基于氧化石墨烯的环糊精型色谱固定相的制备及在对映体分离与亲水色谱中的应用

引用本文: 李强, 李媛媛, 朱楠, 高柱仙, 李添君, 周彤, 马玉龙. 基于氧化石墨烯的环糊精型色谱固定相的制备及在对映体分离与亲水色谱中的应用[J]. 分析化学, 2018, 46(9): 1455-1463. doi: 10.11895/j.issn.0253-3820.181337 shu

Citation: LI Qiang, LI Yuan-Yuan, ZHU Nan, GAO Zhu-Xian, LI Tian-Jun, ZHOU Tong, MA Yu-Long. Preparation of Cyclodextrin Type Stationary Phase Based on Graphene Oxide and Its Application in Enantioseparation and Hydrophilic Chromatography[J]. Chinese Journal of Analytical Chemistry, 2018, 46(9): 1455-1463. doi: 10.11895/j.issn.0253-3820.181337 shu

基于氧化石墨烯的环糊精型色谱固定相的制备及在对映体分离与亲水色谱中的应用

1.
宁夏大学省部共建煤炭高效利用与绿色化工国家重点实验室, 银川 750021;
2.
宁夏大学化学化工学院, 银川 750021
基金项目:
本文系国家自然科学基金项目（No.21465019）、宁夏高等学校科学研究基金（No.NGY201814）、宁夏回族自治区化学工程与技术国内一流学科项目（No.NXYLXK2017A04）和大学生创新创业训练计划项目（No.201810749090）资助

摘要: 将氧化石墨烯（GO）通过酰胺键键合到氨基硅胶上，进一步将β-环糊精（β-CD）化学键合于GO上，制备了一种新型手性固定相材料，采用IR、SEM、TEM、元素分析和热重分析进行了表征。7种对映体得到不同程度的拆分，同时此固定相表现出典型的亲水作用色谱（HILIC）特征，4种核苷小分子在流动相为甲醇-乙腈-水（45∶45∶10，V/V）时得到分离。通过考察流动相组成、温度、pH值对分析物保留的影响，进一步探讨了该固定相的分离机理。在20~60℃时，温度越低越有利于分析物质分离；加入质子化溶剂甲醇，4种分析物的保留时间显著减弱；pH值的改变影响分析物的质子化程度进而改变与固定相作用力和保留时间。结果表明，此色谱固定相中GO和β-CD在手性拆分中具有协同作用，而在HILIC中分析物的保留归因于混合模式的保留机理，包括亲水作用、静电作用、氢键、π-π堆积作用等。

关键词:

English

Preparation of Cyclodextrin Type Stationary Phase Based on Graphene Oxide and Its Application in Enantioseparation and Hydrophilic Chromatography

1.
State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, Ningxia University, Yinchuan 750021, China;
2.
College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China
Received Date: 21 May 2018
Revised Date: 15 July 2018
Fund Project:
This work was supported by the National Natural Science Foundation of China (No. 21465019), the Research Project for Science and Technology of Higher Education of Ningxia Province of China (No. NGY2018014), the National First-rate Discipline Construction Project of Ningxia (Chemical Engineering and Technology, No. NXYLXK2017A04), and the Undergraduate Innovation and Entrepreneurship Training Program (No.201810749090).

Abstract: Graphene oxide (GO) was covalently coupled to the surface of amino silica gel by amide bond. β-Cyclodextrin (β-CD) was further chemically bonded to GO to prepare a novel chiral stationary phase. The resulting material was characterized by Fourier transform-infrared (FT-IR) spectra, scanning electron microscopy (SEM), transmission electron microscopy (TEM), elemental analysis and thermogravimetric analysis (TGA). The separation of seven enantiomers was improved in varying degrees. At the same time, the stationary phase showed typical characteristics of hydrophilic interaction chromatography (HILIC), and four small nucleoside molecules were separated when the mobile phase was methanol-acetonitrile-water (45:45:10, V/V) in HILIC mode. In addition, the separation mechanism of the stationary phase was further explored by studying the effects of mobile phase composition, temperature, and pH on the analyte retention. The low temperature was conducive to the separation of analytes at 20-60℃. The addition of protonated solvent methanol significantly decreased retention time of the four analytes. The pH affected the degree of protonation of the analyte, the interaction among analytes and stationary phase, and retention time of analytes. The results showed that GO and β-CD played a synergistic effect in the chiral resolution of the chromatographic stationary phase. The retention of analytes in HILIC was attributed to their mixed-mode retention mechanisms including hydrophilic interactions, electrostatic interactions, hydrogen bonding, π-π stacking and so on.

Key words:

Cyclodextrin
/ Graphene oxide
/ Chiral stationary phase
/ Enantioseparation
/ Hydrophilic interaction chromatography

