Acta Chim. Sinica ›› 2015, Vol. 73 ›› Issue (11): 1182-1188.DOI: 10.6023/A15080530 Previous Articles     Next Articles



张丽芳a,b, 赵杰c, 王勇a,b   

  1. a 天津大学理学院化学系 天津 300072;
    b 天津化学化工协同创新中心 天津 300072;
    c 天津市农业资源与环境研究所 天津市农业科学院 天津 300192
  • 投稿日期:2015-08-03 发布日期:2015-11-19
  • 通讯作者: 王勇
  • 基金资助:

    项目受国家自然科学基金(No. 21205086)、天津市自然科学基金(No. 13JCQNJC05400)、天津大学自主创新基金(No. 2015XRX-0021)资助.

Construction and Chromatographic Performance of a Novel Triazole Bridged Hybrid Bilayer Cyclodextrin Chiral Stationary Phase

Zhang Lifanga,b, Zhao Jiec, Wang Yonga,b   

  1. a Department of Chemistry, School of Science, Tianjin University, Tianjin 300072;
    b Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072;
    c Tianjin Academy of Agricultural Sciences, Tianjin 300192
  • Received:2015-08-03 Published:2015-11-19
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21205086), Natural Science Foundation of Tianjin, China (No. 13JCQNJC05400) and the Independent Innovation Foundation of Tianjin University (No. 2015XRX-0021).

A novel tandem-inverted triazole-bridged duplex “native-acetylated” hybrid cyclodextrin (CD) stationary phase material (ANCDCSP) was constructed via a surface-up ‘click’ approach. Mono-6-azido-CD was first immobilized onto the pre-dried silica surfaces as the down layer via ether linkage on C2 position, followed by acetylation of the cyclodextrin –OH groups with acetic anhydride. The top layer was fabricated by anchoring the synthesized alkyne functionalized CD onto the down CD layer via organic soluble Cu(I) catalytic 1,3-dipolar cycloaddition reaction (click chemistry) reported by us previously. The obtained crude material was purified by washing with N,N-dimethylformamide (DMF) twice followed by Soxlet extraction with acetone to afford the novel triazole-bridged duplex hybrid CD CSP and its structure was characterized via Fourier Transfer Infrared Spectroscopy (FTIR), thermogravimetric analysis (TG) and elemental analysis (EA). The hybrid bilayer ANCDCSP can provide multiple interaction sites such as H-bonding (OH, C=O, NH), steric effects, dipole-dipole and synergistic effect inclusion complexation, which helps to broaden the CSP’s enantioselectivity profile and enhance the enantioselectivity to some specific analytes. The CSP was applied for HPLC enantioseparation of various chiral compounds such as dansyl amino acids, carboxylic aryl acids, isoxazolines and some other racemates under reversed-phase separation mode using methanol/water and methanol/buffer as the mobile phases. Most of the dansyl amino acids and carboxylic aryl acids as well as bendroflumethiazide can be baseline separated. The isoxazolines, phenyl oxirane, atropine, DL-norleucine methyl ester and benfluorex were partially separated. The resolutions of Dns-Phe, DL-3PhLacA and Bendroflumethiazide reached 5.3, 4.1 and 4.1, respectively. The separation ability of the current CSP is superior to that of the duplex native cyclodextrins chiral stationary phase (DCDCSP) prepared by our group previously, especially in separation of dansyl amino acids, isoxazolines and bendroflumethiazide. Besides, the current CD CSP affords relatively good stability, which was verified by the satisfied reproducibility after 150 runs with or without buffer (pH 4.10).

Key words: click chemistry, bilayer cyclodextrin, chiral stationary phase, enantiorecognition, HPLC ester