氨基甲酸酯功能化离子液体高效液相色谱固定相的制备与初步评价

doi:10.3724/SP.J.1095.2013.30188

摘要/Abstract

摘要： 合成一种了氨基酸衍生物：4,4′-二苯亚甲基桥联-二[2-(1-咪唑基)-3-苯基丙醇氨基甲酸酯](ImPh-Carb)，并将其键合到硅胶上制备了一种新的氨基甲酸酯功能化的离子液体HPLC固定相（ImPh-Carb-Silica）。利用1H NMR、13C NMR、MS和FTIR对ImPh-Carb进行了表征；通过FTIR和元素分析对ImPh-Carb-Silica固定相进行了表征，根据N含量计算得到ImPh-Carb-Silica的键合量为0.19 mmol/g。以5种芳烃、5种酚类化合物和4种有机磷农药为分析物，分别在正相和反相色谱模式下对固定相的色谱分离性能进行了评价，同时考察了流动相的变化与溶质保留因子lg k之间的关系。结果表明，该固定相与溶质分子间存在多重作用力，如疏水、氢键、π-π和偶极-诱导偶极作用等，使其能同时在正相和反相色谱模式下使用；在正相色谱条件下固定相对酚类化合物和有机磷农药表现出较好的分离选择性。

关键词: 氨基甲酸酯功能化离子液体, 固定相, 高效液相色谱, 多重作用机制

Abstract: A new carbamate functionalized ionic liquid stationary phase(ImPh-Carb-Silica) for high-performance liquid chromatography was prepared by bonding 4,4′-diphenylmethylene-bis[2-(1-imidazolyl)-3-phenyl-1-propanol carbamate](ImPh-Carb) onto silica particles. The structure of ImPh-Carb was characterized by 1H NMR,13C NMR, MS and FTIR, and the bonded stationary phase was also characterized by FTIR and element analysis, and the bonding amount of ImPh-Carb-Silica stationary phase was about 0.19 mmol/g, according to the nitrogen content. The chromatographic performances of the stationary phase were evaluated using aromatic hydrocarbons, phenols and organophosphorus pesticides as solutes in reversed-phase and normal-phase chromatographic modes, and the effect of the content of mobile phase on retention factor(lg k) of analytes was studied. The results show that the functionalized ionic liquid stationary phase provides a multiple-interaction mechanism with analytes including hydrophobic, hydrogen bonding, π-π, and dipole-induce/dipole interactions. The stationary phase can be simultaneously performed in reversed-phase and normal-phase chromatographic modes, and it demonstrates its superiority in separation of phenols and organophosphorus pesticides under normal-phase chromatographic mode.

Key words: carbamate functionalized ionic liquid, stationary phase, high-performance liquid chromatography, multiple-interaction mechanism

中图分类号:

O657

刘晓鸽, 王宏雁, 杨光云, 毛璞, 何丽君, 肖咏梅, 屈凌波. 氨基甲酸酯功能化离子液体高效液相色谱固定相的制备与初步评价[J]. 应用化学, DOI: 10.3724/SP.J.1095.2013.30188.

LIU Xiaoge, WNAG Hongyan, YANG Guangyun, MAO Pu, HE Lijun, XIAO Yongmei, QU Lingbo*. Preparation and Evaluation of Carbamate Functionalized Ionic Liquid Stationary for High-performance Liquid Chromatography[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2013.30188.

参考文献

[1] LI Xuehui,ZHAO Dongbin,FEI Zhaofu,et al. Functionalizaton and Application of Ionic Liquids[J]. Sci China（Ser B）,2006,36(3):181-196(in Chinese).

李雪辉，赵东滨，费兆福，等. 离子液体的功能化及其应用[J]. 中国科学（B辑) ，2006,36(3):181-196.

[2] Duchet L,Legeay J C,Carrie D,et al. Synthesis of 3,5-Disubstituted 1,2,4-Oxadiazoles Using Ionic Liquid-phase Organic Synthesis(IoLiPOS) Methodology[J]. Tetrahedron,2010,66(4):986-994.

