吡啶二甲酰胺基桥联双<i>β</i>-环糊精手性固定相的制备和评价

引用本文: 钟慧, 曾庆丽, 张天赐, 双亚洲, 李来生. 吡啶二甲酰胺基桥联双β-环糊精手性固定相的制备和评价[J]. 分析化学, 2022, 50(3): 433-444. doi: 10.19756/j.issn.0253-3820.210787 shu

Citation: ZHONG Hui, ZENG Qing-Li, ZHANG Tian-Ci, SHUANG Ya-Zhou, LI Lai-Sheng. Preparation and Evaluation of a Pyridinediamide Bridged Bis(β-cyclodextrin) Chiral Stationary Phase[J]. Chinese Journal of Analytical Chemistry, 2022, 50(3): 433-444. doi: 10.19756/j.issn.0253-3820.210787 shu

吡啶二甲酰胺基桥联双β-环糊精手性固定相的制备和评价

钟慧 ^1, ,
曾庆丽 ^1, ,
张天赐 ^1, ,
双亚洲 ^1, ,
李来生 ^{1,2,
,}

¹南昌大学化学学院, 南昌 330031;
²南昌大学分析测试中心, 南昌 330047

通讯作者: 李来生,E-mail:lilaishengcn@163.com

基金项目:
国家自然科学基金项目（Nos.31860469，21165012）和江西省科技创新平台项目（No.20192BCD40001）资助。

摘要: 基于吡啶-2，3-二甲酸和6-氨基-β-环糊精的缩合反应，合成了桥联β-环糊精，将其键合到硅胶表面，制备了一种新型的吡啶二甲酰胺基桥联双β-环糊精手性固定相（PyCDP）。以黄烷酮类、三唑类、氨基酸类、β-受体阻滞剂类共38种手性药物和农药作探针，系统评价了此固定相的手性色谱性能，并采用自制的天然环糊精固定相（CDCSP）作为对比。结果表明，PyCDP可在反相和极性有机两种模式下拆分全部38种手性物质，其中2'-羟基黄烷酮、粉唑醇、苯丙氨酸和艾司洛尔对映体的分离度（R_s）分别为2.36、1.98、1.86和1.62，分析时间较短（<30 min）。反相色谱模式下，PyCDP可在15~30℃温度范围通过调节流动相中乙腈体积分数（20%~35%）实现三唑类农药的基线分离，并能将含两个手性中心的三唑醇和联苯三唑醇分别拆分为4个峰。在流动相pH 5.0~6.5范围内，PyCDP可基线拆分易电离的酸性、碱性和极性氨基酸对映体。此外，PyCDP也适用于极性有机模式，如较大位阻的卡维地洛也能被拆分（R_s=1.42），并首次实现了贝凡洛尔在环糊精类固定相上的拆分。而CDCSP只能拆分其中的20种手性物质，且分离度偏低。PyCDP结构中，桥联环糊精上邻近的两个空腔的协同包结作用和吡啶二甲酰胺桥基提供氢键、π-π作用有助于手性分离。研究结果表明，PyCDP是一种多功能的手性分离材料。

关键词:

English

Preparation and Evaluation of a Pyridinediamide Bridged Bis(β-cyclodextrin) Chiral Stationary Phase

¹College of Chemistry, Nanchang University, Nanchang 330031, China;
²Center of Analysis and Testing, Nanchang University, Nanchang 330047, China

Corresponding author: LI Lai-Sheng, lilaishengcn@163.com

Received Date: 12 October 2021
Revised Date: 07 December 2021
Fund Project:
Supported by the National Natural Science Foundation of China (Nos.31860469, 21165012) and the Jiangxi Province Science Technology Innovation Platform Project (No.20192BCD40001).

Abstract: Based on the dehydration condensation reaction between 2,3-pyridinedicarboxylic acid and 6-amino-β-cyclodextrin, a pyridinediamide bridged bis(β-cyclodextrin) was synthesized and then bonded onto silica gel to obtain a novel pyridinediamide bridged bis(β-cyclodextrin) chiral stationary phase (PyCDP). A total of 38 chiral drugs and pesticides including flavanones, triazoles, amino acids and β-blockers were used as chiral probes to systematically evaluate the chiral high performance liquid chromatography (HPLC) performance of the new stationary phase. Additionally, a common native cyclodextrin stationary phase (CDCSP) was also prepared by the similar method for comparsion purpose. The research results showed that the new bridged cyclodextrin stationary phase could resolve all 38 chiral analytes in both reversed-phase and polar organic modes. Among them, the enantiomeric resolution (R_s) of 2'-hydroxyflavanone, flutriafol, phenylalanine and esmolol were 2.36, 1.98, 1.86 and 1.62 within 30 min, respectively. In reversed-phase chromatographic mode, PyCDP could realize the baseline separations of triazole pesticides by adjusting the volume fraction of acetonitrile (20%-35%) in the mobile phase in the temperature range of 15-30℃, and could resolve triadimenol and bitertanol with two chiral centers into four peaks, respectively. PyCDP achieved the complete separations of easily ionized acidic, basic and polar amino acids in the pH range (5.0-6.5) of the mobile phases. In addition, PyCDP was also suitable for polar organic mode. For example, carvedilol (R_s=1.42) with larger steric hindrance could also be resolved, and it was the first time to realize the separation of bevanolol on cyclodextrin stationary phases. However, under the optimized conditions, CDCSP could only resolve 20 chiral substances with lower resolutions. Obviously, the synergistic inclusion of two adjacent cavities on bridged cyclodextrin and the hydrogen bond and π-π effect provided by pyridinediamide bridging group were conducive to chiral separations. PyCDP was a kind of multifunctional chiral separation materials.

