After joining the faculty at Toyohashi University of Technology (TUT) in 1978, the author has found two areas in separation sciences where microcolumn liquid chromatography (micro LC) can be beneficial One is the hyph...After joining the faculty at Toyohashi University of Technology (TUT) in 1978, the author has found two areas in separation sciences where microcolumn liquid chromatography (micro LC) can be beneficial One is the hyphenated techniques between many spectroscopic methods such as mass (MS), infrared (FT IR) and atomic emission (ICP), and micro LC The other one is rather difficult, but basic and theoretical approach which deals with retention mechanism in LC The latter project has especially been giving him a lot of scientific funs and honors in the last 20 years On the occasion of being awarded by The Society for Chromatographic Sciences the author would like to summarize his contributions to this topic which asks us "What Is Chromatographic Retention?展开更多
The enantiomers of a series of fourteen O-ethyl O-(substituted) phenyl N-isopropyl-phosphoroamidothioates have been separated by high performance liquid chromatography (HPLC) on the Pirkle-type chiral stationary phase...The enantiomers of a series of fourteen O-ethyl O-(substituted) phenyl N-isopropyl-phosphoroamidothioates have been separated by high performance liquid chromatography (HPLC) on the Pirkle-type chiral stationary phase. Seven molecular descriptors were calculated and four significant descriptors were chosen to correlate against the experimental lnk' values in order to form the quantitative structure-enantioselectivity retention relationships (QSERRs). Through the QSERRs, the retention and enantioselectivity mechanism were examined.展开更多
The interaction index c which was derived from the fundamental retention equationlogk’ =a + cC_B in reversed--phase high--performancc liquid chromatography (RP-HPLC) quan-titatively describes the difference in the in...The interaction index c which was derived from the fundamental retention equationlogk’ =a + cC_B in reversed--phase high--performancc liquid chromatography (RP-HPLC) quan-titatively describes the difference in the interaction between solute--strong. solvent andsolute--weak solvent; it has shown to be a constant for a specific solute even when columnsystems with different C18 packings are used. The theoretical basis for peak identificationby using interaction index has been proposed, which was based on the a,c values on stan-dard C18 column by utilizing linear a-a plots on column pairs and the linear relationship be-tween parameters a and c for the structural related compounds. Through the establishmentof parameters a,c data based on the standard C18 column for a certain type of compounds,the retention of thesc compounds on various C18 columns can be predicted. Typical exam-ples have been given to verify the correctness of this method.展开更多
In normal phase condition, a series of chiral phosphorus organic compounds have been separated by high-performance liquid chromatography. In order to study the retention and chiral recognition mechanism, the method of...In normal phase condition, a series of chiral phosphorus organic compounds have been separated by high-performance liquid chromatography. In order to study the retention and chiral recognition mechanism, the method of quantitative structure-enantioselectivity retention relationships (QSERRs) has been investigated from the quantitative equations established between the chromatographic retention of enantiomers and their molecular descriptors of physicochemical properties. The results show that on the Pirkle-type chiral stationary phase (CSP) of Sumichiral OA4700, it is the parameter of LUMO that gives the most contribution to the chromatographic retention of O-ethyl O-(substituted) phenyl N-isopropyl phosphoroamidothioates resulting from the interaction of hydrogen bond and (or) π-π interaction. Meanwhile, the chiral recognition is formed from the contribution of logP and LUMO.展开更多
