Preparation and characterization of highly stable hybrid organosilicacellulose derivative-based chiral stationary phase

doi:10.11949/j.issn.0438-1157.20150547

Abstract

Abstract:

Chiral chromatography plays an important role in obtaining optically pure enantiomers. The key to preparative chiral chromatography is the availability of chiral stationary phases (CSPs) with broad chiral recognition, high sample loading as well as solvent tolerance. In order to overcome the shortcoming of traditional coating-type or bonding-type cellulose-based CSPs, a novel hybrid CSP based on cellulose derivative bearing a small amount of 3-(triethoxysilyl)propyl groups was proposed, which was used to crosslink with bis(triethoxysilyl)ethane (BTSE) via a sol-gel reaction. The prepared stationary phase was then evaluated by HPLC. The experimental results indicated that the CSP showed excellent chiral recognition ability and could run steadily at back column pressure more than 2000 psi (1 psi 6894.76 Pa) with flow-rate up to 3 ml·min^-1 in the mobile phase containing 10% chloroform. It was worth mentioning that the selectivity of 2,2,2-trifluoro-1-(9-anthryl)ethanol and trans-stilbene oxide up to 2.99 and 2.48 was achieved, respectively, confirming its excellent chiral recognition performance. In addition, the reported CSP showed a promising packing for application in preparative chromatography such as simulated moving bed chromatography.

Key words: chiral stationary phase, hybrid material, chromatography, separation, mechanical properties, solvent stability

摘要：

合成了含少量3-(三乙氧基硅)丙基氨基甲酸酯的纤维素3,5-二甲基苯基氨基甲酸酯衍生物(CDMPC),并采用1,2-二(三乙氧基硅基)乙烷(BTSE)为偶联剂,通过溶胶-凝胶法成功制备得到新型硅基杂化手性固定相。该固定相的CDMPC含量达60%,在含有10%氯仿的流动相中保持良好的手性识别性能和机械强度。使用其拆分了多种手性化合物,拆分效果优于商品柱Chiralpak IB,其中对2,2,2-三氟-1-(9-蒽基)乙醇和反式二苯乙烯氧化物对映体的分离选择性分别达到2.99和2.48,表明该类硅基杂化类手性固定相在制备色谱领域中有潜在应用前景。

关键词: 手性固定相, 杂化材料, 色谱, 分离, 机械性能, 溶剂耐受性

CLC Number:

O657.7

LUO Fei, WENG Xilun, BAO Zongbi, YANG Yiwen, REN Qilong. Preparation and characterization of highly stable hybrid organosilicacellulose derivative-based chiral stationary phase[J]. CIESC Journal, 2015, 66(11): 4520-4525.

罗飞, 翁西伦, 鲍宗必, 杨亦文, 任其龙. 高稳定性硅基杂化纤维素衍生物手性固定相的制备及其色谱拆分性能[J]. 化工学报, 2015, 66(11): 4520-4525.