1. [1]
  Shah R R, Midgley J M, Branch S K. Adverse Drug React. Toxicol. Rev.,1998,17(2-3):145-148
2. [2]
  Martínez-Girón A B, Marina M L, Crego A L. J. Chromatogr. A,2016,1467:427-435
3. [3]
  Lorenz H, Seidel-Morgenstern A. Angew. Chem. Int. Edit.,2014,53(5):1218-1250
4. [4]
  Li L W, Wu C J, Ma Y, Zhou S H, Li Z, Sun T M. Analyst,2017,142(19):3699-3706
5. [5]
  Qiao L J, Zhou X H, Li X, Du W R, Yu A J, Zhang S S, Wu Y J. Talanta,2017,163:94-101
6. [6]
  Bortocan R, Bonato P S. Electrophoresis,2004,25(16):2848-2853
7. [7]
  Nojavan S, Fakhari A R. Electrophoresis,2011,32(6-7):764-771
8. [8]
  Yu T, Du Y. Chen B. Electrophoresis,2011,32(14):1898-1905
9. [9]
  Kumar A P, Park J H. J. Chromatogr. A,2011,1218(31):5369-5373
10. [10]
  Haginaka J. J. Chromatogr. B,2008,875(1):12-19
11. [11]
  Navarro-Sánchez J, Argente-García A I, Moliner-Martínez Y, Roca-Sanjuán D, Antypov D, Campíns-Falcó P, Rosseinsky M J, Martí-Gastaldo C. J. Am. Chem. Soc.,2017,139(12):4294-4297
12. [12]
  Han X, Huang J J, Yuan C, Liu Y, Cui Y. J. Am. Chem. Soc.,2018,140(3):892-895
13. [13]
  Rao C N R, Sood A K, Subrahmanyam K S, Govindaraj A. Angew. Chem. Int. Edit.,2010,48(42):7752-7777
14. [14]
  Ershova O V, Lillestolen T C, Bichoutskaia E. Phys. Chem. Chem. Phys.,2010,12(24):6483-6491
15. [15]
  Sun Y, Yang S, Zhao G, Wang Q, Wang X. Chem. Asian J.,2013,8(11):2755-2761
16. [16]
  Wang J, Chen Z, Chen B. Environ. Sci. Technol.,2014,48(9):4817-4825
17. [17]
  ZHANG Wei-Bing, GAO Yu, PENG Li, ZHAO Yi-Man, LIU Hai-Yan. Chinese J. Anal. Chem., 2016,44(6):835-841 张维冰, 高羽, 彭丽, 赵祎曼, 刘海燕.分析化学,2016,44(6):835-841
18. [18]
  Zhang X Q, Chen S, Han Q, Ding M Y. J. Chromatogr. A,2013,1307(17):135-143
19. [19]
  Li X X, Yao X B, Xiao Y, Wang Y. Anal. Chim. Acta,2017,990:174-184
20. [20]
  Haiyee Z A, Saim N, Said M, Illias R M, Wan M W A, Hassan O. Food Chem.,2009,114(2):459-465
21. [21]
  WU Zhi-Hua, ZHAO Jie, LI Shen, WANG Yong. Chinese J. Anal.Chem.,2016,44(1):95-102 武志花, 赵杰, 李珅, 王勇.分析化学,2016,44(1):95-102
22. [22]
  Varga G, Fodor G, Ilisz I, Szemán J, Visy J, Szente L, Péter A. J. Pharm. Biomed. Anal.,2012,70:71-76
23. [23]
  ZHOU Ren-Dan, LI Lai-Sheng, CHENG Biao-Ping, NIE Gui-Zhen, ZHANG Hong-Fu. Chinese J. Anal.Chem.,2014,42(7):1102-1109 周仁丹, 李来生, 程彪平, 聂桂珍, 张宏福.分析化学,2014,42(7):1002-1009
24. [24]
  Li Y Y, Wei M M, Chen T, Zhu N, Ma Y L. Talanta,2016,160:72-78
25. [25]
  Ikegami T, Tomomatsu K, Takubo H, Horie K, Tanaka N. J. Chromatogr. A,2008,1184(1-2):474-503
26. [26]
  WU Cheng-Ling, LIU Jian-Fen, ZHANG Zhen-Qing. Chinese J. Anal. Chem.,2015,43(8):1198-1202 吴成玲, 刘建芬, 张真庆.分析化学,2015,43(8):1198-1202
27. [27]
  ZHENG Si-Jia, WANG Qing-Qing, WANG Xiao-Lin, ZHAO Xin-Jie, XU Guo-Wang. Chinese J. Anal. Chem., 2017,45(12):1921-1929 郑思佳, 王晴晴, 王晓琳, 赵欣捷, 许国旺.分析化学,2017,45(12):1921-1929
28. [28]
  Tufi S, Lamoree M, De B J, Leonards P. J. Chromatogr. A,2015,1395:79-87
29. [29]
  Niyogi S, Bekyarova E, Itkis M E, Mcwilliams J L, Hamon M A, Haddon R C. J. Am. Chem. Soc.,2006,128 (24):7720-7721
30. [30]
  Cao Y, Wu S, Liang Y, Yu Y. J. Mol. Struct.,2013,1031(5):9-13
31. [31]
  Zhong Q Q, He L F, Beesley T E, Trahanovsky W S, Sun P, Wang C L, Armstrong D W. J. Chromatogr. A, 2006,1115(1-2):19-45
32. [32]
  Li Y Y, Li Q, Zhu N, Gao Z X, Ma Y L. Chirality, 2018,30(6):996-1004
33. [33]
  Yang F, Yang C X, Yan X P. Talanta,2015,137:136-142

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

基于氧化石墨烯的环糊精型色谱固定相的制备及在对映体分离与亲水色谱中的应用

English

Preparation of Cyclodextrin Type Stationary Phase Based on Graphene Oxide and Its Application in Enantioseparation and Hydrophilic Chromatography

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

基于氧化石墨烯的环糊精型色谱固定相的制备及在对映体分离与亲水色谱中的应用

English

Preparation of Cyclodextrin Type Stationary Phase Based on Graphene Oxide and Its Application in Enantioseparation and Hydrophilic Chromatography

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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