新型表面聚合联萘胺型手性固定相的制备及评价

Preparation of (R)-(+)-1,1′-Binaphthyl-2,2′-diamine Polymer as a Novel Chiral Stationary Phase by Surface-initiated Polymerization and Chromatographic Evaluation

采用(R)-(+)-1,1′-联萘2,2′-二胺(DABN)作为手性单体,以键合在3-氨基硅胶上的4,4′-偶氮-二(4-腈基)戊酸(ACVA)作为引发剂,通过直接引发表面聚合反应,制备了一种新型HPLC刷型手性固定相(CSP-a).采用庚烷-醇-有机调节剂-有机酸为流动相,在柱温30℃和UV254nm检测条件下实现了在CSP-a上联萘酚衍生物、3,5-二硝基苯甲酰-氨基酸甲酯和乙酯以及一种反式环氧乙烷衍生物对映体的色谱拆分,考察了有机调节剂和有机酸对样品在CSP-a上拆分的影响.结果表明,CSP-a对于π-酸及π-碱类化合物都有明显拆分效果,三氟醋酸调节作用优于冰醋酸,流动相中加入CH2Cl2和CHCl3可增强保留,改善分离度.

A novel brush-type chiral stationary phase （CSP-a） for HPLC was prepared by surface-initiated polymerization with （R）-（ ＋ ）-1,1 ′-binaphthyl-2,2′-diamine as a chiral monomer and dichloride of 4,4′-azobis-4-cyanopentanoic acid bonded on the surface of silica gel as a radical initiator. The resolutions of the enantiomers of binaphthol derivatives, N-3,5-dinitrobenzoyl-D, L-amino acid methyl esters and isopropyl esters, and a trans-ethylene oxide derivative on CSP-a were carried out using heptane-alcohol-organic modifier-organic acid as the mobile phases under the detection conditions of the column temperature of 30 ℃ and UV wavelength of 254 nm. The effects of organic modifier and organic acid on the resolutions of the analytes on CSP-a were examined. The results show that CSP-a prepared was effective for the resolutions of the enantiomers of π- acid and π-base derivatives. Trifluoroacetic acid was a better organic modifier than acetic acid. Adding CH2Cl2 and CHCl3 to the mobile phase could increase retention and resolution of the samples on CSP-a.