Citation: Hu Cong, Li Li, Yang Na, Zhang Ziheng, Xie Shengming, Yuan Liming. Chiral Metal-Organic Framework [Cu(S-mal)(bpy)]_n Used for Separation of Racemates in High Performance Liquid Chromatography[J]. Acta Chimica Sinica, ;2016, 74(10): 819-824. doi: 10.6023/A16070349 shu

Chiral Metal-Organic Framework [Cu(S-mal)(bpy)]_n Used for Separation of Racemates in High Performance Liquid Chromatography

1.
Faculty of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500

Corresponding author: Xie Shengming, Yuan Liming,
Received Date: 16 July 2016

Fund Project:

Chiral metal-organic framework materials, as a new type of porous materials, have attracted much attention in the field of chiral separation. In this paper, a homochiral MOF [Cu(S-mal)(bpy)]_n with 3D chiral networks was synthesized by the reaction of ligands (S-malic acid and 4,4'-bipyridine) with copper acetate via a solvothermal method. A packed chiral column for high performance liquid chromatography was fabricated using [Cu(S-mal)(bpy)]_n as stationary phase. Before the packing, the MOF crystals was crushed in ethanol applying soft pressure and then the MOF with suitable particle size (5~10 m) was obtained via solvent suspension. A 4.2 g mass of prepared MOF was suspended in a mixture of hexane and isopropanol. In order to control the packing quality, the suspension of MOF was packed into a stainless steel empty column (25 cm long×4.6 mm i.d.) under 40 MPa using hexane/isopropanol (9:1, V/V) as the slurry solvent according to a conventional high pressure slurry packing procedure. To investigate the chiral recognition ability of this stationary phase, a series of racemic compounds were separated on the chiral MOF column using different ratio of n-hexane/isopropanol as mobile phase. The results showed that the chiral column exhibited good resolving ability towards 17 racemates, including alcohols, ketones, flavonoids, phenols and amines. For instance, the resolution value of 1-(1-naphthyl)ethanol could reach 4.5. Compared with three kinds of homochiral MOFs columns previously reported by our group, this column showed better chiral recognition ability and higher resolution toward racemates, and has a good complementary for chiral separation. The [Cu(S-mal)(bpy)]_n possesses cavities with average dimensions (5 Å×5 Å×6 Å), which were interconnected by narrow windows with diameter ≤3 Å. Therefore, the chiral recognition mostly depends on the surface of the MOF crystal in which the steric fit between the chiral networks and conformation of the solute molecule is the main interactive force. Besides, many other interactions such as the hydro-gen-bondings, dispersion forces, dipole-dipole interaction, and π-π interactions which come from the solutes, chiral stationary phase and the mobile phase may also play some role. The reproducibility and stability of the chiral column were evaluated. The results showed that the chiral column showed good reproducibility and stability for enantioseparation.
- metal-organic framework,
- high performance liquid chromatography,
- S-malic acid,
- chiral separation
1. [1]
  [1] Wei, W. Y.; Fang, J.; Kong, H. N.; Han, J. Y.; Chang, H. Y. Prog. Chem. 2005, 17, 1110(in Chinese). (魏文英, 方键, 孔海宁, 韩金玉, 常贺英, 化学进展, 2005, 17, 1110.)
