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Nonideal behavior of void volume markers in polar-organic chiral HPLC on polysaccharide-based chiral stationary phases

ABSTRACT: Polysaccharide-based chiral stationary phases account for a majority of chiral HPLC separations. Their behavior in normal-phase and reversed-phase modes of separation has been studied extensively. However, much less is known about their behavior in polar-organic mode. In the course of our studies on preparative separation of various cyclic imides, lactams, and acetamides on Chiralcel OD, Chiralcel OJ, Chiralpak AD, and Chiralpak AS stationary phases we sought to determine the void volumes of these columns using commonly used markers, LiNO3, thiourea, and acetone. We were surprised to notice extensive column- and solvent-dependent deviations from ideal (unretained and unexcluded) behavior. These deviations likely result from multiple types of noncovalent interactions possible for these chiral stationary phases. Therefore, great care should be taken when choosing void volume markers for such separations. Our results indicate that with acetonitrile as a mobile phase, acetone is a suitable void volume marker for all four of the above stationary phases. Graphical Abstract

SUBMITTER: Krivoshein A

PROVIDER: S-EPMC8939000 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The applications of polysaccharide phenyl carbamate derivatives as chiral stationary phases (CSPs) for capillary electrochromatography (CEC) are often hindered by longer retention times, especially using a normal-phase (NP) eluent due to very low electroosmotic flow (EOF). Therefore, in this study, we propose an approach for the aforementioned problems by introducing two new types of negatively charged sulfate and sulfonated groups for polysaccharide CSPs. These CSPs were utilized to pack CEC columns for enantioseparation with a NP eluent. Compared to conventional cellulose tris(3,5-dimethylphenyl carbamate) or CDMPC CSPs, the sulfated CDMPC CSP (sulfur content 4.25%, w/w) shortened the analysis time up to 50% but with a significant loss of enantiomeric resolution (approximately 60%). On the other hand, the sulfonated CDMPC CSP (sulfur content 1.76%, w/w) not only provided fast throughput but also maintained excellent resolving power. In addition, its synthesis is much more straightforward than the sulfated one. Furthermore, we studied several stationary phase parameters (CSP loading and silica gel pore size) and mobile phase parameters (including type of mobile phase and its composition) to evaluate the throughput and enantioselectivity. Using the optimized conditions, a chiral pool containing 66 analytes was screened to evaluate the enantioselectivity under three different mobile phase modes (i.e., NP, polar organic phase (POP) and reversed-phase (RP) eluents). Among these mobile phase modes, the RP mode showed the highest success rate, whereas some degree of complementary enantioselectivity was observed with NP and POP. Finally, the feasibility of applying this CSP for CEC-MS enantioseparation using internal tapered column was evaluated with NP, POP and RP eluents. In particular, the NP-CEC-MS provided significantly enhanced sensitivity when methanol was replaced with isopropanol in the sheath liquid. Using aminoglutethimide as model chiral analyte, all three modes of CEC-MS demonstrated excellent durability as well as excellent reproducibility of retention time and enantioselectivity.

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Nonideal behavior of void volume markers in polar-organic chiral HPLC on polysaccharide-based chiral stationary phases

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