Using capillary zone electrophoresis,the enantiomers resolution of 13 pharmaceuticals including non-amide,primary amine,the secondary amine and the tertiary amine was studied with highly sulfated – α(β,γ)-cyclodex...Using capillary zone electrophoresis,the enantiomers resolution of 13 pharmaceuticals including non-amide,primary amine,the secondary amine and the tertiary amine was studied with highly sulfated – α(β,γ)-cyclodextrins(HS-α(β,γ)-CD) as chiral selector,It was found a good resolution effect for the amide chiral pharmaceuticals,especially for tertiary amine.Through the primary analysis of chiral resolution mechanism,it was believed there be the static gravitational action in addition to space matches and hydrogen bonding between highly sulfated cyclodextrins and the amine drugs.With mobility shift method,Determination of binding constants between chlorpheniramine,hydrochloride isoprenaline,naphthylethylamine and HS-β-CD showed that the binding constant order of chlorpheniramine > hydrochloride isoprenaline > naphthylethylamine,and that highly sulfonated cyclodextrins and the tertiary amine the strongest action force.展开更多
In the pharmaceutical industry, the analysis of atropisomers is of considerable interest from both scientific and regulatory perspectives. The compound of interest contains two stereogenic axes due to the hindered rot...In the pharmaceutical industry, the analysis of atropisomers is of considerable interest from both scientific and regulatory perspectives. The compound of interest contains two stereogenic axes due to the hindered rotation around the single bonds connecting the aryl groups, which results in four potential configurational isomers(atropisomers). The separation of the four atropisomers was achieved on a derivatized β-cyclodextrin bonded stationary phase. Further investigation showed that low temperature conditions, including sample preparation(-70 °C), sample storage(-70 °C), and chromatographic separation(6 °C), were critical to preventing interconversion. LC-UV-laser polarimetric analysis identified peaks 1 and 2 as a pair of enantiomers and peaks3 and 4 as another. Thermodynamic analysis of the retention data indicated that the separation of the pairs of enantiomers is primarily enthalpy controlled as indicated by the positive slope of the van't Huff plot. The difference in absolute Δ(Δ H), ranged from 2.20 k J/mol to 2.42 k J/mol.展开更多
Five chiral stationary phases (CSPs) were used to separate the enantiomers of a series of O,O-diethyl (p-methyl-benzenesulfonamindo)-aryl(alkyl)-methylphosphonates. A chiral recognition mechanism was presented to expl...Five chiral stationary phases (CSPs) were used to separate the enantiomers of a series of O,O-diethyl (p-methyl-benzenesulfonamindo)-aryl(alkyl)-methylphosphonates. A chiral recognition mechanism was presented to explain the resolution of these compounds. Results show that CSP with strong π-acceptor 3,5-dinitrobenzoyl group and high steric hindrance has the best resolution ability in chiral separation of O,O-diethyl (p-methylbenzenesulfonamindo)-aryl(alkyl)-methylphosphonates. When a CSP has just a strong π-acceptor 3,5-dinitrobenzoyl or high steric hindrance it does not have good chiral resolution ability. The chiral recognition is more difficult when the CSP has more than one asymmetric center.展开更多
文摘Using capillary zone electrophoresis,the enantiomers resolution of 13 pharmaceuticals including non-amide,primary amine,the secondary amine and the tertiary amine was studied with highly sulfated – α(β,γ)-cyclodextrins(HS-α(β,γ)-CD) as chiral selector,It was found a good resolution effect for the amide chiral pharmaceuticals,especially for tertiary amine.Through the primary analysis of chiral resolution mechanism,it was believed there be the static gravitational action in addition to space matches and hydrogen bonding between highly sulfated cyclodextrins and the amine drugs.With mobility shift method,Determination of binding constants between chlorpheniramine,hydrochloride isoprenaline,naphthylethylamine and HS-β-CD showed that the binding constant order of chlorpheniramine > hydrochloride isoprenaline > naphthylethylamine,and that highly sulfonated cyclodextrins and the tertiary amine the strongest action force.
文摘In the pharmaceutical industry, the analysis of atropisomers is of considerable interest from both scientific and regulatory perspectives. The compound of interest contains two stereogenic axes due to the hindered rotation around the single bonds connecting the aryl groups, which results in four potential configurational isomers(atropisomers). The separation of the four atropisomers was achieved on a derivatized β-cyclodextrin bonded stationary phase. Further investigation showed that low temperature conditions, including sample preparation(-70 °C), sample storage(-70 °C), and chromatographic separation(6 °C), were critical to preventing interconversion. LC-UV-laser polarimetric analysis identified peaks 1 and 2 as a pair of enantiomers and peaks3 and 4 as another. Thermodynamic analysis of the retention data indicated that the separation of the pairs of enantiomers is primarily enthalpy controlled as indicated by the positive slope of the van't Huff plot. The difference in absolute Δ(Δ H), ranged from 2.20 k J/mol to 2.42 k J/mol.
基金Project supported by the National Natural Science Foundation of China.
文摘Five chiral stationary phases (CSPs) were used to separate the enantiomers of a series of O,O-diethyl (p-methyl-benzenesulfonamindo)-aryl(alkyl)-methylphosphonates. A chiral recognition mechanism was presented to explain the resolution of these compounds. Results show that CSP with strong π-acceptor 3,5-dinitrobenzoyl group and high steric hindrance has the best resolution ability in chiral separation of O,O-diethyl (p-methylbenzenesulfonamindo)-aryl(alkyl)-methylphosphonates. When a CSP has just a strong π-acceptor 3,5-dinitrobenzoyl or high steric hindrance it does not have good chiral resolution ability. The chiral recognition is more difficult when the CSP has more than one asymmetric center.