2. [2]
  [2] Mu, C. Z.; Xu, F.; Lei, W. Prog. Chem. 2007, 19, 1345(in Chinese). (穆翠枝, 徐峰, 雷威, 化学进展, 2007, 19, 1345.)
3. [3]
  [3] Mueller, U.; Schubert, M.; Teich, F.; Puetter, H.; Schierle-Arndt, K.; Pastre, J. J. Mater. Chem. 2006, 16, 626.
4. [4]
  [4] Qi, X. Y.; Li, X. J.; Bai, Y.; Liu, H. W. Chin. J. Chromatogr. 2016, 34, 10(in Chinese). (祁晓月, 李先江, 白玉, 刘虎威, 色谱, 2016, 34, 10.)
5. [5]
  [5] Xie, S. M.; Yuan, L. M. Prog. Chem. 2013, 25, 1763(in Chinese). (谢生明, 袁黎明, 化学进展, 2013, 25, 1763.)
6. [6]
  [6] Li, X. J.; He, C. F.; Huang, B.; Lin, Z. Y. Chem. Ind. Eng. Prog. 2016, 35, 586(in Chinese). (李小娟, 何长发, 黄斌, 林振宇, 刘以凡, 林春香, 化工进展, 2016, 35, 586.)
7. [7]
  [7] Pham, M. H.; Vuong, G. T.; Fontaine, F. G. Cryst. Growth Des. 2011, 12, 1008.
8. [8]
  [8] Lee, J. Y.; Pan, L.; Huang, X. Y. Adv. Funct. Mater. 2011, 21, 993.
9. [9]
  [9] Xiang, Z. H.; Hu, Z.; Cao, D. P. Angew. Chem., Int. Ed. 201l, 50, 491.
10. [10]
  [10] Bao, Z.; Yu, L.; Ren, Q. J. Coll. Inter. Sci. 2011, 353, 549.
11. [11]
  [11] Kim, H.; Park, J.; Jung, Y. Phys. Chem. Chem. Phys. 2013, 15, 19644.
12. [12]
  [12] Wang, B.; Lv, X. L.; Feng, D. W.; Xie, L. H.; Zhang, J.; Li, M.; Xie, Y. B.; Li, J. R.; Zhou, H. C. J. Am. Chem. Soc. 2016, 138, 6204.
13. [13]
  [13] Jia, J. T.; Wang, L.; Zhao, Q.; Sun, F. X.; Zhu, G. S. Acta Chim. Sinica 2013, 71, 1492(in Chinese). (贾江涛, 王蕾, 赵晴, 孙福兴, 朱广山, 化学学报, 2013, 71, 1492.)
14. [14]
  [14] Xu, J.; Shimakoshi, H.; Hisaeda, Y. J. Organomet. Chem. 2015, 782, 89.
15. [15]
  [15] Karimi, Z.; Morsali, A. J. Mater Chem. A 2013, 1, 3047.
16. [16]
  [16] Guo, R. M.; Bai, J. Q.; Zhang, H.; Xie, Y. B.; Li, J. R. Prog. Chem. 2016, 28, 232(in Chinese). (郭瑞梅, 白金泉, 张恒, 谢亚勃, 李建荣, 化学进展, 2016, 28, 232.)
17. [17]
  [17] Huang, G.; Chen, Y. Z.; Jiang, H. L. Acta Chim. Sinica 2016, 74, 113(in Chinese). (黄刚, 陈玉贞, 江海龙, 化学学报, 2016, 74, 113.)
18. [18]
  [18] Qian, J. J.; Qiu, L. G.; Wang, Y. M. Dalton Trans. 2014, 43, 3978.
19. [19]
  [19] Nickerl, G.; Senkovska, I.; Kaskel, S. Chem. Commun. 2015, 51, 2280.
20. [20]
  [20] Ezuhara, T.; Endo, K.; Aoyama, Y. J. Am. Chem. Soc. 1999, 121, 3279.
21. [21]
  [21] Dai, R. J.; Tong, B.; Tang, L.; Deng, Y. L.; Fu, R. N. Acta Chim. Sinica 2006, 64, 1248(in Chinese). (戴荣继, 佟斌, 唐力, 邓玉林, 傅若农, 化学学报, 2006, 64, 1248.)
22. [22]
  [22] Gu, Z. Y.; Jiang, D. Q.; Wang, H. F.; Cui, X. Y.; Yan, X. P. J. Phys. Chem. C 2010, 114, 311.
23. [23]
  [23] Gu, Z. Y.; Yang, C. X.; Chang, N.; Yan, X. P. Acc. Chem. Res. 2012, 45, 734.
24. [24]
  [24] Li, J. R.; Sculley, J.; Zhou, H. C. Chem. Rev. 2012, 112, 869.
25. [25]
  [25] Gu, Z. Y.; Yan, X. P. Angew. Chem., Int. Ed. 2010, 49, 1477.
26. [26]
  [26] Zhao, W. W.; Zhang, C. Y.; Yan, Z. G.; Bai, L. P.; Wang, X. Y.; Huang, H. L.; Zhou, Y. Y.; Xie, Y. B.; Li, F. S.; Li, J. R. J. Chromatogr. A 2014, 1370, 121.
27. [27]
  [27] Zhu, Z. J.; Wang, Q. Q.; Kang, J. W. Acta Chim. Sinica 2008, 66, 1845(in Chinese). (朱智甲, 王倩倩, 康经武, 化学学报, 2008, 66, 1845.)
28. [28]
  [28] Ezuhara, T.; Endo, K.; Aoyama, Y. J. Am. Chem. Soc. 1999, 121, 3279.
29. [29]
  [29] Nuzhdin, A. L.; Dybtsev, D. N.; Bryliakov, K. P. J. Am. Chem. Soc. 2007, 129, 12958.
30. [30]
  [30] Padmanaban, M.; Müller, P.; Lieder, C.; Gedrich, K.; Grunker, R.; Bon, V.; Senkovska, I.; Baumgartner, S.; Opelt, S.; Paasch, S.; Brunner, E.; Glorius, F.; Klemm, E.; Kaskel, S. Chem. Commun. 2011, 47, 12089.
