Quantum chemistry parameters of 28 alkyl（1-phenylsulfonyl） cycloalkane-carboxy-lates were computed at the 6-31G＊ level in fully optimal manner using B3LYP method of density functional theory （DFT）. With GQSARF2.0...Quantum chemistry parameters of 28 alkyl（1-phenylsulfonyl） cycloalkane-carboxy-lates were computed at the 6-31G＊ level in fully optimal manner using B3LYP method of density functional theory （DFT）. With GQSARF2.0 program, the correlation equations that can predict n-octanol/water partition coefficient （lgKow） were developed using the structural and thermodynamic parameters of 28 alkyl（1-phenylsulfonyl） cycloalkane-carboxylates with experimental data of lgKow as theoretical descriptors; the correlation coefficient （R^2） was 0.9452 and the cross-validation squared correlation coefficient （Rcv^2） 0.9312. Furthermore, a four-variable model from MEDV was obtained, of which R2 = 0.9497 and Rov^2 =0.9388. The models were validated by variance inflation factor （VIF） and t-test. Cross-validation indicates that the correlation and predicting ability of the model based on both DFT method and MEDV are more advantageous than those obtained from semi-empirical AM1 method.展开更多
The logarithms of retention factors normalized to a hypothetical pure water eluent(log k w) were determined on a reversed phase high performance liquid chromatography(RP HPLC) column (Li Chrosorb RP 18 column...The logarithms of retention factors normalized to a hypothetical pure water eluent(log k w) were determined on a reversed phase high performance liquid chromatography(RP HPLC) column (Li Chrosorb RP 18 column) for 20 new α\|branched phenylsulfonyl acetates. The atomic charge method was applied to develop quantitative structure retention relationships(QSRRs). Among the available geometric and electronic descriptors, surface area (S), ovality (O), and the charge of carboxyl group(Q OC ) are significant. In the model, the contribution of surface area (S) is the greatest. The molecular mechanism of retention was demonstrated through the model. With the correlation coefficient ( r 2 adj , adjusted for degrees of freedom) of 0.964, the standard error of 0.164 and the F value of 170.39, the model has good predictive capacity.展开更多
Octanol/water partition coefficients,adsorption coefficients for soils and sediments and acute toxicities to Daphnia magna of 28 alkyl (1-phenylsulfonyl) cycloalkane-carboxylates were measured. These properties were c...Octanol/water partition coefficients,adsorption coefficients for soils and sediments and acute toxicities to Daphnia magna of 28 alkyl (1-phenylsulfonyl) cycloalkane-carboxylates were measured. These properties were correlated by linear solvation energy relationship (LSER) and chromatographic retention data determined by reverse-phase high performance liquid chromatography (RP-HPLC). The accuracy and range of applicability of these two quantitative structure-activity relationship (QSAR) methods were compared in this paper.展开更多
The key intermediate, 2-isopropyl-2-(3-methyl-1-benzoxyl-5-phenylsulfonyl-3E-pentenyl)-1, 3-dithiocycllohexane(Ⅲ), for the total synthesis of Sarcophytol-A (1)was prepared through 7 steps from acetone. The key steps ...The key intermediate, 2-isopropyl-2-(3-methyl-1-benzoxyl-5-phenylsulfonyl-3E-pentenyl)-1, 3-dithiocycllohexane(Ⅲ), for the total synthesis of Sarcophytol-A (1)was prepared through 7 steps from acetone. The key steps are nucleophilic addition of 2-1ithio-2-isopropyl-1,3-dithiocyclohexane to aldehyde 5 and double bond migration reaction of allylic alcohol 9 and 10.展开更多
The interaction between 4-（4-hydroxybut-2-ynyloxy）-3-（phenylsulfonyl）-1,2,5-oxadiazole-2-oxide （FB） and bovine serum albumin （BSA） was studied by spectroscopic methods including fluorescence and UV-Vis absorpt...The interaction between 4-（4-hydroxybut-2-ynyloxy）-3-（phenylsulfonyl）-1,2,5-oxadiazole-2-oxide （FB） and bovine serum albumin （BSA） was studied by spectroscopic methods including fluorescence and UV-Vis absorption spectroscopy. The quenching mechanism of fluorescence of BSA by FB was considered to be a dynamic quenching procedure. The number of binding sites n and apparent binding constant K were measured by fluorescence quenching method. The results indicate that there is FB molecular binding with BSA, and forming 1 ： 1 complex. The thermodynamic parameters such as △H, △G and △S, etc., were calculated, The results indicate that the binding reaction is mainly entropy-driven and hydrophobic forces play major role in the binding reaction, The distance r between donor （BSA） and acceptor （FB） was obtained according to Forster theory of non-radioactive energy transfer.展开更多
bis(phenylsulfonyl)-1,2,5-oxadiazole-2-oxide,the NO donor,was synthesized by etherealization of thiophenol,oxidation,and then cyclization with an overall yield of 70%. This process is simpler and the yield of product ...bis(phenylsulfonyl)-1,2,5-oxadiazole-2-oxide,the NO donor,was synthesized by etherealization of thiophenol,oxidation,and then cyclization with an overall yield of 70%. This process is simpler and the yield of product is higher than that previously reported.展开更多