Key words:

1. [1]
  SHEN Q, WANG L, ZHOU H, JIANG H D, YU L S, ZENG S. Acta Pharmacol. Sin., 2013, 34(8):998-1006.SHEN Q, WANG L, ZHOU H, JIANG H D, YU L S, ZENG S. Acta Pharmacol. Sin., 2013, 34(8):998-1006.
2. [2]
  CALCATERRA A, D'ACQUARICA I. J. Pharmaceut. Biomed., 2018, 147:323-340.CALCATERRA A, D'ACQUARICA I. J. Pharmaceut. Biomed., 2018, 147:323-340.
3. [3]
  CHEN F X, BAI Q X, WANG Q F, CHEN S Y, MA X X, CAI C L, WANG D N, WAQAS A, GONG P. Curr. Pharm. Biotechnol., 2020, 21(15):1632-1644.CHEN F X, BAI Q X, WANG Q F, CHEN S Y, MA X X, CAI C L, WANG D N, WAQAS A, GONG P. Curr. Pharm. Biotechnol., 2020, 21(15):1632-1644.
4. [4]
  TANG J, PANG L M, ZHOU J, ZHANG S P, TANG W H. Anal. Chim. Acta, 2016, 946:96-103.TANG J, PANG L M, ZHOU J, ZHANG S P, TANG W H. Anal. Chim. Acta, 2016, 946:96-103.
5. [5]
  YIN Chun-Chun, YANG Tian-Tian, ZHANG Jin-Ming, ZHANG Jun. Chin. J. Chromatogr., 2020, 38(4):478-483. 尹春春, 杨田田, 张金明, 张军. 色谱, 2020, 38(4):478-483.
6. [6]
  ZHAO B J, LI L, WANG Y T, ZHOU Z M. Chin. Chem. Lett., 2019, 30(3):643-649.ZHAO B J, LI L, WANG Y T, ZHOU Z M. Chin. Chem. Lett., 2019, 30(3):643-649.
7. [7]
  HERRERA B A, BRUNA T C, SIERPE R A, LANG E P, URZUA M, FLORES M I, JARA P S, YUTRONIC N I. Carbohydr. Polym., 2020, 233:115865.HERRERA B A, BRUNA T C, SIERPE R A, LANG E P, URZUA M, FLORES M I, JARA P S, YUTRONIC N I. Carbohydr. Polym., 2020, 233:115865.
8. [8]
  SCRIBA G K E. J. Chromatogr. A, 2016, 1467:56-78.SCRIBA G K E. J. Chromatogr. A, 2016, 1467:56-78.
9. [9]
  ARMSTRONG D W, ALAK A, DEMOND W, HINZE W L, RIEHL T E. J. Liq. Chromatogr., 1985, 8(2):261-269.ARMSTRONG D W, ALAK A, DEMOND W, HINZE W L, RIEHL T E. J. Liq. Chromatogr., 1985, 8(2):261-269.
10. [10]
  PANG L M, ZHOU J, TANG J, NG S C, TANG W H. J. Chromatogr. A, 2014, 1363:119-127.PANG L M, ZHOU J, TANG J, NG S C, TANG W H. J. Chromatogr. A, 2014, 1363:119-127.
11. [11]
  SUN P, WANG C, ARMSTRONG D W, PETER A, FORRO E. J. Liq. Chromatogr. Relat. Technol., 2006,29(13):1847-1860.SUN P, WANG C, ARMSTRONG D W, PETER A, FORRO E. J. Liq. Chromatogr. Relat. Technol., 2006,29(13):1847-1860.
12. [12]
  ZHOU J, YANG B, TANG J, TANG W H. New J. Chem., 2018, 42(5):3526-3533.ZHOU J, YANG B, TANG J, TANG W H. New J. Chem., 2018, 42(5):3526-3533.
13. [13]
  CHEN M, LU X L, MA X F, XIAO Y, WANG Y. Analyst, 2021, 146(9):3025-3033.CHEN M, LU X L, MA X F, XIAO Y, WANG Y. Analyst, 2021, 146(9):3025-3033.
14. [14]
  LAI X H, TANG W H, NG S C. J. Chromatogr. A, 2011, 1218(33):5597-5601.LAI X H, TANG W H, NG S C. J. Chromatogr. A, 2011, 1218(33):5597-5601.
15. [15]
  BRESLOW R, GREENSPOON N, GUO T, ZARZYCKI R. J. Am. Chem. Soc., 1989, 111(21):8296-8297.BRESLOW R, GREENSPOON N, GUO T, ZARZYCKI R. J. Am. Chem. Soc., 1989, 111(21):8296-8297.
16. [16]
  ZHAO Y, GU J, YANG Y C, ZHU H Y, HUANG R, JING B. J. Mol. Struct., 2009, 930(1-3):72-77.ZHAO Y, GU J, YANG Y C, ZHU H Y, HUANG R, JING B. J. Mol. Struct., 2009, 930(1-3):72-77.
17. [17]
  CHEN G S, JIANG M. Chem. Soc. Rev., 2011, 40(5):2254-2266.CHEN G S, JIANG M. Chem. Soc. Rev., 2011, 40(5):2254-2266.
