Zhang Ning, Guo Siyu, Gong Bolin
School of Chemistry and Chemical Engineering, North Minzu University No. 204 Wenchang North Street, Xixia District Yinchuan 750021 China
RSC Adv. 2021 Nov 5;11(57):35754-35764. doi: 10.1039/d1ra04697g. eCollection 2021 Nov 4.
A bridged bis(β-cyclodextrin) ligand was firstly synthesized a thiol-ene click chemistry reaction between allyl-ureido-β-cyclodextrin and 4-4'-thiobisthiophenol, which was then bonded onto a 5 μm spherical silica gel to obtain a novel bridged bis(β-cyclodextrin) chiral stationary phase (HTCDP). The structures of HTCDP and the bridged bis(β-cyclodextrin) ligand were characterized by the H nuclear magnetic resonance (H NMR), solid state C nuclear magnetic resonance (C NMR) spectra spectrum, scanning electron microscope, elemental analysis, mass spectrometry, infrared spectrometry and thermogravimetric analysis. The performance of HTCDP in enantioseparation was systematically examined by separating 21 chiral compounds, including 8 flavanones, 8 triazole pesticides and 5 other common chiral drugs (benzoin, praziquantel, 1-1'-bi-2-naphthol, Tröger's base and bicalutamide) in the reversed-phase chromatographic mode. By optimizing the chromatographic conditions such as formic acid content, mobile phase composition, pH values and column temperature, 19 analytes were completely separated with high resolution (1.50-4.48), in which the enantiomeric resolution of silymarin, 4-hydroxyflavanone, 2-hydroxyflavanone and flavanone were up to 4.34, 4.48, 3.89 and 3.06 within 35 min, respectively. Compared to the native β-CD chiral stationary phase (CDCSP), HTCDP had superior enantiomer separation and chiral recognition abilities. For example, HTCDP completely separated 5 other common chiral drugs, 2 flavanones and 3 triazole pesticides that CDCSP failed to separate. Unlike CDCSP, which has a small cavity (0.65 nm), the two cavities in HTCDP joined by the aryl connector could synergistically accommodate relatively bulky chiral analytes. Thus, HTCDP may have a broader prospect in enantiomeric separation, analysis and detection.
首先通过烯丙基脲基-β-环糊精与4,4'-硫代双苯酚之间的硫醇-烯点击化学反应合成了一种桥连双(β-环糊精)配体，然后将其键合到5μm球形硅胶上，得到一种新型桥连双(β-环糊精)手性固定相(HTCDP)。通过氢核磁共振(H NMR)、固态碳核磁共振(¹³C NMR)光谱、扫描电子显微镜、元素分析、质谱、红外光谱和热重分析对HTCDP和桥连双(β-环糊精)配体的结构进行了表征。通过在反相色谱模式下分离21种手性化合物，包括8种黄烷酮、8种三唑类农药和5种其他常见手性药物(苯偶姻、吡喹酮、1,1'-联-2-萘酚、特罗格碱和比卡鲁胺)，系统地考察了HTCDP的对映体分离性能。通过优化甲酸含量、流动相组成、pH值和柱温等色谱条件，19种分析物以高分辨率(1.50 - 4.48)完全分离，其中水飞蓟宾、4-羟基黄烷酮、2-羟基黄烷酮和黄烷酮的对映体分辨率在35分钟内分别高达4.34、4.48、3.89和3.