本文应用线性溶剂化能相关(linear solvation energy relationship)法研究了32种苯砜基化合物的溶解度及分配系数与溶剂化显色参数之间的相关性.结果表明,溶解度和分配系数与溶剂化显色参数(solvatochromic parameters)呈良好的线性关系...本文应用线性溶剂化能相关(linear solvation energy relationship)法研究了32种苯砜基化合物的溶解度及分配系数与溶剂化显色参数之间的相关性.结果表明,溶解度和分配系数与溶剂化显色参数(solvatochromic parameters)呈良好的线性关系,测定值与估算值吻合得很好.展开更多
基金Supported by the Key Program of National Natural Science Foundation of China (No. 20737001)the National Science Foundation for Post-doctoral Scientists of China (No. 2003033486)
文摘Quantum chemistry parameters of 28 alkyl（1-phenylsulfonyl） cycloalkane-carboxy-lates were computed at the 6-31G＊ level in fully optimal manner using B3LYP method of density functional theory （DFT）. With GQSARF2.0 program, the correlation equations that can predict n-octanol/water partition coefficient （lgKow） were developed using the structural and thermodynamic parameters of 28 alkyl（1-phenylsulfonyl） cycloalkane-carboxylates with experimental data of lgKow as theoretical descriptors; the correlation coefficient （R^2） was 0.9452 and the cross-validation squared correlation coefficient （Rcv^2） 0.9312. Furthermore, a four-variable model from MEDV was obtained, of which R2 = 0.9497 and Rov^2 =0.9388. The models were validated by variance inflation factor （VIF） and t-test. Cross-validation indicates that the correlation and predicting ability of the model based on both DFT method and MEDV are more advantageous than those obtained from semi-empirical AM1 method.
基金TheNationalNaturalScienceFoundationofChina (No .2 9837180 )
文摘The logarithms of retention factors normalized to a hypothetical pure water eluent(log k w) were determined on a reversed phase high performance liquid chromatography(RP HPLC) column (Li Chrosorb RP 18 column) for 20 new α\|branched phenylsulfonyl acetates. The atomic charge method was applied to develop quantitative structure retention relationships(QSRRs). Among the available geometric and electronic descriptors, surface area (S), ovality (O), and the charge of carboxyl group(Q OC ) are significant. In the model, the contribution of surface area (S) is the greatest. The molecular mechanism of retention was demonstrated through the model. With the correlation coefficient ( r 2 adj , adjusted for degrees of freedom) of 0.964, the standard error of 0.164 and the F value of 170.39, the model has good predictive capacity.
文摘Octanol/water partition coefficients,adsorption coefficients for soils and sediments and acute toxicities to Daphnia magna of 28 alkyl (1-phenylsulfonyl) cycloalkane-carboxylates were measured. These properties were correlated by linear solvation energy relationship (LSER) and chromatographic retention data determined by reverse-phase high performance liquid chromatography (RP-HPLC). The accuracy and range of applicability of these two quantitative structure-activity relationship (QSAR) methods were compared in this paper.
基金Supported by the National Natural Science Foundation of China State Educational Commission Foundation of China
文摘The key intermediate, 2-isopropyl-2-(3-methyl-1-benzoxyl-5-phenylsulfonyl-3E-pentenyl)-1, 3-dithiocycllohexane(Ⅲ), for the total synthesis of Sarcophytol-A (1)was prepared through 7 steps from acetone. The key steps are nucleophilic addition of 2-1ithio-2-isopropyl-1,3-dithiocyclohexane to aldehyde 5 and double bond migration reaction of allylic alcohol 9 and 10.
基金Project supported by the National Natural Science Foundation of China （Nos. 30570015, 20373051 ）, the Natural Science Foundation of Hubei Province （Nos. 2006ABA333, 2005ABC002）, and the Science Foundation of Hubei Provincial Educational Department （No. D200528003）, and the Science Research Foundation of Chinese Ministry of Education （No. [2006]8IRT0543）.
文摘The interaction between 4-（4-hydroxybut-2-ynyloxy）-3-（phenylsulfonyl）-1,2,5-oxadiazole-2-oxide （FB） and bovine serum albumin （BSA） was studied by spectroscopic methods including fluorescence and UV-Vis absorption spectroscopy. The quenching mechanism of fluorescence of BSA by FB was considered to be a dynamic quenching procedure. The number of binding sites n and apparent binding constant K were measured by fluorescence quenching method. The results indicate that there is FB molecular binding with BSA, and forming 1 ： 1 complex. The thermodynamic parameters such as △H, △G and △S, etc., were calculated, The results indicate that the binding reaction is mainly entropy-driven and hydrophobic forces play major role in the binding reaction, The distance r between donor （BSA） and acceptor （FB） was obtained according to Forster theory of non-radioactive energy transfer.
文摘bis(phenylsulfonyl)-1,2,5-oxadiazole-2-oxide,the NO donor,was synthesized by etherealization of thiophenol,oxidation,and then cyclization with an overall yield of 70%. This process is simpler and the yield of product is higher than that previously reported.
文摘本文应用线性溶剂化能相关(linear solvation energy relationship)法研究了32种苯砜基化合物的溶解度及分配系数与溶剂化显色参数之间的相关性.结果表明,溶解度和分配系数与溶剂化显色参数(solvatochromic parameters)呈良好的线性关系,测定值与估算值吻合得很好.
