期刊
ELECTROPHORESIS
卷 42, 期 17-18, 页码 1853-1863出版社
WILEY
DOI: 10.1002/elps.202100049
关键词
Bipyridines; Electrostatic potential; Enantiomer elution order; Molecular dynamics; Polysaccharide‐ based chiral stationary phases
This study investigated the enantioseparation of 2'-(4-pyridyl)- and 2'-(4-hydroxyphenyl)-TCIBPs on various chiral columns, exploring the factors influencing the selectivity between enantiomers, including the polymer backbone and side chain substituent properties. Findings showed that the cellulose and amylose tris(3,5-dimethylphenylcarbamate) influenced the elution order of analytes, highlighting the importance of polysaccharide backbone in enantioseparation.
2'-(4-Pyridyl)- and 2'-(4-hydroxyphenyl)-TCIBPs (TCIBP = 3,3',5,5'-tetrachloro-2-iodo-4,4'-bipyridyl) are chiral compounds that showed interesting inhibition activity against transthyretin fibrillation in vitro. We became interested in their enantioseparation since we noticed that the M-stereoisomer is more effective than the P-enantiomer. Based thereon, we recently reported the enantioseparation of 2'-substituted TCIBP derivatives with amylose-based chiral columns. Following this study, herein we describe the comparative enantioseparation of both 2'-(4-pyridyl)- and 2'-(4-hydroxyphenyl)-TCIBPs on four cellulose phenylcarbamate-based chiral columns aiming to explore the effect of the polymer backbone, as well as the nature and position of substituents on the side groups on the enantioseparability of these compounds. In the frame of this project, the impact of subtle variations of analyte and polysaccharide structures, and mobile phase (MP) polarity on retention and selectivity was evaluated. The effect of temperature on retention and selectivity was also considered, and overall thermodynamic parameters associated with the analyte adsorption onto the CSP surface were derived from van 't Hoff plots. Interesting cases of enantiomer elution order (EEO) reversal were observed. In particular, the EEO was shown to be dependent on polysaccharide backbone, the elution sequence of the two analytes being P-M and M-P on cellulose and amylose tris(3,5-dimethylphenylcarbamate), respectively. In this regard, a theoretical investigation based on molecular dynamics (MD) simulations was performed by using amylose and cellulose tris(3,5-dimethylphenylcarbamate) nonamers as virtual models of the polysaccharide-based selectors. This exploration at the molecular level shed light on the origin of the enantiodiscrimination processes.
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