Li Wenhui, Huang Yu, Xiang Yuqian, Yan Xiaohui, Li Yanshuo, Wu Dapeng
State Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-products, School of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang 315211, China.
State Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-products, School of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang 315211, China.
J Chromatogr A. 2023 Mar 15;1692:463845. doi: 10.1016/j.chroma.2023.463845. Epub 2023 Feb 9.
In this work, the vacuum-assisted thermal bonding method was proposed for the covalent coupling of β-cyclodextrin (β-CD) (CD-CSP), hexamethylene diisocyanate cross-linked β-CD (HDI-CSP) and 3, 5-dimethylphenyl isocyanate modified β-CD (DMPI-CSP) onto the isocyanate silane modified silica gel. Under vacuum conditions, the side reaction due to the water residue from the organic solvent, air, reaction vessels and silica gel could be avoided, and the optimal temperature and time of vacuum-assisted thermal bonding method were determined as 160°C and 3 h. These three CSPs were characterized by FT-IR, TGA, elemental analysis and the nitrogen adsorption-desorption isotherms. The surface coverage of CD-CSP and HDI-CSP on silica gel was determined as ∼0.2 μmol m, respectively. The chromatographic performances of these three CSPs were systematically evaluated by separating 7 flavanones, 9 triazoles and 6 chiral alcohols enantiomers under the reversed-phase condition. It was found that the chiral resolution ability of CD-CSP, HDI-CSP and DMPI-CSP was complementary to each other. Among them, CD-CSP could separate all 7 flavanones enantiomers with the resolution of 1.09-2.48. HDI-CSP had a good separation performance for triazoles enantiomers with one chiral center. DMPI-CSP showed excellent separation performance for chiral alcohol enantiomers, among which the resolution of trans-1, 3-diphenyl-2-propen-1-ol reached 12.01. Generally, the vacuum-assisted thermal bonding had been demonstrated as a direct and efficient method for the preparation of chiral stationary phases of β-CD and its derivatives.
在本工作中，提出了真空辅助热键合法，用于将β-环糊精（β-CD）（CD-CSP）、六亚甲基二异氰酸酯交联β-环糊精（HDI-CSP）和3,5-二甲基苯基异氰酸酯改性β-环糊精（DMPI-CSP）共价偶联到异氰酸酯硅烷改性硅胶上。在真空条件下，可避免因有机溶剂、空气、反应容器和硅胶中的残留水分引起的副反应，并确定真空辅助热键合法的最佳温度和时间分别为160°C和3 h。通过傅里叶变换红外光谱（FT-IR）、热重分析（TGA）、元素分析和氮吸附-脱附等温线对这三种手性固定相进行了表征。测定了CD-CSP和HDI-CSP在硅胶上的表面覆盖率分别约为0.2 μmol/m²。通过在反相条件下分离7种黄烷酮、9种三唑和6种手性醇对映体，系统评价了这三种手性固定相的色谱性能。发现CD-CSP、HDI-CSP和DMPI-CSP的手性拆分能力相互补充。其中，CD-CSP能分离所有7种黄烷酮对映体，分离度为1.09 - 2.48。HDI-CSP对具有一个手性中心的三唑对映体具有良好的分离性能。DMPI-CSP对手性醇对映体表现出优异的分离性能，其中反式-1,3-二苯基-2-丙烯-1-醇的分离度达到12.01。总体而言，真空辅助热键合法已被证明是一种直接有效的制备β-环糊精及其衍生物手性固定相的方法。
