Citation: Jun-Hui Zhang, Rui-Xue Liang, Bin Huang, Li-Qin Yu, Juan Chen, Bang-Jin Wang, Sheng-Ming Xie, Li-Ming Yuan. Preparation of a homochiral metal-organic cage and its bonded silicas for efficient enantioseparation in high-performance liquid chromatography and gas chromatography[J]. Chinese Chemical Letters, ;2026, 37(1): 111146. doi: 10.1016/j.cclet.2025.111146 shu

Preparation of a homochiral metal-organic cage and its bonded silicas for efficient enantioseparation in high-performance liquid chromatography and gas chromatography

Yunnan Key Laboratory of Modern Separation Analysis and Substance Transformation, College of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, China

zjh19861202@126.com

wangbangjin711@163.com

xieshengming_2006@163.com

Received Date: 17 July 2024
Revised Date: 7 February 2025
Accepted Date: 26 March 2025
Available Online: 26 March 2025

Figures(8)

Developing a chiral material as versatile and universal chiral stationary phase (CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance. In this study, we demonstrated for the first time that a chiral metal-organic cage (MOC), [Zn₆M₄], as a universal chiral recognition material for both multi-mode high-performance liquid chromatography (HPLC) and capillary gas chromatography (GC) enantioseparation. Two novel HPLC CSPs with different bonding arms (CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn₆M₄] onto thiolated silica via thiol-ene click chemistry. Meanwhile, a capillary GC column statically coated with the chiral MOC [Zn₆M₄] was also fabricated. The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC (NP-HPLC) and reversed phase (RP-HPLC) but also in GC, and various racemates were well separated, including alcohols, diols, esters, ketones, ethers, amines, and epoxides. Importantly, CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation, which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns, suggesting the great potential of the two prepared CSPs in enantioseparation. This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC, and also paves the way to expand the potential applications of MOCs.
- Chiral metal-organic cage,
- Chiral stationary phase,
- Chiral separation,
- High-performance liquid chromatography,
- Gas chromatography
1. [1]
  T.J. Ward, K.D. Ward, Anal. Chem. 84 (2012) 626–635. doi: 10.1021/ac202892w
2. [2]
  H. Lorenz, A. Seidel-Morgenstern, Angew. Chem. Int. Ed. 53 (2014) 1218–1250. doi: 10.1002/anie.201302823
3. [3]
  J. Shen, Y. Okamoto, Chem. Rev. 116 (2016) 1094–1138. doi: 10.1021/acs.chemrev.5b00317
4. [4]
  J. Sui, N. Wang, J. Wang, et al., Chem. Sci. 14 (2023) 11955–12003. doi: 10.1039/D3SC01630G
5. [5]
  V. Schurig, H.P. Nowotny, Angew. Chem. Int. Ed. 29 (1990) 939–957. doi: 10.1002/anie.199009393
6. [6]
  X.B. Zheng, H. Zhang, Y. Zhang, et al., Anal. Chem. 88 (2016) 4955–4964. doi: 10.1021/acs.analchem.6b00897
7. [7]
  H. Li, X. Wang, C. Shi, et al., Chin. Chem. Lett. 34 (2023) 107606. doi: 10.1016/j.cclet.2022.06.029
8. [8]
  D.W. Armstrong, T.J. Ward, R.D. Armstrong, et al., Science 232 (1986) 1132–1135. doi: 10.1126/science.3704640
9. [9]
  B. Chankvetadze, TrAC Trends Anal. Chem. 122 (2020) 115709. doi: 10.1016/j.trac.2019.115709
10. [10]
  Y. Okamoto, E. Yashima, Angew. Chem. Int. Ed. 37 (1998) 1020–1043. doi: 10.1002/(SICI)1521-3773(19980504)37:8<1020::AID-ANIE1020>3.0.CO;2-5
11. [11]