The mechanisms of adsorption of pesticides（dimethoate, metalaxyl, atrazine, malathion and prometryn） and heavy metals（Cu, Cd, Pb, Zn and Ni） coexisting in sediments, with pesticides as target pollutants, and the i...The mechanisms of adsorption of pesticides（dimethoate, metalaxyl, atrazine, malathion and prometryn） and heavy metals（Cu, Cd, Pb, Zn and Ni） coexisting in sediments, with pesticides as target pollutants, and the influence of their main effects and double-order interaction effects were studied using the experimental design module in the Minitab software package with a 2^10-3 fractional factorial design method at resolution V. The main, double-order interaction, synergistic and antagonistic effect values of pollutant concentrations influencing the adsorption of pesticides were set as dependent variables, while various quantum chemical parameters of pesticides were set as independent variables, and two-dimensional quantitative structure activity relationship（2D-QSAR） models were established by stepwise regression to reveal the adsorption mechanisms of pesticides in a composite contamination system. The main effects of pollutants concentration played the primary role in the adsorption of dimethoate and malathion（the rates of contributions were 53.54% and 56.46%, respectively）, while double-order interaction effects were primarily responsible for metalaxyl, atrazine and prometryn adsorption（the rates of contributions were 79.05%, 60.21% and 57.89%, respectively） in the pesticide/heavy metals coexisting sediment system. The synergistic effects of the main effects and double-order interaction effects of pollutants concentration（synergistic effects） played a leading role in adsorption of malathion and prometryn（the rates of contributions were 70.61% and 69.61%, respectively）, while an- tagonistic effects of the main effects and double-order interaction effects of pollutants（antagonistic effects） played a dominant role in the adsorption of dimethoate, metalaxyl and atrazine（the rates of contributions were 58.82%, 56.89% and 58.24%, respectively）. Moreover, the correlation coefficient value（R2） ranged from 0.986 to 0.999（〉0.8783） in the 2D-QSAR model, while the standard deviation（SD） ranged from 0.006 to 0.066 and the Ftest values were 22.684-199.544, indicating the model has good predictive ability and fit. The 2D-QSAR model revealed a significant correlation（P=0.05） between the main effects of pollutants concentrations on pesticides adsorption（main effect values） and the most positive hydrogen atomic charge（qa＋）, the highest occupied molecular orbital energy（EHOMO） and the dipole moment（μ）. Furthermore, double-order interaction effect values of pollutant concentrations influenced the adsorption of pesticides（double-order interaction effect values）, and the most positive atomic charge（q＋）, qH＋, and the lowest unoccupied molecular orbital energy（ELMO） were significantly correlated. The qw, EHOMO and μ of pesticides were found to be significant factors promoting pesticides adsorption, while the q＋ and ELVMO of pesticides were significant inhibiting factors（P=0,05）. Overall, this study provides a theoretical basis for further realization of combined pollution control of pesticide pollutants in complex environmental systems.展开更多
