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K Kiruthiga P Aravindan S Anandan P Maruthamuthu 《Research on Chemical Intermediates》2006,32(2):115-135
N,N,N′,N′-Tetramethylbenzidine (TMB) is an aromatic amine that undergoes oxidation by various oxidizing agents such as Ce4+, MnO−4, Cr2O2−7; HSO−5, S2O−8, H2O2, Cl2, Br2 and I2, thereby serving as a reducing substrate. One-electron oxidation of TMB results in a radical cation (TMB˙+), and on further oxidation leads to the product dication (TMB++) were monitored by stopped-flow spectrophotometer at the absorption wavelength of TMB˙+(λmax; 460 nm). ESR data was also provided to confirm the formation of radical cation. The rates of both the formation and decay
of TMB˙+ have been followed by a total second-order kinetics, a first-order dependence each on [TMB] (or) [TMB˙+] and [oxidant]. The kinetic and transition state parameters have been evaluated for the effects of pH and temperature on
the formation and decay of TMB˙+ and discussed with suitable reaction mechanisms. Also, the rate constants for the reactions of the radical cation with various
reducing agents such as sulfite (SO2−3), thiosulfate (S2O2−3), dithionite (S2O2−4) and disulfite (S2O2−5) and ascorbic acid (vitamin C, AH2 were determined. Besides these, this article also explains how TMB acts as a better electron relay than unsubstituted benzidine,
even though both of them undergo one-electron oxidation and are used in the chemical routes to solar energy conversions. The
observed rate constants for electron transfer were correlated theoretically using Marcus theory. The observed and calculated
rate constants have good correlation. 相似文献
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A new method is discussed to obtain the interior solution of Einstein-Maxwell equations for a charged static sphere from a known particular solutions of a similar kind. Beginning with a charged fluid interior solution reported by Patel and Pandya [11], a new interior Reissner-Nördstrom metric is obtained using this method and physical aspects of it are extensively discussed. 相似文献
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采用快速混合停流技术,考察了pH=7.4,V(CH~3CN):V(H~2O)=1:1的混合溶剂中水溶性锰卟啉Mn^I^I^I(TMPyP)与单氧给体NaOCl及KHSO~5构建的细胞色素P-450模拟酶体系催化氧化活性物种的生成及催化烯烃DPBD环氧化过程。实验表明,在反应进行中存在着两种中间体:oxo-Mn^V(Por.)(1)和oxo-Mn^I^V(Por.)(2),但两者的催化活性有差异,在催化烯烃DPBD环氧化反应中,对于Mn^I^I^I(TMPyP)-NaOCl体系起催化作用的主要作用的主要是中间体1,而对于Mn^I^I^I(TNPyP)-KHSO~5体系两种中间体均与烯烃配位生成环氧化产物,并且该体系催化活性较高。 相似文献
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苯甲酰基五氟丙酰基亚甲基三苯基胂的亚甲基上带有两个强吸电子基团.由甲醇-水溶液中获得的该化合物单晶属三斜晶系,空间群为PI;晶胞参数a=12.292A,b=13.457A,c=15.318A,α=90.562°,β=90.516°,γ=92.82°;Ζ=4.用四圆衍射仪收集X射线衍射强度数据,用重原子法进行结构测定,用块对角矩阵阻尼最小二乘法进行结构修正.对8393个独立的可观测衍射点,最后的R因子为0.061.叶立德碳原子具有sp~2杂化的平面构型.As-C(1)键长为1.888A,比As=C双键长得多,也比已报道的其它胂叶立德的相应键长为长,表明“ylene”型结构的贡献较小.强吸电子基团的存在有利于负电荷的离域化,导致化学稳定性的增加. 相似文献
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We apply a technique, due to Stephani, for generating solutions of the Einstein-perfect-fluid equations. This technique is similar to the vacuum solution generating techniques of Ehlers, Harrison, Geroch and others. We start with a seed solution of the Einstein-perfect-fluid equations with a Killing vector. The seed solution must either have (i) a spacelike Killing vector and equation of state P = or (ii) a timelike Killing vector and equation of state + 3P = 0. The new solution generated by this technique then has the same Killing vector and the same equation of state. We choose several simple seed solutions with these equations of state and where the Killing vector has no twist. The new solutions are twisting versions of the seed solutions. 相似文献
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