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961.
The present paper employed density function theory to investigate two reaction pathways for isomerization of enol ester proposed by Yang(path a) and the present authors(path a), respectively. The base catalytic effects of solvent triethylamine on these two reactions were also evaluated. It is demonstrated that path B is more preferable than path a due to low barrier height for the rate-determining step. 相似文献
962.
In this paper, we used bond-length equalization, aromatic stabilization energies (ASE) and nucleus-independent chemical shifts
(NICS), calculated with (density functional theory) B3LYP levels at the 6-311+G** basis set, to evaluate the aromaticity of a set of 38 five-member planar π-electron aromatic systems: sila-, aza- and phospha-
derivatives and their parent systems. The result revealed statistically significant correlations among the above three criteria,
and the order of aromaticity of the whole set was: Aza- derivatives rings > Phospha- derivatives rings > Sila- derivatives
rings > Carbon-containing rings; NICS(0.6) and NICS(0.8) had the same results in evaluating the order of aromaticity in our
case. 相似文献
963.
1—酰基—4—氯环己烷与取代芳烃的区域与立体选择性反应 总被引:2,自引:0,他引:2
从环己烯合成了1-酰基-4-氯环己烷,发现在其在AlCl3催化与苯,氯苯,溴苯等优先生成反式1-芳基-4-酰基环己烷,与联苯反应时选择性较差。 相似文献
964.
用恒电位电流衰减法及激光扫描光电化学显微技术研究了在于PH=12.5及13.8的模拟混凝土孔溶液中钢筋钝化化膜的生长动力学及相应的破坏过程,实验结果表明,钢筋钝化膜的生长过程存在两个主要阶段,各阶段膜厚均与生长时间存在正比对数关系,但当t<30秒和t>30秒时,膜的生长表出出不同的动力学特征,在钝化发生点蚀前,钝化膜的微区光电流一定的预兆,腐蚀抑制剂NaNO2影响膜的生长过程及膜厚,能提高钢筋的抗 相似文献
965.
在前人工作的基础上, 改进了液上空间气相色谱测活度系数的方法, 实验测定了TBP. 稀释剂和水形成的多个二元系、三元系和四元系的活度系数和密度. 选用的稀释剂有n-C_6H_(14)、n-C_7H_(16)、n-C_8H_(18)、C_6H_6、cy-C_6H_(12)、CCl_4和CHCl_3. 在Pierotti理论的基础上, 采用新的硬球作用表达式和径向分布函数, 并计及分子间的排斥能、色散能、取向能和诱导能, 建立了简单的活度系数模型, 并用于TBP和稀释剂体系的计算. 从二元系回归得到的分子参数较好地预测了三元系的活度系数. 相似文献
966.
利用合成的巯基含量为2.2~2.5%的高巯基粉状巯基棉,对水中超痕量汞进行富集测定。流速可达100mL·min~(-1),检出限为0.5×10~(-12),加标回收率为90~104%。 相似文献
967.
Mutation of the active-site residue Cys38 of N-Ada converts it from a sacrificial DNA repair protein to an enzyme that uses methanethiol as an external sacrificial reagent to repair DNA methyl phosphotriesters catalytically. 相似文献
968.
969.
Electrochemical studies on the interaction of heparin with crystal violet and its analytical application 总被引:1,自引:0,他引:1
In this paper, crystal violet (CV) was used to determine heparin concentration by linear sweep voltammetry on a dropping mercury
electrode (DME). In Britton-Robinson (B-R) buffer solution, pH 3.0, CV had a well-defined second-order derivative linear sweep
voltammetric reductive wave at −0.74 V (vs. SCE). After the addition of heparin to the CV solution, the reductive peak current
decreased greatly with the positive movement of the peak potential and without appearance of new peaks in the scanning potential
range. Based on the decrease in the reductive peak current, a new voltammetric method for the determination of heparin was
established. The conditions for the interaction and the electrochemical detection were optimized, and interfering substances
were investigated. Under the optimal conditions, the decrease in reductive peak currents of CV was proportional to heparin
concentration in the range 0.1–8.0 mg/L with the linear regression equation Δip″(nA) = 400.42 + 1563.11c (mg/L), (n = 14, γ = 0.993). The detection limit was 0.092 mg/L. This new method was further successfully applied to the determination of heparin
content in heparin sodium injection samples with satisfactory results. The binding ratio and binding mechanism were also studied
by the electrochemical method.
The text was submitted by the authors in English. 相似文献
970.
Wei SUN Ya Qin DING Kui JIAO 《中国化学快报》2005,16(11):1515-1518
The interaction of phenosafranine (PSF) with a glycosaminoglycans of heparin (Hep) in aqueous solution has been characterized by UV-Vis absorption spectrophotometry and cyclic voltammetry in pH 1.5 Britton-Robinson (B-R) buffer solution. The addition of Hep caused decrease of the absorbance of PSF at 532 nm and the redox peak current of PSF. The study showed that an supramolecular complex of PSF-Hep was formed because of the electrostatic attraction of negatively charged Hep with the positively charged PSF, which resulted in the decrease of the equilibrium concentration of PSF in solutions, and the decrease of the absorbance or the peak current of PSF. The stoichiometry of the Hep/PSF complex was further calculated by voltammetric data with the result of 1:1 complex. 相似文献