坏程度. 相似文献
158.
The copolymerization of acrylonitrile (AN) in dimethylformamide (DMF) was retarded by the presence of itaconic acid (IA) comonomer. Addition of TEA helped overcome the retardation at enhanced concentrations of IA in the feed. The monomer reactivity ratios determined by both terminal and penultimate models revealed that the overall monomer reactivity’s are practically unaffected by the presence of TEA. The penultimate-unit effect for radicals terminated in AN was enhanced by the presence of TEA. Higher TEA concentrations helped regain the reactivities of AN and IA to AN-radical to the state in pure DMF. The penultimate model could explain the feed-copolymer composition profile for the whole range. Whereas IA systematically retarded the polymerization rate at all concentration regime in DMF, it increased the rate at higher IA concentration in DMF/TEA system. For a given IA concentration, the polymerization rate decreased as the solvent is enriched in TEA. The copolymers synthesized in the presence of TEA, manifested higher cyclization temperature and consequently lower char residue, attributed to the incorporation of TEA in the polymer by means of salt formation with IA moiety camouflaging the catalytic effect of the -COOH group in cyclization reaction. 13C-NMR studies confirmed the incorporation of the TEA molecules in the polymer chain. 相似文献
159.
160.
A novel conjugation-elongated bis(ethylenedithio)tetraselenafulvalene (BETS) type donor, 2,5-bis(4,5-ethylenedithio-1,3-diselenol-2-ylidene)-2,3,4,5-tetrahydrothiophene (BEDT-HBDST) and its magnetic and non-magnetic anion salts, (BEDT-HBDST)2MX4 (MX4−=FeCl4−, GaCl4−, FeBr4− and GaBr4−), were prepared. These four salts are isostructural and belong to the space group of P2/c. They showed semiconducting behavior with small activation energies (59-64 meV). The band structures of these salts are quasi one-dimensional and there is a midgap between the upper band and the lower band, since the degree of dimerization is significant in the stacking direction. The MX4− ions are located between the donor columns and near to the ethylenedithio moieties of the donor molecules. The magnetic susceptibilities of the FeCl4− and FeBr4− salts follow the Curie-Weiss law with Curie constants of 4.6 and 4.8 emu K mol−1 (sum of the spins of S=5/2 and S=1/2) and negative Weiss temperatures of θ=−1.2 and −4.9 K, respectively, revealing a weak antiferromagnetic interaction of 3d spins of the FeCl4− and FeBr4− anions. The Fe?Fe (6.66-7.60 Å), Cl?Cl (4.81-4.82 Å) and Br?Br (4.74-4.77 Å) distances in the crystal structures of these salts are significantly long. Therefore, the direct magnetic interaction between the 3d spins of the nearest neighboring Fe3+ ions appears to be not readily accessible. 相似文献