De novo synthesis of microspheical cellulose 3,5-dichlorophenylcarbamates: An organic-inorganic hybrid chiral stationary phase for enantiospearation
De novo synthesis of microspheical cellulose 3,5-dichlorophenylcarbamates: An organic-inorganic hybrid chiral stationary phase for enantiospearation
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微球纤维素 3,5-二氯苯基氨基甲酸酯的从头合成：用于对映分离的有机-无机杂化手性固定相
DOI：
10.1016/j.seppur.2019.116480
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发表时间：
2020-05
期刊：
影响因子：
--
通讯作者：
YiwenYang
中科院分区：
文献类型：
--
作者：
XiaoxiaoYu;YehuiWang;QiweiYang;ZhiguoZhang;QilongRen;ZongbiBao;YiwenYang
高效液相色谱（HPLC）是获得光学纯对映体的最有效方法之一，具有高机械强度和优良手性识别性能的手性固定相（CSP）是制备型手性色谱发展的关键。传统的手性固定相通过包覆或固定在大孔硅胶上制备，存在比表面积小、洗脱剂选择范围窄等缺点，而基于溶胶-凝胶化学的有机-无机杂化材料具有高的手性选择剂密度和优异的机械强度。本文以纤维素3，5-二氯苯基氨基甲酸酯和正硅酸乙酯（TEOS）为前体，通过溶胶-凝胶反应和封端工艺，制备了具有良好手性拆分能力和高机械强度的有机-无机杂化手性固定相。采用29 Si CP/MAS NMR、FT-IR、TGA、SEM、EDX和BET比表面积分析等手段对合成的纤维素CSP进行了表征。采用高效液相色谱法对反式-2，3-二苯基环氧乙烷、2-苯基环己酮和安息香等7种典型手性对映体进行了分离性能评价，结果表明，杂化CSP对反式-2，3-二苯基环氧乙烷、2-苯基环己酮和安息香的手性识别能力与固定化CSP和市售Chiralpak IC相当，甚至更高，分离因子（α）分别为1.65、1.44和1.10。一系列的表征和结果表明，本工作中制备的有机硅杂化手性固定相具有足够的手性识别能力，对映体分离。
High-performance liquid chromatography (HPLC) is one of the most powerful methods to obtain optically pure enantiomers, and chiral stationary phase (CSP) with high mechanical strength and excellent chiral recognition performance is a key for the development of preparative chiral chromatography. Compared to traditional CSPs prepared by coating or immobilizing onto macro-porous silica gel with disadvantages of a limited specific surface area and narrow range of eluents, organic-inorganic hybrids materials on basis of sol-gel chemistry may feature a high density of chiral selectors and excellent mechanical strength. Herein, we reported a de novo synthesis strategy for preparing organic-inorganic hybrid CSPs with good chiral resolution ability and high mechanical strength by sol-gel reactions followed by an end-capping process to eliminate the residual silica hydroxyl groups using cellulose 3,5-dichlorophenylcarbamates and tetraethyl orthosilicate (TEOS) as precursors. The synthesized cellulose-derived CSP was comprehensively characterized by29Si CP/MAS NMR, FT-IR, TGA, SEM, EDX and BET surface area analysis. Furthermore, seven typical enantiomers were used to evaluate the enantioseparation ability of hybrid CSPs by HPLC, which demonstrated that the hybrid CSPs exhibited similar and even higher chiral recognition abilities to immobilized-type CSP and commercially available Chiralpak IC, such as trans-2,3-diphenyloxirane, 2-phenylcyclohexanone, and benzoin with separation factor (α) of 1.65, 1.44 and 1.10. A series of characterization and results indicated that the organosilica hybrid CSPs prepared in this work have adequate chiral recognition ability for enantioseparation.
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