以定量构效关系理论和实验室内急性毒性试验相结合研究了六种有机磷农药对四尾栅藻(S.quadricanda)和多刺裸腹溞(Moina macrocopa)的生态毒性。有机磷农药的毒性取决于磷原子的电正性,各取代基种类和构象对电荷分布作用显著。根据构效...以定量构效关系理论和实验室内急性毒性试验相结合研究了六种有机磷农药对四尾栅藻(S.quadricanda)和多刺裸腹溞(Moina macrocopa)的生态毒性。有机磷农药的毒性取决于磷原子的电正性,各取代基种类和构象对电荷分布作用显著。根据构效关系原理,磷氧双键(P=O)被磷硫双键(P=S)取代后毒性降低;羟基(-OH)被甲、乙、丙氧基(-CH3O、-CH3CH2O、-CH3CH2CH2O)取代后有机磷农药毒性依次增强;磷氧单键(P-O)毒性高于磷碳单键(P-C)。该实验中毒死蜱、辛硫磷(-CH3CH2O)毒性高于其它四种(-CH3O),敌敌畏和敌百虫(P=O)毒性高于乐果(P=S),敌敌畏(P-O)又高于敌百虫(P-C),甘氨酸异丙胺盐取代羟基(-OH)的草甘膦毒性最低。毒性试验结果表明,毒死蜱、辛硫磷、敌百虫、敌敌畏、乐果、草甘膦异丙胺盐对四尾栅藻的96 h EC50分别为6.34、6.62、59.53、82.12、141.37和7.25 mg.L-1。它们对多刺裸腹溞的48 h LC50分别为0.20、0.12、0.28、0.17、1.12和5.03 mg.L-1。六种有机磷农药对多刺裸腹溞的毒性强度结果与QSAR分析具有较高的一致性,即表征有机磷农药毒性特征的取代基团作用的毒性强弱顺序为:-OH>=O>-O;对四尾栅藻毒性试验结果中,由于草甘膦异丙胺盐作用于植物类靶位点的特殊性,导致其对四尾栅藻毒性显著增强。综合以上研究,以构效关系理论和浮游生物毒性试验相结合进行有机磷农药的生态风险评价将更加便捷和准确。展开更多
文摘After joining the faculty at Toyohashi University of Technology (TUT) in 1978, the author has found two areas in separation sciences where microcolumn liquid chromatography (micro LC) can be beneficial One is the hyphenated techniques between many spectroscopic methods such as mass (MS), infrared (FT IR) and atomic emission (ICP), and micro LC The other one is rather difficult, but basic and theoretical approach which deals with retention mechanism in LC The latter project has especially been giving him a lot of scientific funs and honors in the last 20 years On the occasion of being awarded by The Society for Chromatographic Sciences the author would like to summarize his contributions to this topic which asks us "What Is Chromatographic Retention?
文摘The enantiomers of a series of fourteen O-ethyl O-(substituted) phenyl N-isopropyl-phosphoroamidothioates have been separated by high performance liquid chromatography (HPLC) on the Pirkle-type chiral stationary phase. Seven molecular descriptors were calculated and four significant descriptors were chosen to correlate against the experimental lnk' values in order to form the quantitative structure-enantioselectivity retention relationships (QSERRs). Through the QSERRs, the retention and enantioselectivity mechanism were examined.
文摘The interaction index c which was derived from the fundamental retention equationlogk’ =a + cC_B in reversed--phase high--performancc liquid chromatography (RP-HPLC) quan-titatively describes the difference in the interaction between solute--strong. solvent andsolute--weak solvent; it has shown to be a constant for a specific solute even when columnsystems with different C18 packings are used. The theoretical basis for peak identificationby using interaction index has been proposed, which was based on the a,c values on stan-dard C18 column by utilizing linear a-a plots on column pairs and the linear relationship be-tween parameters a and c for the structural related compounds. Through the establishmentof parameters a,c data based on the standard C18 column for a certain type of compounds,the retention of thesc compounds on various C18 columns can be predicted. Typical exam-ples have been given to verify the correctness of this method.
基金the Foundation for University Key Teacher by the Ministry of Education of China and Natural Science Foundation of Tianjin (Grant No. 983603311).
文摘In normal phase condition, a series of chiral phosphorus organic compounds have been separated by high-performance liquid chromatography. In order to study the retention and chiral recognition mechanism, the method of quantitative structure-enantioselectivity retention relationships (QSERRs) has been investigated from the quantitative equations established between the chromatographic retention of enantiomers and their molecular descriptors of physicochemical properties. The results show that on the Pirkle-type chiral stationary phase (CSP) of Sumichiral OA4700, it is the parameter of LUMO that gives the most contribution to the chromatographic retention of O-ethyl O-(substituted) phenyl N-isopropyl phosphoroamidothioates resulting from the interaction of hydrogen bond and (or) π-π interaction. Meanwhile, the chiral recognition is formed from the contribution of logP and LUMO.
