Engineering Thiol–Ene Click Chemistry for the Fabrication of Novel Structurally Well-Defined Multifunctional Cyclodextrin Separation Materials for Enhanced Enantioseparation

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• 作者：Xiaobin Yao ; Hao Zheng ; Yang Zhang ; Xiaofei Ma ; Yin Xiao ; Yong Wang
• 刊名：Analytical Chemistry
• 出版年：2016
• 出版时间：May 3, 2016
• 年：2016
• 卷：88
• 期：9
• 页码：4955-4964
• 全文大小：445K
• 年卷期：0
• ISSN：1520-6882

文摘

The preparation of two novel multifunctional cyclodextrin (CD) separation materials and their ultimate enantioseparation performances in high performance liquid chromatography are reported. A mild thiol–ene click reaction was used to anchor 1-allylimidazolium-per(p-methyl)phenylcarbamoylated-β-CD and 1-allylimidazolium-per(p-chloride)phenylcarbamoylated-β-CD onto thiol-modified porous silica giving structurally well-defined stable cationic multifunctional CD chiral stationary phases (CSP1 and CSP2 respectively). These covalently bonded CD phases have typical interaction modes such as H-bonding, π–π effect, electrostatic and dipole–dipole interactions as well as steric effects which result in superior chiral resolution for a variety of chiral compounds in different separation modes. In a reverse-phase mode, both CSPs exhibited excellent separation abilities for isoxazolines, flavonoids, β-blockers, and some other neutral and basic racemates. In a polar-organic mode, isoxazolines and flavonoids were well resolved. CSP1 with an electron-rich phenyl substitution on the CD rims gave a better resolution for isoxazolines whereas CSP2 with an electron-deficient phenyl substitution on the CD rims gave better resolution for flavonoids. Among isoxazolines, 4ClPh-OPr gained a high selectivity and resolution up to 18.6 and 38.7, respectively, which is an amazing result for CD enantioseparation materials.