Citation: En-ting Deng, Wan-ying Bi, Bo Liu, Li-li Zhang, Jun Shen. Investigation of Chiral Recognition Mechanism of Polysaccharide Derivatives Based on Molecular Simulation[J]. Acta Polymerica Sinica, ;2020, 51(2): 214-220. doi: 10.11777/j.issn1000-3304.2019.19116 shu

Investigation of Chiral Recognition Mechanism of Polysaccharide Derivatives Based on Molecular Simulation

En-ting Deng ^† ,
Wan-ying Bi ^† ,
Bo Liu ,
Li-li Zhang ^, ,
Jun Shen ^,

Polymer Materials Research Center, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001

Corresponding author: Li-li Zhang, zhanglili1984@hrbeu.edu.cn Jun Shen, shenjun@hrbeu.edu.cn
Received Date: 12 June 2019
Revised Date: 5 August 2019

As one of the most powerful and popular chiral stationary phases (CSPs), phenylcarbamate derivatives of cellulose and amylose exhibit high chiral recognition ability and have realized efficent enantioseparation for almost 80% chiral compounds. To develop novel enantioseparation materials with high chiral recognition ability, it is of crucial importance to elucidate the chiral recognition mechanism for CSPs. Based on this, cellulose tris(phenylcarbamate) and amylose tris(phenylcarbamate) were synthesized by traditional esterification method in this study. The structures and degrees of substitution of the polysaccharide derivatives were characterized by ¹H-NMR, implying that the obtained cellulose and amylose deivatives possessed regular higher order structures and almost complete substitution of phenylcarbamate pendants at three positions on the glucose units. The obtained polysaccharide derivatives were then coated on aminopropyl silica gel to prepare the chiral stationary phases (CSPs). The chiral recognition abilities of the derivatives were evaluated by the high performance liquid chromatography (HPLC) based on the separation of racemic 1-(9-anthryl)-2,2,2-trifluoroethanol (Rac-1). Then, based on the molecular mechanics and the molecular dynamics, molecular simulation of the higher order sturucture of polysaccharide derivatives were performed using Materials Studio software. The optimized conformation for the interaction between polysaccharide derivatives and enantiomers of Rac-1 was achieved by the molecular simulation according to the FTIR and XRD results. The molecular simulation results agreed well with the chiral recognition ability and elution order of enantiomers by HPLC. It indicated that the chiral recognition was significantly dependent on the synergistic interactions between polysaccharide derivatives and enantiomers of Rac-1 at the chiral grooves formed by the carbamate substituents and aromatic rings of the polysaccharide derivatives with different stabilities. This study may contribute to a better understanding for the chiral recognition mechanism of polymer-based CSPs.
- Chiral recognition mechanism,
- Enantioseparation,
- Molecular simulation,
- Polysaccharide
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