硝酸氯冰溶胶水解反应过程的计算模拟

用二级微扰(MP2)和密度泛函理论(B3LYP),辅以不同的基组,对硝酸氯在冰表面上水解反应的机理进行了理论计算研究.根据关键部位化学键的松弛效应和关键原子的电荷分布,对冰表面催化的原因进行了深入分析.水分子一方面作为桥,辅助分子间质子发生迁移;另一方面作为连续介质,通过偶极相互作用加快硝酸氯的水解过程.     

2，6－二氨基吡啶与苦基氯的反应历程研究

对２，６－二氨基吡啶与苦基氯的反应历程进行了研究。通过二氨基吡啶与几种多硝基卤代苯的反应、溶剂效应、ＮａＦ的促进作用和紫外光谱吸收，证实该反应属于芳香族亲核取代反应类型，按加成－消除历程进行，反应过渡态涉及一个Ｍｃｉｓｅｎｈｅｉｍｅｒ络合物。     

HTPB／TDI,HDI聚合反应动力学研究

对端羟基聚丁二烯／甲苯二异氰酸酯，端羟基聚丁二烯／己二异氰酸酯甲苯溶液体系进行了反应动力学研究，用基团分析方法计算了相应体系的活化能，并对无催化剂和有催化剂的体系作了比较。结果表明，二丁基二月桂酸象对上述体系有强的催化作用，使体系的活化能降低，反应速度加快。对于对端差基聚丁二烯／甲苯二异氰酸酯体系，无催化剂时前后期反应活化能分别为２９．１ｋＪ／ｍｏｌ、３７．４ｋＪ／ｍｏｌ，有催化剂时前后期反应活化     

Substituent effects on the kinetics for the chemiluminescence reaction of 6-arylimidazo[1,2-a]pyrazin-3(7H)-ones (Cypridina luciferin analogues): support for the single electron transfer (SET)-oxygenation mechanism with triplet molecular oxygen

Kinetics of chemiluminescence reactions of 2-methyl-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one (1c, Cypridina luciferin analogue) and substituent effects of the 6-aryl group of derivatives 1 strongly suggest that the rate-determining step is a single electron transfer from an anion derived from 1 to a triplet molecular oxygen (O₂) in the oxygenation process.     

极性介质中醋酸乙烯酯的辐照引发分散聚合

用钴 60γ射线引发醋酸乙烯酯的分散聚合 ,通过选择各种极性溶剂体系 ,确立了醋酸乙烯酯在极性介质中稳定的分散聚合体系 .对异丙醇 水体系 ,聚合物分子量随剂量率的降低、稳定剂含量的增加、单体浓度的增大、反应温度的升高以及醇水比的降低而增加 .运用XPS、元素分析等表征聚合物粒子 ,及通过辐射接枝理论的分析 ,可以判断稳定剂所起的稳定作用主要是以物理吸附为主     

Oxygenolysis of flavonoid compounds: DFT description of the mechanism for quercetin.

Flavonoids are naturally occurring phenol derivatives present in substantial amounts in a large variety of plants, fruits and vegetables daily eaten by humans. Most of these compounds exhibit several interesting biological activities, such as antiradical and antioxidant actions. Indeed, by complexation with specific enzymes, flavonoids are notably liable to metabolize molecular dioxygen. On the basis of experimental results describing oxygenolysis of the flavonoid quercetin, activated by the enzyme quercetin 2,3-dioxygenase (2,3-QD),ur attention has focused on the role of metal center in the activation of the substrate quercetin. Thus, in the present study, by means of DFT calculations at the B3LYP/ 6-31(+)G* level on model molecular systems, we describe different mechanisms for dioxygen metabolization by quercetin. Stationary points are described, and energetic and structural analyses along the reaction paths are reported. Our calculations show that the copper cation must act as an oxidant towards the substrate and that the reaction proceeds through a 1,3-cycloaddition.     

Gradient extremals and valley floor bifurcations on potential energy surfaces

Gradient extremals are curves in configuration space denned by the condition that the gradient of the potential energy is an eigenvector of the Hessian matrix. Solutions of a corresponding equation go along a valley floor or along a crest of a ridge, if the norm of the gradient is a minimum, and along a cirque or a cliff or a flank of one of the two if the gradient norm is a maximum. Properties of gradient extremals are discussed for simple 2D model surfaces including the problem of valley bifurcations.     

均相催化反应在任一给定形状微电极上的稳态电化学行为

根据反应层的概念对在任一给定形状微电极上进行的准一级和二级均相催化反应机理(EC'')的稳态电化学行为进行了研究。本方法简便易行,不需要解复杂方程的数学技巧。利用推导出的这些方程,可计算准一级和二级均相催化反应的动力学常数。