Structure screening and performance restoration of chiral separation materials based on chitosan derivatives

Abstract

In order to screen chiral selector structure and find structure-property relationship, ten chitosan 3,6-bis(phenylcarbamate)-2-(cyclopropylformamide)s were synthesized from which corresponding chiral stationary phases were prepared. Enantioseparation capability and mobile phase tolerability of the chiral stationary phases were evaluated. The chiral selectors with 3-chloro-4-methylphenyl, 4-chlorophenyl, 3-chlorophenyl, 3,5-dichlorophenyl and 4-trifluoromethoxyphenyl groups demonstrated powerful enantioseparation capability. Enantioseparation capability was found to be dependent on a match between the substituent at C2 and the one attached to phenyl group at C3/C6 of glucose unit in the chitosan derivatives. Moreover, the tolerability tests revealed that the developed chiral stationary phases were highly tolerable to pure ethyl acetate, pure acetone and n-hexane/tetrahydrofuran of various ratios. In addition, n-hexane/tetrahydrofuran was found to be a modifier to adjust suprastructure of the chitosan derivatives, resulting in an improvement or restoration in enantioseparation. This observation implies n-hexane/tetrahydrofuran may make a damaged chiral selector restore its enantioseparation capability.

Keywords: Chiral separation; Chitosan; High-performance liquid chromatography; Polysaccharide; Structure-property relationship.