  S. Tang, X. Mei, W. Chen, et al., Talanta 185 (2018) 42–52. doi: 10.1016/j.talanta.2018.03.048
12. [12]
  M.H. Hyun, J. Chromatogr. A 1467 (2016) 19–32. doi: 10.1016/j.chroma.2016.07.049
13. [13]
  H. Frank, G.J. Nicholson, E. Bayer, J. Chromatogr. Sci. 15 (1977) 174–176. doi: 10.1093/chromsci/15.5.174
14. [14]
  B. Huang, K. Li, Q.Y. Ma, et al., Anal. Chem. 95 (2023) 13289–13296. doi: 10.1021/acs.analchem.3c02438
15. [15]
  V. Schurig, Angew. Chem. Int. Ed. 23 (1984) 747–780. doi: 10.1002/anie.198407473
16. [16]
  Z.Y. Gu, X.P. Yan, Angew. Chem. Int. Ed. 49 (2010) 1477–1480. doi: 10.1002/anie.200906560
17. [17]
  Z.R. Tao, J.X. Wu, Y.J. Zhao, et al., Nat. Commun. 10 (2019) 2911. doi: 10.1038/s41467-019-10971-x
18. [18]
  H. Jiang, K. Yang, X. Zhao, et al., J. Am. Chem. Soc. 143 (2021) 390–398. doi: 10.1021/jacs.0c11276
19. [19]
  C. Liu, K. Quan, H. Li, et al., Chem. Commun. 58 (2022) 13111–13114. doi: 10.1039/D2CC05149D
20. [20]
  C. Zeng, H. Yang, M. Xu, et al., Chin. Chem. Lett. 37 (2026) 110064. doi: 10.1016/j.cclet.2024.110064
21. [21]
  C. Yuan, Z. Wang, W. Xiong, et al., J. Am. Chem. Soc. 145 (2023) 18956–18967. doi: 10.1021/jacs.3c05973
22. [22]
  Y. Chen, S. Huang, L. Xia, et al., Anal. Chem. 96 (2024) 1380–1389. doi: 10.1021/acs.analchem.3c05227
23. [23]
  H.L. Qian, C.X. Yang, X.P. Yan, Nat. Commun. 7 (2016) 12104. doi: 10.1038/ncomms12104
24. [24]
  J. Xu, G. Feng, D. Ao, et al., Adv. Mater. 36 (2024) 2406256. doi: 10.1002/adma.202406256
25. [25]
  Y.P. Yang, J.K. Chen, P. Guo, et al., Microchim. Acta 189 (2022) 360. doi: 10.1007/s00604-022-05448-6
26. [26]
  Y.Y. Cui, X.Q. He, C.X. Yang, et al., TrAC Trends Anal. Chem. 139 (2021) 116268. doi: 10.1016/j.trac.2021.116268
27. [27]
  A.J. Gosselin, C.A. Rowland, E.D. Bloch, Chem. Rev. 120 (2020) 8987–9014. doi: 10.1021/acs.chemrev.9b00803
28. [28]
  C. Li, Y. Wang, Y. Lu, Chin. Chem. Lett. 31 (2020) 1183–1187. doi: 10.1016/j.cclet.2019.09.034
29. [29]
  S. Lee, H. Jeong, D. Nam, et al., Chem. Soc. Rev. 50 (2021) 528–555. doi: 10.1039/D0CS00443J
30. [30]
  J. Liu, Z. Wang, P. Cheng, et al., Nat. Rev. Chem. 6 (2022) 339–356. doi: 10.1038/s41570-022-00380-y
31. [31]
  W.M. Bloch, R. Babarao, M.L. Schneider, Chem. Sci. 11 (2020) 3664–3671. doi: 10.1039/D0SC00070A
32. [32]
  G. Liu, Y.D. Yuan, J. Wang, et al., J. Am. Chem. Soc. 140 (2018) 6231–6234. doi: 10.1021/jacs.8b03517
33. [33]
  K. Wu, K. Li, Y.J. Hou, et al., Nat. Commun. 7 (2016) 10487. doi: 10.1038/ncomms10487
34. [34]
  D. Preston, J.E.M. Lewis, J.D. Crowley, J. Am. Chem. Soc. 139 (2017) 2379–2386. doi: 10.1021/jacs.6b11982
35. [35]
  D.J. Bell, L.S. Natrajan, I.A. Riddell, Coord. Chem. Rev. 472 (2022) 214786. doi: 10.1016/j.ccr.2022.214786
36. [36]
  G. Wu, Y. Chen, S. Fang, et al., Angew. Chem. Int. Ed. 60 (2021) 16594–16599. doi: 10.1002/anie.202104164
37. [37]
  Y.L. Lai, J. Su, L.X. Wu, et al., Chin. Chem. Lett. 35 (2024) 108326. doi: 10.1016/j.cclet.2023.108326
38. [38]
  D. He, L. Zhang, T. Liu, et al., Angew. Chem. Int. Ed. 61 (2022) e202202450. doi: 10.1002/anie.202202450
39. [39]
  C. Zhu, H. Tang, K. Yang, et al., J. Am. Chem. Soc. 143 (2021) 12560–12566. doi: 10.1021/jacs.1c03652
40. [40]
  Y. Li, H. Jiang, W. Zhang, et al., J. Am. Chem. Soc. 146 (2024) 3147–3159. doi: 10.1021/jacs.3c10734
41. [41]
  T. Feng, X. Li, J. Wu, et al., Chin. Chem. Lett. 31 (2020) 95–98. doi: 10.1016/j.cclet.2019.04.059
42. [42]