[3] Gao R F,Zheng J B. Direct electrochemistry of Myoglobinbased on DNA Accumulation on Carbon Ionic Liquid Electrode[J]. Electrochem Commun,2009,11(7):1527-1529.

[4] Buhler G,Zharkouskaya A,Feldmann C. Ionic Liquid Based Approach to Nanoscale Functional Materials [J]. Solid State Sci,2008,10(4):461-465.

[5] He L J,Zhang W Z,Zhao L,et al. Effect of 1-Alkyl-3-methylimidazolium-based Ionic Liquids as the Eluent on the Separation of Ephedrines by Liquid Chromatography[J]. J Chromatogr A,2003,1007(1/2):39-45.

[6] Zhang W Z,He L J,Gu Y L,et al. Effect of Ionic Liquids as Mobile Phase Additives on Retention of Catecholamines in Reversed-phase Highperformance Liquid Chromatography[J]. Anal Lett,2003,36(4):827-838.

[7] Obert A,Roth D,Ehrig M,et al. Selectivity Enhancement in the Catalytic Hydrogenation of Propionitrile Using Ionic Liquid Multiphase Reaction Systems[J]. Appl Catal,2009,356(1):43-51.

[8] Berthod A,Ruiz-A′ngel M J,Carda-Broch S. Ionic Liquids in Separation Techniques[J]. J Chromatogr A,2008,1184(1/2):6-18.

[9] WANG Xusheng,QIU Hongdeng,LIU Xia,et al. Separation of Bases, Phenols and Pharmaceuticals on Ionic Liquid-modified Silica Stationary Phase with Pure Water as Mobile Phase[J]. Chinese J Chromatogr,2011,29(3):269-272(in Chinese).

王旭生，邱洪灯，刘霞，等. 咪唑离子液体键合硅胶固定相纯水洗脱分离碱基、酚类和药物化合物[J]. 色谱,2011,29(3):269-272.

[10] Qiu H D,Jiang Q,Wei Z,et al. Preparation and Evaluation of a Silica-based 1-Aalkyl-3-(propyl-3-sulfonate) Imidazolium Zwitterionic Stationary Phase for High-performance Liquid Chromatography[J]. J Chromatogr A,2007,1163:63-69.

[11] Qiu H D,Jiang S X,Liu X. N-Methylimidazolium Anion-exchange Stationary Phase for High-performance Liquid Chromatography[J]. J Chromatogr A,2006,1103:265-270.

[12] Qiu H D,Takafuji M,Liu X,et al. Investigation of π-π and Ion-dipole Interactions on 1-Allyl-3-butylimidazolium Ionic Liquid-modified Silica Stationary Phase in Reversed-phase Liquid Chromatography[J]. J Chromatogr A,2011,1217(32):5190-5196.

[13] LI Laisheng,CHEN Xiongquan，YANG Hanrong,et al. Preparation and Characterization of a Baicalin-bonded Stationary Phase for High Performance Liquid Chromatograph[J]. Chinese J Anal Chem,2007,35(9):1279-1284(in Chinese).

李来生,陈雄全,杨汉荣,等. 黄芩苷键合硅胶固定相的制备和表征[J]. 分析化学,2007,35(9):1279-1284.

[14] Hansch C,Leo A,Hoekman D, Exploring QSAR-Hydrophobic, Electronic and Steric Constants[M]. Washington,D.C:American Chemical Society,1995.

[15] He L J,Zhang M L,Liu L H,et al. Two New Azamacrocycle-based Stationary Phases for High-performance Liquid Chromatography:Preparation and Comparative Evaluation[J]. J Chromatogr A,2012,1270:186-193.

[16] He L J,Zhang J,Sun Y J,et al. A Multiple-function Stationary Phase Based on Perhydro-26-membered Hexaazamacrocycle for High Performance Liquid Chromatography[J]. J Chromatogr A,2010,1217:5971-5977.