31. [31]
  [31] Tanaka, K.; Muraoka, T.; Hirayama, D.; Ohnish, A. Chem. Commun. 2012, 48, 8577.
32. [32]
  [32] Zhou, L. L.; Sun, W. Z.; Wang, J. Y.; Yuan, L. M. Acta Chim. Sinica 2008, 66, 2309(in Chinese). (周玲玲, 孙文卓, 王剑瑜, 袁黎明, 化学学报, 2008, 66, 2309.)
33. [33]
  [33] Zhang, M.; Pu, Z. J.; Chen, X. L.; Gong, X. L.; Zhu, A. X.; Yuan, L. M. Chem. Commun. 2013, 49, 5201.
34. [34]
  [34] Zhang, M.; Zhang, J. H.; Zhang, Y.; Wang, B. J.; Xie, S. M.; Yuan, L. M. J. Chromatogr. A 2014, 1325, 163.
35. [35]
  [35] Kong, J.; Zhang, M.; Duan, A. H.; zhang, J. H.; Yang, R.; Yuan, L. M. J. Sep. Sci. 2015, 38, 556.
36. [36]
  [36] Nong, R. Y.; Kong, J.; Zhang, J. H.; Chen, L.; Tang, B.; Xie, S. M.; Yuan, L. M. Chem. J. Chin. Univ. 2016, 37, 19(in Chinese). (农蕊瑜, 孔娇, 章俊辉, 陈玲, 汤波, 谢生明, 袁黎明, 高等学校化学学报, 2016, 37, 19.)
37. [37]
  [37] Ma, S.; Shen, S.; Lee, H.; Eriksson, M.; Zeng, X.; Xu, J.; Fandrick, K.; Yee, N.; Senanayake, C.; Grinberg, N. J. Chromatogr. A 2009, 1216, 3784.
38. [38]
  [38] Chankvetadze, B. J. Chromatogr. A 2012, 1269, 26.
39. [39]
  [39] Zavakhina, M. S.; Samsonenko, D. G.; Virovets, A. V.; Dybtsev, D. N.; Fedin, V. P. J. Solid State Chem. 2014, 210, 125.
40. [40]
  [40] Xie, S. M.; Zhang, X. H.; Zhang, Z. J.; Yuan, L. M. Anal. Lett. 2013, 46, 753.
1. [1]
  Fan Wu , Wenchang Tian , Jin Liu , Qiuting Zhang , YanHui Zhong , Zian Lin . Core-Shell Structured Covalent Organic Framework-Coated Silica Microspheres as Mixed-Mode Stationary Phase for High Performance Liquid Chromatography. University Chemistry, 2024, 39(11): 319-326. doi: 10.12461/PKU.DXHX202403031
2. [2]
  Keying Qu , Jie Li , Ziqiu Lai , Kai Chen . Unveiling the Mystery of Chirality from Tartaric Acid. University Chemistry, 2024, 39(9): 369-378. doi: 10.12461/PKU.DXHX202310091
3. [3]
  Peiran ZHAO , Yuqian LIU , Cheng HE , Chunying DUAN . A functionalized Eu³⁺ metal-organic framework for selective fluorescent detection of pyrene. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 713-724. doi: 10.11862/CJIC.20230355
4. [4]
  Xilin Zhao , Xingyu Tu , Zongxuan Li , Rui Dong , Bo Jiang , Zhiwei Miao . Research Progress in Enantioselective Synthesis of Axial Chiral Compounds. University Chemistry, 2024, 39(11): 158-173. doi: 10.12461/PKU.DXHX202403106
5. [5]
  Wenxiu Yang , Jinfeng Zhang , Quanlong Xu , Yun Yang , Lijie Zhang . Bimetallic AuCu Alloy Decorated Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312014-. doi: 10.3866/PKU.WHXB202312014
6. [6]
  Aiai WANG , Lu ZHAO , Yunfeng BAI , Feng FENG . Research progress of bimetallic organic framework in tumor diagnosis and treatment. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1825-1839. doi: 10.11862/CJIC.20240225
7. [7]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . Kinetic Resolution Enabled by Photoexcited Chiral Copper Complex-Mediated Alkene E→Z Isomerization: A Comprehensive Chemistry Experiment for Undergraduate Students. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
8. [8]
  Tiantian MA , Sumei LI , Chengyu ZHANG , Lu XU , Yiyan BAI , Yunlong FU , Wenjuan JI , Haiying YANG . Methyl-functionalized Cd-based metal-organic framework for highly sensitive electrochemical sensing of dopamine. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 725-735. doi: 10.11862/CJIC.20230351