  M. Zhang, M.L. Saha, M. Wang, et al., J. Am. Chem. Soc. 139 (2017) 5067–5074. doi: 10.1021/jacs.6b12536
43. [43]
  N. Ahmad, H.A. Younus, A.H. Chughtai, et al., Chem. Soc. Rev. 44 (2015) 9–25. doi: 10.1039/C4CS00222A
44. [44]
  S.M. Xie, N. Fu, L. Li, B.Y. Yuan, et al., Anal. Chem. 90 (2018) 9182–9188. doi: 10.1021/acs.analchem.8b01670
45. [45]
  B. Tang, X. Zhang, L. Geng, et al., J. Chromatogr. A 1636 (2021) 461792. doi: 10.1016/j.chroma.2020.461792
46. [46]
  Z.H. Luo, Y.L. Zhu, X.Y. Ran, Talanta 277 (2024) 126388. doi: 10.1016/j.talanta.2024.126388
47. [47]
  A.C. Eaby, D.C. Myburgh, A. Kosimov, et al., Nature 616 (2023) 288–292. doi: 10.1038/s41586-023-05749-7
48. [48]
  D. He, H. Ji, T. Liu, et al., J. Am. Chem. Soc. 146 (2024) 17438–17445. doi: 10.1021/jacs.4c04928
49. [49]
  H. Liu, J. Chen, M. Chen, et al., Anal. Chim. Acta 1274 (2023) 341496. doi: 10.1016/j.aca.2023.341496
50. [50]
  J. Zhou, J. Tang, W. Tang, TrAC-Trends Anal. Chem. 65 (2015) 22–29. doi: 10.1016/j.trac.2014.10.009
51. [51]
  X. Li, X. Jin, X. Yao, et al., J. Chromatogr. A 1467 (2016) 279–287. doi: 10.1016/j.chroma.2016.06.074
52. [52]
  H. Zhou, J. Chen, H. Li, et al., Talanta 211 (2020) 120743. doi: 10.1016/j.talanta.2020.120743
1. [1]
  Qiuting Zhang , Fan Wu , Jin Liu , Hang Su , Yanhui Zhong , Zian Lin . Facile synthesis of single-crystal 3D covalent organic frameworks as stationary phases for high-performance liquid chromatographic separation. Chinese Chemical Letters, 2025, 36(8): 110649-. doi: 10.1016/j.cclet.2024.110649
2. [2]
  Sha-Sha Meng , Xiao-Yi Fu , Hai-Yue Wei , Ming Xu , Zhi-Yuan Gu . Improving the separation ability of MOF-based stationary phases by increasing the thermodynamic differentiation of analytes. Chinese Chemical Letters, 2025, 36(9): 110720-. doi: 10.1016/j.cclet.2024.110720
3. [3]
  Chu Zeng , Han Yang , Ming Xu , Zhi-Yuan Gu . Optimizing COF crystallinity for high-resolution GC separation. Chinese Chemical Letters, 2026, 37(1): 110064-. doi: 10.1016/j.cclet.2024.110064
4. [4]
  Zhefei Hu , Jingwen Liao , Jiawen Zhou , Lulu Zhao , Yanjuan Liu , Yuefei Zhang , Wei Chen , Sheng Tang . A new green approach to synthesizing MIP-202@porous silica microspheres for positional isomer/enantiomer/hydrophilic separation. Chinese Chemical Letters, 2025, 36(1): 109985-. doi: 10.1016/j.cclet.2024.109985
5. [5]
  Zhao-Xia Lian , Xue-Zhi Wang , Chuang-Wei Zhou , Jiayu Li , Ming-De Li , Xiao-Ping Zhou , Dan Li . Producing circularly polarized luminescence by radiative energy transfer from achiral metal-organic cage to chiral organic molecules. Chinese Chemical Letters, 2024, 35(8): 109063-. doi: 10.1016/j.cclet.2023.109063
6. [6]
  Tong Zhang , Xiaojing Liang , Licheng Wang , Shuai Wang , Xiaoxiao Liu , Yong Guo . An ionic liquid assisted hydrogel functionalized silica stationary phase for mixed-mode liquid chromatography. Chinese Chemical Letters, 2025, 36(1): 109889-. doi: 10.1016/j.cclet.2024.109889
7. [7]
  Wangyan Hu , Ke Li , Xiangnan Dou , Ning Li , Xiayan Wang . Nano-sized stationary phase packings retained by single-particle frit for microchip liquid chromatography. Chinese Chemical Letters, 2024, 35(4): 108806-. doi: 10.1016/j.cclet.2023.108806
8. [8]
  Genlin Sun , Yachun Luo , Zhihong Yan , Hongdeng Qiu , Weiyang Tang . Chiral metal-organic frameworks-based materials for chromatographic enantioseparation. Chinese Chemical Letters, 2024, 35(12): 109787-. doi: 10.1016/j.cclet.2024.109787
