R&D Center for Pharmaceuticals, School of Chemical Engineering and the Environment, Beijing Institute of Technology, Beijing 100081, China.
Analyst. 2011 Dec 7;136(23):5017-24. doi: 10.1039/c1an15570a. Epub 2011 Oct 11.
A novel cyclodextrin (CD) derivative, mono-6-deoxy-benzimide-β-CD (MB-β-CD), in which a rigid substituent was linked to the narrow edge of the CD with a flexible H(2)C-N group, was successfully synthesized through the condensation of mono-6-deoxy-6-amino-β-cyclodextrin and benzaldehyde. To evaluate its enantioseparation abilities and investigate the role of the CD substituents and linkage in chiral recognition, MB-β-CD and mono-6-deoxyphenylimine-β-CD (MP-β-CD) with a rigid linkage were compared in the separation of 36 chiral compounds in a methanol/water mobile phase. The separation results showed that most of the analytes with rigid structures afforded better enantioresolutions on the MP-β-CD (with a rigid linkage) chiral stationary phase (CSP), while better enantioseparations for analytes with flexible structures and big steric hindrance were obtained on the MB-β-CD (with a flexible linkage) CSP. The former exhibited a specificity for the analyte structures, while the latter was more adaptable. Molecular dynamics simulations were performed to further understand the discrimination process and the function of the CD side arm.
一种新型的环糊精（CD）衍生物，单-6-脱氧苯并咪唑-β-CD（MB-β-CD），其中一个刚性取代基通过柔性的 H(2)C-N 基团连接到 CD 的窄边缘上，通过单-6-脱氧-6-氨基-β-环糊精和苯甲醛的缩合成功合成。为了评估其对映体分离能力，并研究 CD 取代基和连接在手性识别中的作用，在甲醇/水流动相中比较了 MB-β-CD 和具有刚性连接的单-6-脱氧苯并脒-β-CD（MP-β-CD）对 36 种手性化合物的分离。分离结果表明，大多数具有刚性结构的分析物在 MP-β-CD（具有刚性连接）手性固定相（CSP）上得到了更好的对映体分辨率，而对于具有柔性结构和大空间位阻的分析物，则在 MB-β-CD（具有柔性连接）CSP 上得到了更好的对映体分离。前者表现出对分析物结构的特异性，而后者则更具适应性。进行了分子动力学模拟，以进一步了解手性识别过程和 CD 侧臂的功能。