18. [18]
  WILSON D, PERLSON L, BRESLOW R. Bioorg. Med. Chem., 2003, 11(12):2649-2653.WILSON D, PERLSON L, BRESLOW R. Bioorg. Med. Chem., 2003, 11(12):2649-2653.
19. [19]
  SUN M, ZHANG H Y, LIU B W, LIU Y. Macromolecules, 2013, 46(11):4268-4275.SUN M, ZHANG H Y, LIU B W, LIU Y. Macromolecules, 2013, 46(11):4268-4275.
20. [20]
  AI Ping, HAN Li-Na, ZI Min, MENG Lei, ZI Fu-Ting, YUAN Li-Ming. Chin. J. Anal. Chem., 2006, 34(10):1459-1462. 艾萍, 韩丽娜, 字敏, 孟磊, 字富庭, 袁黎明. 分析化学, 2006, 34(10):1459-1462.
21. [21]
  ZHOU Ren-Dan, LI Lai-Sheng, CHENG Biao-Ping, NIE Gui-Zhen, ZHANG Hong-Fu. Acta Chim. Sinica, 2014, 72(6):720-730. 周仁丹, 李来生, 程彪平, 聂桂珍, 张宏福. 化学学报, 2014, 72(6):720-730.
22. [22]
  SHUANG Ya-Zhou, WANG Hui, ZHANG Tian-Ci, LI Lai-Sheng. Chin. J. Chromatogr., 2020, 38(4):464-475. 双亚洲, 王惠, 张天赐, 李来生. 色谱, 2020, 38(4):464-475.
23. [23]
  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.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.
24. [24]
  ZHAO D Y, HUO Q S, FENG J L, CHMELKA B F, STUCKY G D. J. Am. Chem. Soc., 1998, 120(24):6024-6036.ZHAO D Y, HUO Q S, FENG J L, CHMELKA B F, STUCKY G D. J. Am. Chem. Soc., 1998, 120(24):6024-6036.
25. [25]
  SHUANG Y Z, LIAO Y Q, WANG H, WANGY X, LI L S. Chirality, 2020, 32(2):168-184.SHUANG Y Z, LIAO Y Q, WANG H, WANGY X, LI L S. Chirality, 2020, 32(2):168-184.
26. [26]
  NG S C, CHEN L, ZHANG L F, CHING C B. Tetrahedron Lett., 2002, 43(4):677-681.NG S C, CHEN L, ZHANG L F, CHING C B. Tetrahedron Lett., 2002, 43(4):677-681.
27. [27]
  FANALI C, FANALI S, CHANKVETADZE B. Chromatographia, 2016, 79(3-4):119-124.FANALI C, FANALI S, CHANKVETADZE B. Chromatographia, 2016, 79(3-4):119-124.
28. [28]
  MERINO M E D, ECHEVARRIA R N, LUBOMIRSKY E, PADRO J M, CASTELLS C B. Microchem. J., 2019, 149:103970.MERINO M E D, ECHEVARRIA R N, LUBOMIRSKY E, PADRO J M, CASTELLS C B. Microchem. J., 2019, 149:103970.
29. [29]
  CHANG Y X, BAI B, DU L M, JING X, LI C F, FU Y L. Asian J. Chem., 2013, 25(18):10067-10070.CHANG Y X, BAI B, DU L M, JING X, LI C F, FU Y L. Asian J. Chem., 2013, 25(18):10067-10070.
30. [30]
  YAO X B, TAN T T Y, WANG Y. J. Chromatogr. A, 2014, 1326:80-88.YAO X B, TAN T T Y, WANG Y. J. Chromatogr. A, 2014, 1326:80-88.

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

吡啶二甲酰胺基桥联双β-环糊精手性固定相的制备和评价

通讯作者: 李来生,E-mail:lilaishengcn@163.com

English

Preparation and Evaluation of a Pyridinediamide Bridged Bis(β-cyclodextrin) Chiral Stationary Phase

Corresponding author: LI Lai-Sheng, lilaishengcn@163.com

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

吡啶二甲酰胺基桥联双β-环糊精手性固定相的制备和评价

通讯作者: 李来生,E-mail:lilaishengcn@163.com

English

Preparation and Evaluation of a Pyridinediamide Bridged Bis(β-cyclodextrin) Chiral Stationary Phase

Corresponding author: LI Lai-Sheng, lilaishengcn@163.com

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

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

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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