9. [9]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
10. [10]
  Wendian XIE , Yuehua LONG , Jianyang XIE , Liqun XING , Shixiong SHE , Yan YANG , Zhihao HUANG . Preparation and ion separation performance of oligoether chains enriched covalent organic framework membrane. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1528-1536. doi: 10.11862/CJIC.20240050
11. [11]
  Yanhui Zhong , Ran Wang , Zian Lin . Analysis of Halogenated Quinone Compounds in Environmental Water by Dispersive Solid-Phase Extraction with Liquid Chromatography-Triple Quadrupole Mass Spectrometry. University Chemistry, 2024, 39(11): 296-303. doi: 10.12461/PKU.DXHX202402017
12. [12]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431
13. [13]
  Xiaoling LUO , Pintian ZOU , Xiaoyan WANG , Zheng LIU , Xiangfei KONG , Qun TANG , Sheng WANG . Synthesis, crystal structures, and properties of lanthanide metal-organic frameworks based on 2, 5-dibromoterephthalic acid ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1143-1150. doi: 10.11862/CJIC.20230271
14. [14]
  Jing SU , Bingrong LI , Yiyan BAI , Wenjuan JI , Haiying YANG , Zhefeng Fan . Highly sensitive electrochemical dopamine sensor based on a highly stable In-based metal-organic framework with amino-enriched pores. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1337-1346. doi: 10.11862/CJIC.20230414
15. [15]
  Youlin SI , Shuquan SUN , Junsong YANG , Zijun BIE , Yan CHEN , Li LUO . Synthesis and adsorption properties of Zn(Ⅱ) metal-organic framework based on 3, 3', 5, 5'-tetraimidazolyl biphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1755-1762. doi: 10.11862/CJIC.20240061
16. [16]
  Renxiao Liang , Zhe Zhong , Zhangling Jin , Lijuan Shi , Yixia Jia . A Palladium/Chiral Phosphoric Acid Relay Catalysis for the One-Pot Three-Step Synthesis of Chiral Tetrahydroquinoline. University Chemistry, 2024, 39(5): 209-217. doi: 10.3866/PKU.DXHX202311024
17. [17]
  Haiying Wang , Andrew C.-H. Sue . How to Visually Identify Homochiral Crystals. University Chemistry, 2024, 39(3): 78-85. doi: 10.3866/PKU.DXHX202309004
18. [18]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
19. [19]
  Shengbiao Zheng , Liang Li , Nini Zhang , Ruimin Bao , Ruizhang Hu , Jing Tang . Metal-Organic Framework-Derived Materials Modified Electrode for Electrochemical Sensing of Tert-Butylhydroquinone: A Recommended Comprehensive Chemistry Experiment for Translating Research Results. University Chemistry, 2024, 39(7): 345-353. doi: 10.3866/PKU.DXHX202310096
20. [20]
  Conghao Shi , Ranran Wang , Juli Jiang , Leyong Wang . The Illustration on Stereoisomers of Macrocycles Containing Multiple Chiral Centers via Tröger Base-based Macrocycles. University Chemistry, 2024, 39(7): 394-397. doi: 10.3866/PKU.DXHX202311034

Get Citation

PDF

XML

Metrics

PDF Downloads(8)
Abstract views(2164)
HTML views(283)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Chiral Metal-Organic Framework [Cu(S-mal)(bpy)]n Used for Separation of Racemates in High Performance Liquid Chromatography

Metrics

通讯作者: 陈斌, bchen63@163.com

Chiral Metal-Organic Framework [Cu(S-mal)(bpy)]_n Used for Separation of Racemates in High Performance Liquid Chromatography