The capacity factors （k＇） of fourteen types ofhalogenated thiophenols in different phases of methanol-water eluent were determined by reversed phased high-performance liquid chromatography （RP-HPLC） and the relat...The capacity factors （k＇） of fourteen types ofhalogenated thiophenols in different phases of methanol-water eluent were determined by reversed phased high-performance liquid chromatography （RP-HPLC） and the relationships between the logarithm of capacity factor lgK＇ and methanol ratio ψ were analyzed. A fair linear relationship is found between lgK＇ and ψ, and the correlation coefficients R2 of the constructed linear equations are all greater than 0.990. Relationship between the chromatographic data lgKw＇ when extrapolated to pure water and n-octanol/water partition coefficient lgKow obtained by the group contribution method has shown a good linear correlation with R2= 0.956. The structure parameters of fourteen halogenated thiophenols were calculated by using DFT, and the correlation equation of lgKw＇ and structure parameters was obtained by using SPSS, lgKw＇ = -0.409 ＋ 0.039a and R2 = 0.981, meaning that lgKw＇ is mainly determined by the polarizability α.展开更多
The synthesis of a series of unsaturated 4-methylene-1,3-dioxolanes has been realized and the addition of thiophenol to the synthesized compounds in the presence of radical initiators has been carried out. It has been...The synthesis of a series of unsaturated 4-methylene-1,3-dioxolanes has been realized and the addition of thiophenol to the synthesized compounds in the presence of radical initiators has been carried out. It has been established the behavior of the addition reaction both with opening of dioxolane cycle and without it. The influence of nature of substituents of С2-carbon atom of dioxolane cycle, ratio of the initial reagents and temperature on direction of the addition reaction has been studied. The adducts obtained as a result of the addition reaction have a linear and cyclic structure, which have been established by data of the chemical and spectral analyses. It has been found that the ratio dioxolane compound: thiophenol, reaction temperature and nature of the functional substituent influences on quantity of these adducts.展开更多
Microbial transformation of gastrodin by Mucor spinosus strain 3.3450, resulted in a product with a transformation rate close to 100 per cent. This product was identified as p-hydroxy benzyl alcohol on the basis of it...Microbial transformation of gastrodin by Mucor spinosus strain 3.3450, resulted in a product with a transformation rate close to 100 per cent. This product was identified as p-hydroxy benzyl alcohol on the basis of its 1H, 13C NMR and EI-MS spectral data. It could be inferred that the enzyme responsible for the biotransforma-tion reaction was a kind of extracellular and constitutive enzyme since the transformation reaction of the substrate could be carried out in cell free extracts of the fermentation broth of the Mucor spinosus.展开更多
The oxidation of thiophenol（RSH） to phenyl disulfide catalyzed by Co（Ⅱ） tetrakis（propyl-oxycarbonyl）phthalocyanine[CoPc（COOC3H7）4] in the presence of molecular oxygen was studied in synthetic bilayer membrane...The oxidation of thiophenol（RSH） to phenyl disulfide catalyzed by Co（Ⅱ） tetrakis（propyl-oxycarbonyl）phthalocyanine[CoPc（COOC3H7）4] in the presence of molecular oxygen was studied in synthetic bilayer membrane of vesicle, which is composed of hexadecyl 2-hydroxy-3-chloropropyl phosphate, SDS micelle, ethanol and benzene respectively. The catalytic activities followed the order of \{CoPc（COOC\}3H7）4 in the bilayer membrane>ethanol>benzene, and in the bilayer membraneSDS micelle. UV-Vis spectroscopic studies reveal that the catalytic oxidation proceeds through RS--CoPc-O2 intermediate. The catalytic activity of CoPc（COOC3H7）4 in the bilayer membrane of vesicle higher than that in the other media is considered to be attributable to the disaggregation of CoPc（COOC3H7）4 incorporated into the bilayer membrane and the easier H+ dissociation of RSH on the polar surface of the bilayer membrane bordered by bulk aqueous phase.展开更多
由于煤氧化反应的初始阶段就是煤吸附O2的过程,可通过抑制O2的吸附来抑制煤的氧化自燃。应用Gaussian 03程序,采用密度泛函(DFT)方法,在B3LYP/6-31G(d,p)水平下研究分析Zn2+与煤中α位硫酚结构的作用机理,并以活化能作为指标表征Zn2+抑...由于煤氧化反应的初始阶段就是煤吸附O2的过程,可通过抑制O2的吸附来抑制煤的氧化自燃。应用Gaussian 03程序,采用密度泛函(DFT)方法,在B3LYP/6-31G(d,p)水平下研究分析Zn2+与煤中α位硫酚结构的作用机理,并以活化能作为指标表征Zn2+抑控煤中α位硫酚结构氧化的效果。由计算结果可知,α-萘硫酚结构中S原子LP(2)轨道上的孤对电子向Zn的LP*(6)空轨道转移,通过sp杂化形成σZn-S配位键,配位键的二阶稳定化能为266.60 k J/mol。当α-萘硫酚结构氧化时,首先与O2发生物理吸附形成复合物ComplexⅠ并释放20.12 k J/mol的能量,然后复合物ComplexⅠ的分子间发生化学作用,导致O2分子被化学吸附在—SH基上,所需活化能Ea=62.71k J/mol。[Zn SH8C10]2+配合物物理吸附O2释放的能量减少了14.92 k J/mol,且形成化学吸附所需的活化能增加了47.62 k J/mol,Zn2+对煤中α位硫酚氧化具有明显的控制作用。展开更多
文摘The capacity factors （k＇） of fourteen types ofhalogenated thiophenols in different phases of methanol-water eluent were determined by reversed phased high-performance liquid chromatography （RP-HPLC） and the relationships between the logarithm of capacity factor lgK＇ and methanol ratio ψ were analyzed. A fair linear relationship is found between lgK＇ and ψ, and the correlation coefficients R2 of the constructed linear equations are all greater than 0.990. Relationship between the chromatographic data lgKw＇ when extrapolated to pure water and n-octanol/water partition coefficient lgKow obtained by the group contribution method has shown a good linear correlation with R2= 0.956. The structure parameters of fourteen halogenated thiophenols were calculated by using DFT, and the correlation equation of lgKw＇ and structure parameters was obtained by using SPSS, lgKw＇ = -0.409 ＋ 0.039a and R2 = 0.981, meaning that lgKw＇ is mainly determined by the polarizability α.
