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

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.

N-Acylated chitosan bis(arylcarbamate)s: A class of promising chiral separation materials with powerful enantioseparation capability and high eluents tolerability.

In order to comprehensively understand the influence of coordination of the substituent at 2-position with those at 3- and 6-positions on the properties of chitosan derivatives, a series of chitosan 3,6-bis(arylcarbamate)-2-(amide)s (CACAs) and the related chiral stationary phases (CSPs) were prepared and reported in the present study. Specifically, chitosan was N-acylated with carboxylic acid anhydrides, and then further derivatized with various aryl isocyanates to afford CACAs, from which a class of coated-type CSPs were prepared. When the substituent introduced on the acyl group at 2-position and those on the phenyl group of the carbamates at 3- and 6-positions were fittingly combined, these prepared CACAs based CSPs would exhibit powerful chiral recognition ability, further resulting in a class of promising chiral separation materials with excellent enantioseparation performance. Meanwhile, these newly developed materials with suitable molecular weight also bear a high tolerability towards organic solvents, even including pure tetrahydrofuran, thus broadening their application in enantiomeric separation.