9. [9]
  Xue-Zhi Wang , Yi-Tong Liu , Chuang-Wei Zhou , Bei Wang , Dong Luo , Mo Xie , Meng-Ying Sun , Yong-Liang Huang , Jie Luo , Yan Wu , Shuixing Zhang , Xiao-Ping Zhou , Dan Li . Amplified circularly polarized luminescence of chiral metal-organic frameworks via post-synthetic installing pillars. Chinese Chemical Letters, 2024, 35(10): 109380-. doi: 10.1016/j.cclet.2023.109380
10. [10]
  Zhiwen Li , Jingjing Zhang , Gao Li . Dynamic assembly of chiral golden knots. Chinese Journal of Structural Chemistry, 2024, 43(7): 100300-100300. doi: 10.1016/j.cjsc.2024.100300
11. [11]
  Bo Luo , Mingfang Ma , Aiyou Hao , Pengyao Xing . Arene-perfluoroarene force driven chiral transfer, chiral amplification and chiral inversion. Chinese Chemical Letters, 2026, 37(1): 111736-. doi: 10.1016/j.cclet.2025.111736
12. [12]
  Fuxing Yang , Mengjie Gong , Yifei Zhang , Bangchi Wei , Nan Huang , Jun Jiang . Organocatalytic enantioselective construction of axially chiral phosphorodithiolated styrenes. Chinese Chemical Letters, 2026, 37(1): 111219-. doi: 10.1016/j.cclet.2025.111219
13. [13]
  Ning Zhang , Mengjie Qin , Jiawen Zhu , Xuejing Lou , Xiao Tian , Wende Ma , Youmei Wang , Minghua Lu , Zongwei Cai . Thickness-controllable synthesis of metal-organic framework based hollow nanoflowers with magnetic core via liquid phase epitaxy for phosphopeptides enrichment. Chinese Chemical Letters, 2025, 36(4): 110177-. doi: 10.1016/j.cclet.2024.110177
14. [14]
  Xiaoyan Peng , Xuanhao Wu , Fan Yang , Yefei Tian , Mingming Zhang , Hongye Yuan . Gas sensors based on metal-organic frameworks: challenges and opportunities. Chinese Journal of Structural Chemistry, 2024, 43(3): 100251-100251. doi: 10.1016/j.cjsc.2024.100251
15. [15]
  Long Jin , Jian Han , Dongmei Fang , Min Wang , Jian Liao . Pd-catalyzed asymmetric carbonyl alkynylation: Synthesis of axial chiral ynones. Chinese Chemical Letters, 2024, 35(6): 109212-. doi: 10.1016/j.cclet.2023.109212
16. [16]
  Chuan-Zhi Ni , Ruo-Ming Li , Fang-Qi Zhang , Qu-Ao-Wei Li , Yuan-Yuan Zhu , Jie Zeng , Shuang-Xi Gu . A chiral fluorescent probe for molecular recognition of basic amino acids in solutions and cells. Chinese Chemical Letters, 2024, 35(10): 109862-. doi: 10.1016/j.cclet.2024.109862
17. [17]
  Wenying Cui , Zhetong Jin , Wentao Fu , Chengshuo Shen . Flag-hinge-like highly luminescent chiral nanographenes with twist geometry. Chinese Chemical Letters, 2024, 35(11): 109667-. doi: 10.1016/j.cclet.2024.109667
18. [18]
  Teng-Yu Huang , Junliang Sun , De-Xian Wang , Qi-Qiang Wang . Recent progress in chiral zeolites: Structure, synthesis, characterization and applications. Chinese Chemical Letters, 2024, 35(12): 109758-. doi: 10.1016/j.cclet.2024.109758
19. [19]
  Chuang LIU , Lichao SUN , Qingfeng ZHANG . Chiral inorganic nanocatalysts for electrochemical and enzyme-mimicked biosensing. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 59-78. doi: 10.11862/CJIC.20240406
20. [20]
  Cong Gao , Zijian Zhu , Siwei Li , Zheng Xi , Qingqing Sun , Jie Han , Rong Guo . Chiral supramolecular catalysts of helical nanoribbon: More twist, higher enantioselectivity. Chinese Chemical Letters, 2025, 36(3): 109968-. doi: 10.1016/j.cclet.2024.109968

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(5)
HTML views(1)

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