Article

Chiral separations in polar organic solvent chromatography: updating a screening strategy with new chlorine-containing polysaccharide-based selectors.

Department of Analytical Chemistry and Pharmaceutical Technology, Vrije Universiteit Brussel, Laarbeeklaan 103, B-1090 Brussels, Belgium.
Journal of Chromatography B (Impact Factor: 2.49). 09/2008; 875(1):57-64. DOI: 10.1016/j.jchromb.2008.07.038
Source: PubMed

ABSTRACT The screening conditions of an existing column and mobile phase selection strategy for chiral drug substances in polar organic solvent liquid chromatography (POSC) were tested for their applicability on two new chlorine-containing polysaccharide-based stationary phases. The selectors of these phases are cellulose tris(3-chloro-4-methylphenylcarbamate) and amylose tris(5-chloro-2-methylphenylcarbamate). The enantioselectivity of these phases is compared to that of the four phases (Chiralpak AD-RH, Chiralcel OD-RH, Chiralpak AS-RH and Chiralcel OJ-RH) used in the earlier defined strategy. A test set of 62 structurally diverse chiral drug substances is analyzed using the screening conditions of the strategy on the six phases. The results confirm that the acetonitrile-based mobile phase provides a higher success rate and better resolutions than the methanol-based also on the new phases. However, the importance of the methanol-based mobile phase cannot be neglected for complementarity reasons; the two mobile phases insure enantioselectivity for different compounds. A third (ethanol-based) mobile phase, not part of the strategy, was also used to screen the two new phases. The joint results led to different possibilities to upgrade the current screening strategy so that improved success rates are obtained. The chlorine-containing chiral stationary phases demonstrated to have an added value to the screening process since they provided enantioresolution for compounds not resolved by non-chlorine-containing ones.

0 Bookmarks
 · 
63 Views
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: In an earlier part of this study (performance evaluation) it was observed, for home-made capillary electrochromatography (CEC) columns, that smaller particle diameters do not always generate higher efficiencies. This phenomenon was further examined in this study, evaluating Van Deemter curves. Naphthalene and trans-stilbene oxide were analyzed on four 3 µm and four 5 µm chlorinated polysaccharide-based chiral stationary phases (CSPs) applying voltages ranging from 5 to 30 kV. Neither the 3 nor the 5 µm packings generated systematically the highest efficiencies. The varying column efficiencies were optimized by evaluating nine packing procedures for both 3 and 5 µm CSPs. Again it was observed that smaller particle-size packings were not necessarily beneficial for the efficiency of the CEC analysis. This observation was statistically evaluated. A variability study evaluated different precision estimates related to column packing and replicate measurement conditions. The best columns with the highest efficiencies (for chiral separations) and good precision, that is, the lowest RSD values, were generated by the packing procedure in which an MeOH-slurry and a water rinsing step of 8 h were applied. Copyright © 2013 John Wiley & Sons, Ltd.
    Biomedical Chromatography 10/2013; · 1.95 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: A direct chiral LC-UV method was optimized for the determination of salbutamol (SAL) β2 -agonist in environmental water. Two commercially available columns were evaluated: teicoplanin Chirobiotic-T™ (150 × 2.1 mm i.d., 5 µm) and vancomycin Chirobiotic-V™ (150 × 2.1 mm i.d., 5 µm). Finally, teicoplanin chiral stationary phase was selected for SAL enantiomer resolution. In order to preserve its integrity and maintain the column performance for longer time, the use of additives such as triethylamine (TEA) in the mobile phase was avoided. Experimental design was applied to simultaneously evaluate the influence of several parameters involved in enantiomer separation and to establish the conditions for acceptable resolution and performance in short analysis time. Optimum mobile phase was methanol-20 mM ammonium acetate buffer at pH 4.5 (98:2, v/v). A solid-phase extraction procedure for sample pre-concentration and clean-up allowed the determination of chiral SAL residues in natural water samples spiked at low concentrations in the range 1.0-20 ng mL(-1) . Reproducible recoveries, between 77 and 98%, were obtained and matrix effect was negligible. Injection of sample solutions at low elution strength permitted the SAL enantioresolution in the natural water complex matrix with satisfactory sensitivity and precision. Copyright © 2013 John Wiley & Sons, Ltd.
    Biomedical Chromatography 05/2013; · 1.95 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: In this study, the screening steps of chiral separation strategies with polysaccharide-based chiral stationary phases were applied on boron cluster compounds in normal-phase liquid chromatography (NPLC) and polar organic solvents chromatography (POSC). Since the screening steps were initially developed to analyze organic compounds, their applicability for boron clusters was investigated. Overall, the screening steps in NPLC were applicable for the separation of zwitterions, while for anions mostly no elution was observed. A hypothesis for the latter behavior is precipitation of anions in the nonpolar mobile phases. Ten out of 11 compounds could be partially or baseline separated on the NPLC screening systems. In POSC, all zwitterions were separated on at least one of the screening systems, with an overall lower retention as in NPLC. Anions were detected but not separated in the majority of the experiments. Also their retention on the chiral stationary phases was very limited. This study showed that the chiral discrimination potential of chemically modified polysaccharides is meaningful for chiral separations of structurally chiral boron cluster species, but needs further systematic research, in which recognition mechanisms should be further explored. In addition, some unusual peaks also indicated that conditions with a high separation efficiency must first be searched for some of the tested systems. Copyright © 2014 John Wiley & Sons, Ltd.
    Biomedical Chromatography 01/2014; · 1.95 Impact Factor