References 25

[1]	Ikai T, Okamoto Y. Structure control of polysaccharide derivatives for efficient separation of enantiomers by chromatography [J]. Chemical Reviews, 2009, 109 (11): 6077-6101.
[2]	Lorenz H, Seidel Morgenstern A. Processes to separate enantiomers [J]. Angewandte Chemie International Edition, 2014, 53 (5): 1218-1250.
[3]	He Yongzhu (何永祝), Pang Hao (庞浩), Liao Bing (廖兵). Progress in cellulose-based chiral stationary phases [J]. Progress in Chemistry (化学进展), 2006, 18: 957-965.
[4]	Zhang Guojun (张国俊), Ruan Zhengang (阮振刚), Gao Xue (高学), Ji Shulan (纪树兰), Liu Zhongzhou (刘忠洲). Chiral separation with affinity membrane technology and chiral selective solid membrane [J]. Chemical Industry and Engineering Progress (化工进展), 2008, 27 (6): 797-803.
[5]	Cavazzini A, Pasti L, Massi A, Marchetti N, Dondi F. Recent applications in chiral high performance liquid chromatography: a review [J]. Analytica Chimica Acta, 2011, 706 (2): 205-222.
[6]	Huang Bei (黄蓓), Yang Lirong (杨立荣), Wu Jianping (吴坚平). Chiral resolution techniques in industrial practice [J]. Chemical Industry and Engineering Progress (化工进展), 2002, 21 (6): 375-380.
[7]	Zheng Xi (郑熙), Hu Xiaoling (胡小玲). Development of membranes for chiral resolution [J]. Chemical Industry and Engineering Progress (化工进展), 2008, 27 (11): 1703-1709.
[8]	Qi Xuan (亓晅), Luo Guangsheng (骆广生). Advances on enantioseparation of amino acid by solid membrane [J]. Chemical Industry and Engineering Progress (化工进展), 2004, 23 (9): 963-967.
[9]	Schiel J E, Mallik R, Soman S, Joseph K S, Hage D S. Applications of silica supports in affinity chromatography [J]. Journal of Separation Science, 2006, 29 (6): 719-737.
[10]	Stringham R. The use of polysaccharide phases in the separation of enantiomers[C]. 2006: 257-290.
[11]	Subramani-An G. Chiral Separation Techniques: A Practical Approach[M]. 3rd ed. Weinheim: Wiley-VCH, 2007.
[12]	Wei Feng (危凤), Shen Bo (沈波), Chen Mingjie (陈明杰), Zhou Xianbo (周先波), Wu Pingdong (吴平东). Omeprazole resolution by simulated moving bed chromatography [J]. Journal of Chemical Industry and Engineering (China) (化工学报), 2005, 56 (9): 1699-1702.
[13]	Li Xiaogang, Liu Yiping, Hu Changdi, Bai Lianyang, Gao Bida, Huang Kelong. Direct optical resolution of chiral pesticides by high performance liquid chromatography [J]. Chinese Journal of Chemical Engineering, 2011, 19 (4): 603-609.
[14]	Qi Yuan (祁媛). Synthesis and application of the composite chitosan of chiral stationary phase [D]. Lanzhou: Lanzhou Jiaotong University, 2013.
[15]	Lei Ming (雷鸣). Preparation of chiral stationary phase based on amino acid ligand [D]. Wuxi: Jiangnan University, 2012.
[16]	Yashima E, Okamoto Y. Chiral discrimination on polysaccharides derivatives [J]. Bulletin of the Chemical Society of Japan, 1995, 68 (12): 3289-3307.
[17]	Yashima E, Yamamoto C, Okamoto Y. Polysaccharide-based chiral LC columns [J]. Synlett., 1998, (4): 344-360.
[18]	Yashima E. Polysaccharide-based chiral stationary phases for high performance liquid chromatographic enantioseparation [J]. Journal of Chromatography A, 2001, 906 (1): 105-125.
[19]	Schulte M, Ditz R, Devant R M, Kinkel J N, Charton F. Comparison of the specific productivity of different chiral stationary phases used for simulated moving-bed chromatography [J]. Journal of Chromatography A, 1997, 769 (1): 93-100.
[20]	Francotte E R. Enantioselective chromatography as a powerful alternative for the preparation of drug enantiomers [J]. Journal of Chromatography A, 2001, 906 (1): 379-397.
[21]	Weng Xilun (翁西伦), Bao Zongbi (鲍宗必), Luo Fei (罗飞), Su Baogen (苏宝根), Yang Yiwen (杨亦文), Ren Qilong (任其龙). Progress in preparation and applications of cellulose derivatives based chiral stationary phase [J]. Progress in Chemistry (化学进展), 2014, 26 (2/3): 415-423
[22]	Ikai T, Yamamoto C, Kamigaito M, Okamoto Y. Organic-inorganic hybrid materials for efficient enantioseparation using cellulose 3,5-dimethylphenyl carbamate and tetraethyl orthosilicate [J]. Chemistry-An Asian Journal, 2008, 3 (8/9): 1494-1499.
[23]	Weng X, Bao Z, Xing H, Zhang Z, Yang Q, Su B, Yang Y, Ren Q. Synthesis and characterization of cellulose 3, 5-dimethylphenylcarbamate silica hybrid spheres for enantioseparation of chiral β-blockers [J]. Journal of Chromatography A, 2013, 1321: 38-47.
[24]	Weng X, Bao Z, Zhang Z, Su B, Xing H, Yang Q, Yang Y, Ren Q. Preparation of porous cellulose 3, 5-dimethylphenyl carbamate hybrid organosilica particles for chromatographic applications [J]. Journal of Materials Chemistry B, 2015, 3 (4): 620-628.
[25]	Jin Zhaolei (金召磊), Hu Fangfang (胡芳芳), Wang Yibo (汪一波),Liu Guihua (刘贵花), Wang Fang (王芳), Pan Fuyou (潘富友), Tang Shouwan (唐守万). Preparation and evaluation of amylose and cellulose tris(3-trifluoromethylphenylcarbamates)-based chiral stationary phases [J]. Journal of Chromato (色谱), 2011, 29: 1087-1092.