文摘The mechanisms of adsorption of pesticides（dimethoate, metalaxyl, atrazine, malathion and prometryn） and heavy metals（Cu, Cd, Pb, Zn and Ni） coexisting in sediments, with pesticides as target pollutants, and the influence of their main effects and double-order interaction effects were studied using the experimental design module in the Minitab software package with a 2^10-3 fractional factorial design method at resolution V. The main, double-order interaction, synergistic and antagonistic effect values of pollutant concentrations influencing the adsorption of pesticides were set as dependent variables, while various quantum chemical parameters of pesticides were set as independent variables, and two-dimensional quantitative structure activity relationship（2D-QSAR） models were established by stepwise regression to reveal the adsorption mechanisms of pesticides in a composite contamination system. The main effects of pollutants concentration played the primary role in the adsorption of dimethoate and malathion（the rates of contributions were 53.54% and 56.46%, respectively）, while double-order interaction effects were primarily responsible for metalaxyl, atrazine and prometryn adsorption（the rates of contributions were 79.05%, 60.21% and 57.89%, respectively） in the pesticide/heavy metals coexisting sediment system. The synergistic effects of the main effects and double-order interaction effects of pollutants concentration（synergistic effects） played a leading role in adsorption of malathion and prometryn（the rates of contributions were 70.61% and 69.61%, respectively）, while an- tagonistic effects of the main effects and double-order interaction effects of pollutants（antagonistic effects） played a dominant role in the adsorption of dimethoate, metalaxyl and atrazine（the rates of contributions were 58.82%, 56.89% and 58.24%, respectively）. Moreover, the correlation coefficient value（R2） ranged from 0.986 to 0.999（〉0.8783） in the 2D-QSAR model, while the standard deviation（SD） ranged from 0.006 to 0.066 and the Ftest values were 22.684-199.544, indicating the model has good predictive ability and fit. The 2D-QSAR model revealed a significant correlation（P=0.05） between the main effects of pollutants concentrations on pesticides adsorption（main effect values） and the most positive hydrogen atomic charge（qa＋）, the highest occupied molecular orbital energy（EHOMO） and the dipole moment（μ）. Furthermore, double-order interaction effect values of pollutant concentrations influenced the adsorption of pesticides（double-order interaction effect values）, and the most positive atomic charge（q＋）, qH＋, and the lowest unoccupied molecular orbital energy（ELMO） were significantly correlated. The qw, EHOMO and μ of pesticides were found to be significant factors promoting pesticides adsorption, while the q＋ and ELVMO of pesticides were significant inhibiting factors（P=0,05）. Overall, this study provides a theoretical basis for further realization of combined pollution control of pesticide pollutants in complex environmental systems.
文摘以定量构效关系理论和实验室内急性毒性试验相结合研究了六种有机磷农药对四尾栅藻(S.quadricanda)和多刺裸腹溞(Moina macrocopa)的生态毒性。有机磷农药的毒性取决于磷原子的电正性,各取代基种类和构象对电荷分布作用显著。根据构效关系原理,磷氧双键(P=O)被磷硫双键(P=S)取代后毒性降低;羟基(-OH)被甲、乙、丙氧基(-CH3O、-CH3CH2O、-CH3CH2CH2O)取代后有机磷农药毒性依次增强;磷氧单键(P-O)毒性高于磷碳单键(P-C)。该实验中毒死蜱、辛硫磷(-CH3CH2O)毒性高于其它四种(-CH3O),敌敌畏和敌百虫(P=O)毒性高于乐果(P=S),敌敌畏(P-O)又高于敌百虫(P-C),甘氨酸异丙胺盐取代羟基(-OH)的草甘膦毒性最低。毒性试验结果表明,毒死蜱、辛硫磷、敌百虫、敌敌畏、乐果、草甘膦异丙胺盐对四尾栅藻的96 h EC50分别为6.34、6.62、59.53、82.12、141.37和7.25 mg.L-1。它们对多刺裸腹溞的48 h LC50分别为0.20、0.12、0.28、0.17、1.12和5.03 mg.L-1。六种有机磷农药对多刺裸腹溞的毒性强度结果与QSAR分析具有较高的一致性,即表征有机磷农药毒性特征的取代基团作用的毒性强弱顺序为:-OH>=O>-O;对四尾栅藻毒性试验结果中,由于草甘膦异丙胺盐作用于植物类靶位点的特殊性,导致其对四尾栅藻毒性显著增强。综合以上研究,以构效关系理论和浮游生物毒性试验相结合进行有机磷农药的生态风险评价将更加便捷和准确。