文摘The synthesis of a series of unsaturated 4-methylene-1,3-dioxolanes has been realized and the addition of thiophenol to the synthesized compounds in the presence of radical initiators has been carried out. It has been established the behavior of the addition reaction both with opening of dioxolane cycle and without it. The influence of nature of substituents of С2-carbon atom of dioxolane cycle, ratio of the initial reagents and temperature on direction of the addition reaction has been studied. The adducts obtained as a result of the addition reaction have a linear and cyclic structure, which have been established by data of the chemical and spectral analyses. It has been found that the ratio dioxolane compound: thiophenol, reaction temperature and nature of the functional substituent influences on quantity of these adducts.
基金The National Outstanding Youth Foundation by NSF of ChinaTrans-Century Training Program Foundation for Talents by the Ministry of Education for financial support.
文摘Microbial transformation of gastrodin by Mucor spinosus strain 3.3450, resulted in a product with a transformation rate close to 100 per cent. This product was identified as p-hydroxy benzyl alcohol on the basis of its 1H, 13C NMR and EI-MS spectral data. It could be inferred that the enzyme responsible for the biotransforma-tion reaction was a kind of extracellular and constitutive enzyme since the transformation reaction of the substrate could be carried out in cell free extracts of the fermentation broth of the Mucor spinosus.
文摘The oxidation of thiophenol（RSH） to phenyl disulfide catalyzed by Co（Ⅱ） tetrakis（propyl-oxycarbonyl）phthalocyanine[CoPc（COOC3H7）4] in the presence of molecular oxygen was studied in synthetic bilayer membrane of vesicle, which is composed of hexadecyl 2-hydroxy-3-chloropropyl phosphate, SDS micelle, ethanol and benzene respectively. The catalytic activities followed the order of \{CoPc（COOC\}3H7）4 in the bilayer membrane>ethanol>benzene, and in the bilayer membraneSDS micelle. UV-Vis spectroscopic studies reveal that the catalytic oxidation proceeds through RS--CoPc-O2 intermediate. The catalytic activity of CoPc（COOC3H7）4 in the bilayer membrane of vesicle higher than that in the other media is considered to be attributable to the disaggregation of CoPc（COOC3H7）4 incorporated into the bilayer membrane and the easier H+ dissociation of RSH on the polar surface of the bilayer membrane bordered by bulk aqueous phase.
文摘由于煤氧化反应的初始阶段就是煤吸附O2的过程,可通过抑制O2的吸附来抑制煤的氧化自燃。应用Gaussian 03程序,采用密度泛函(DFT)方法,在B3LYP/6-31G(d,p)水平下研究分析Zn2+与煤中α位硫酚结构的作用机理,并以活化能作为指标表征Zn2+抑控煤中α位硫酚结构氧化的效果。由计算结果可知,α-萘硫酚结构中S原子LP(2)轨道上的孤对电子向Zn的LP*(6)空轨道转移,通过sp杂化形成σZn-S配位键,配位键的二阶稳定化能为266.60 k J/mol。当α-萘硫酚结构氧化时,首先与O2发生物理吸附形成复合物ComplexⅠ并释放20.12 k J/mol的能量,然后复合物ComplexⅠ的分子间发生化学作用,导致O2分子被化学吸附在—SH基上,所需活化能Ea=62.71k J/mol。[Zn SH8C10]2+配合物物理吸附O2释放的能量减少了14.92 k J/mol,且形成化学吸附所需的活化能增加了47.62 k J/mol,Zn2+对煤中α位硫酚氧化具有明显的控制作用。
