The intramolecularly bridged alkyl cobaltic complexes are one of important coenzyme B12 model coplexes. In this paper, study on the thermolytic reaction of aqua(3 bromopropyl)cobaloximes in solution revealed that a ne...The intramolecularly bridged alkyl cobaltic complexes are one of important coenzyme B12 model coplexes. In this paper, study on the thermolytic reaction of aqua(3 bromopropyl)cobaloximes in solution revealed that a new intramolecularly bridged alkyl cobaloximes complex was formed and the reaction is influenced by tempertature and solvent. Adding cyclodxtrin has no obvious effect to the rate of the reaction, but various products with different axial bases were obtained. The intramolecularly bridged alkyl cobaloxime complex (bromo(O trimethylene dimethy lglyoxime)(dimethylglyoximate)cobalt?) was characterized by EA and ESI MS. Thermogravimetric analysis of this complex found that a carbon radical that from homolysis of the Co C bond is retained in the proximity of CoⅡ complex, which is very similar to the behavior of coenzyme B12.展开更多
【目的】为了探究驱避机理,此前选择萜类驱避化合物及与DEET（避蚊胺）具有类似结构的酰胺类驱避化合物,开展了驱避化合物与引诱气味组分（L-乳酸、羧酸等）缔合作用对驱避活性影响的研究。为了扩大驱避化合物的类型,本研究选择另外一...【目的】为了探究驱避机理,此前选择萜类驱避化合物及与DEET（避蚊胺）具有类似结构的酰胺类驱避化合物,开展了驱避化合物与引诱气味组分（L-乳酸、羧酸等）缔合作用对驱避活性影响的研究。为了扩大驱避化合物的类型,本研究选择另外一组43个酰胺类驱避化合物,计算了它们与蚊虫引诱物氨之间的双分子缔合作用,以及该缔合作用对驱避活性的影响,从而为驱避机理研究提供帮助。【方法】用Gaussian 03软件优化驱避化合物单体和双分子缔合体的三维结构式;通过Ampac和Codessa软件建立结构与驱避活性之间的定量构效关系模型。【结果】驱避化合物与氨分子的缔合距离、角度和缔合能量分别是2.2-3.0,128-180°和14-25 k J/mol;最佳四参数模型中R2为0.8987,其中2个参数来自驱避化合物单体,分别是（1/6）X GAMMA polarizability（DIP）和ESPminimum net atomic charge for an H atom,另外2个参数来自双分子缔合体,分别是ESP-DPSA-2 difference in CPSAs（PPSA2-PNSA2）[Quantum-Chemical PC]和Minimum valency of a C atom。模型检验中训练集和测试集的相关系数平方的平均值分别为0.9013和0.8666。【结论】驱避化合物与氨分子之间存在弱氢键力缔合作用,驱避化合物分子的极化度及其与氨分子之间的极性相互作用、缔合体中分子间键相互作用及其电荷分布均对驱避活性产生显著影响,说明双分子缔合对驱避活性具有显著影响。模型检验表明最佳四参数模型具有良好的稳定性和预测能力。本研究可为寻找新型蚊虫驱避剂和揭示蚊虫驱避剂的作用机理提供参考。展开更多
Two long carbon chain alkyl (aqua) Costa type organocobalt complexes (R=C 6H 13 and C 8H 17 ) have been synthesized for the first time and characterized by elemental analysis, UV Vis and 1H NMR. Their inclusion behavi...Two long carbon chain alkyl (aqua) Costa type organocobalt complexes (R=C 6H 13 and C 8H 17 ) have been synthesized for the first time and characterized by elemental analysis, UV Vis and 1H NMR. Their inclusion behavior with β cyclodextrin was studied by 1H NMR methods. It was indicated that in aqueous solution supramolecular adducts have been formed, in which the alkyl groups of the guests were included into the cavity of β CD. Cyclic voltammetry methods was also used to study the electrochemical properties of organocobalt complexes in the absence and presence of β CD. [WT5HZ]展开更多
文摘The intramolecularly bridged alkyl cobaltic complexes are one of important coenzyme B12 model coplexes. In this paper, study on the thermolytic reaction of aqua(3 bromopropyl)cobaloximes in solution revealed that a new intramolecularly bridged alkyl cobaloximes complex was formed and the reaction is influenced by tempertature and solvent. Adding cyclodxtrin has no obvious effect to the rate of the reaction, but various products with different axial bases were obtained. The intramolecularly bridged alkyl cobaloxime complex (bromo(O trimethylene dimethy lglyoxime)(dimethylglyoximate)cobalt?) was characterized by EA and ESI MS. Thermogravimetric analysis of this complex found that a carbon radical that from homolysis of the Co C bond is retained in the proximity of CoⅡ complex, which is very similar to the behavior of coenzyme B12.
文摘【目的】为了探究驱避机理,此前选择萜类驱避化合物及与DEET（避蚊胺）具有类似结构的酰胺类驱避化合物,开展了驱避化合物与引诱气味组分（L-乳酸、羧酸等）缔合作用对驱避活性影响的研究。为了扩大驱避化合物的类型,本研究选择另外一组43个酰胺类驱避化合物,计算了它们与蚊虫引诱物氨之间的双分子缔合作用,以及该缔合作用对驱避活性的影响,从而为驱避机理研究提供帮助。【方法】用Gaussian 03软件优化驱避化合物单体和双分子缔合体的三维结构式;通过Ampac和Codessa软件建立结构与驱避活性之间的定量构效关系模型。【结果】驱避化合物与氨分子的缔合距离、角度和缔合能量分别是2.2-3.0,128-180°和14-25 k J/mol;最佳四参数模型中R2为0.8987,其中2个参数来自驱避化合物单体,分别是（1/6）X GAMMA polarizability（DIP）和ESPminimum net atomic charge for an H atom,另外2个参数来自双分子缔合体,分别是ESP-DPSA-2 difference in CPSAs（PPSA2-PNSA2）[Quantum-Chemical PC]和Minimum valency of a C atom。模型检验中训练集和测试集的相关系数平方的平均值分别为0.9013和0.8666。【结论】驱避化合物与氨分子之间存在弱氢键力缔合作用,驱避化合物分子的极化度及其与氨分子之间的极性相互作用、缔合体中分子间键相互作用及其电荷分布均对驱避活性产生显著影响,说明双分子缔合对驱避活性具有显著影响。模型检验表明最佳四参数模型具有良好的稳定性和预测能力。本研究可为寻找新型蚊虫驱避剂和揭示蚊虫驱避剂的作用机理提供参考。
文摘Two long carbon chain alkyl (aqua) Costa type organocobalt complexes (R=C 6H 13 and C 8H 17 ) have been synthesized for the first time and characterized by elemental analysis, UV Vis and 1H NMR. Their inclusion behavior with β cyclodextrin was studied by 1H NMR methods. It was indicated that in aqueous solution supramolecular adducts have been formed, in which the alkyl groups of the guests were included into the cavity of β CD. Cyclic voltammetry methods was also used to study the electrochemical properties of organocobalt complexes in the absence and presence of β CD. [WT5HZ]
