Evaluation of cyclodextrins modified with dichloro-, dimethyl-, and chloromethylphenylcarbamate groups as chiral stationary phases for capillary electrochromatography.

Capillary electrochromatography using cyclodextrins modified with dichloro-, dimethyl-, and chloromethylcarbamate groups were used for the enantiomeric separation of standard analytes. The chiral selector was chemically bonded to aminopropylsilanized silica particles, and these chiral stationary phases (CSPs), mixed with aminopropylsilanized silica (1:1 wt:wt), were packed into 100-microm-i.d. fused-silica capillaries. The effect of the type of cyclodextrin, the nature and position of the substituents on the phenyl ring, and the binding mode of cyclodextrin phenylcarbamates onto the silica gel surface on the chiral recognition were studied. Experimental parameters such as organic solvent concentration were varied in order to better understand the mechanism contributing to the chiral recognition of these CSPs. Good enantioseparations were achieved for a racemic flavanone (FLA) and trans-cyclopropanedicarboxylic acid dianilide (CAD).

Comparative study on the application of capillary liquid chromatography and capillary electrochromatography for investigation of enantiomeric purity of the contraceptive drug levonorgestrel.

In the last few years, it has been shown that capillary electrochromatography (CEC) is a promising technique for enantioseparations. However, to date almost no studies are published on a critical comparison of CEC and its pressure-driven counterpart, capillary liquid chromatography (CLC) for real samples. In this study, the goal was to compare CLC and CEC for the determination of the enantiomeric purity of the contraceptive drug levonorgestrel and its pharmaceutical formulation. The study prevailed that not all potential advantages of CEC over CLC can easily be transformed in a real gain of detection limit of the enantiomeric impurity. However, certain advantages of CEC over CLC have been unambiguously shown.

Enantioseparations in nonaqueous capillary liquid chromatography and capillary electrochromatography using cellulose tris(3,5-dimethylphenylcarbamate) as chiral stationary phase.

The potential of the widely used chiral stationary phase for high-performance liquid chromatography (HPLC) enantioseparations, cellulose tris(3,5-dimethylphenylcarbamate) (CDMPC, sold under the trade name Chiralcel OD) was evaluated under the conditions of nonaqueous capillary electrochromatography (CEC). The effect of the particle size of the silica gel, the loading of CDMPC on the silica gel and nature of the organic solvent, as well as electrolyte salts on the separation characteristics were investigated. This study illustrates the applicability of CDMPC for obtaining highly efficient enantioseparations under the conditions of nonaqueous CEC. Comparative study of enantioseparations in capillary liquid chromatography (CLC) and CEC indicated the significant advantages of CEC such as higher plate number at the similar linear flow rates of the mobile phase as well as better tolerance of higher linear flow rates.

Comparative HPLC enantioseparation of new chiral hydantoin derivatives on three different polysaccharide type chiral stationary phases.

The enantioseparation of eighteen new chiral hydantoin derivatives was studied on three different polysaccharide type chiral stationary phases (CSP) Chiralpak AD, Chiralcel OD and Chiralcel OJ in the normal-phase HPLC mode. Chiralpak AD material exhibited the most universal chiral resolving ability and allowed the enantioseparation of 17 out of 18 compounds followed by Chiralcel OD (10 enantioseparations of 12 tested compounds) and Chiralcel OJ (eight enantioseparation from 13 tested analytes). Some complementary separations were observed and all of 18 compounds could be resolved at least with one of the three chiral CSP under the conditions of this study. With regard to the structure of the analytes, bulky electron rich substituents at C5 of the hydantoin nucleus appear to favor stereoselective interactions.

Comparative enantioseparation of selected chiral drugs on four different polysaccharide-type chiral stationary phases using polar organic mobile phases.

The enantiomers of randomly selected chiral drugs and drug analogs of various structural and pharmacological groups were resolved on four different polysaccharide-type chiral stationary phases (CSP) using pure methanol and acetonitrile as mobile phases. Polysaccharide phenylester type CSP, Chiralcel-OJ although resolving the enantiomers of some chiral drugs was less universal in the combination with methanol and acetonitrile as mobile phases. Among polysaccharide phenylcarabamates amylose tris(3,5-dimethylphenylcarbamate) (Chiralpak-AD) was superior over the corresponding cellulose derivative, cellulose tris(3,5-dimethylphenylcarbamate) (Chiralcel-OD). However, another derivative of cellulose, namely, cellulose tris(3,5-dichlorophenylcarbamate) (CDCPC) exhibited higher chiral recognition ability compared to Chiralpak-AD material. This study confirms previous findings about the applicability of polysaccharide type CSPs in so called polar organic mode as well as shows high potential of CDCPC as a practically useful CSP for High performance liquid chromatography (HPLC) enantioseparations.

Simultaneous enantioseparation of cis-diltiazem hydrochloride and its metabolite cis-desacetyldiltiazem using high-performance liquid chromatography and capillary electrophoresis.

Two alternative methods were developed using high-performance liquid chromatography (HPLC) and capillary electrophoresis (CE) for a simultaneous enantioselective determination of Ca(2+) blocking chiral drug cis-diltiazem hydrochloride (DLT) and its degradation product and metabolite cis-desacetyldiltiazem (Desac-DLT). The methods were compared from the viewpoint of analytical performance. The identification of HPLC peaks were performed using off-line electrospray ionization mass spectrometry. In addition, CE method was evaluated for quantitative determination of minor enantiomeric impurities in pharmacologically active (+)-cis-DLT.