Citation: Qian Liu, Yi Shi, Kaiya Wang, Xiao-Yu Hu. Tailoring cascade hydrolysis and cyclization efficiency in confined spaces via spatial and electrostatic regulation[J]. Chinese Chemical Letters, ;2025, 36(12): 111462. doi: 10.1016/j.cclet.2025.111462 shu

Tailoring cascade hydrolysis and cyclization efficiency in confined spaces via spatial and electrostatic regulation

Qian Liu ^{a, 1} ,
Yi Shi ^{b, 1} ,
Kaiya Wang ^{a, *,} ,
Xiao-Yu Hu ^{a, c, *,}

a.
College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 211106, China
b.
School of Physics, Peking University, Beijing 100871, China
c.
College of Chemistry and Materials, Jiangxi Normal University, Nanchang 330022, China

kwang6@nuaa.edu.cn

huxy@nuaa.edu.cn

Received Date: 8 April 2025
Revised Date: 7 June 2025
Accepted Date: 13 June 2025
Available Online: 14 June 2025

Figures(5)

Intramolecular end-to-end reactions of long-chain linear precursors remain challenging due to their inherent tendency to undergo intermolecular reactions. Herein, we investigated the cascade hydrolysis and intramolecular cyclization reactions of three guests with varying lengths within the well-defined nanocavities of cavitands in aqueous solution. Driven by hydrophobic effect, these guests were encapsulated within the dimeric capsules, adopting distinct conformations and orientations due to spatial constraints. Specifically, the shorter guest maintained an extended linear geometry, whereas the longer guests adopted a folded binding mode. Upon initiating the reaction, the terminal residue of the shorter guest displayed lower reactivity, while the longer guests, preorganized within the cavity, underwent efficient cyclization, resulting in significant differences in reaction kinetics. Furthermore, electrostatic potential fields played a critical role in modulating reaction rates, with the positively charged cavitand accelerating the reaction more efficiently compared to its negatively charged counterpart, likely due to stabilization of the anionic transition state. This study provides an effective strategy for designing enzyme-mimetic nanoreactors through the utilization of well-defined nanospaces.
- Supramolecular,
- Cavitand,
- Intramolecular cyclization,
- Cascade reaction,
- Spatial and electrostatic regulation
1. [1]
  B. Hauer, ACS Catal. 10 (2020) 8418–8427. doi: 10.1021/acscatal.0c01708
2. [2]
  G.W. Gokel, W.M. Leevy, M.E. Weber, Chem. Rev. 104 (2004) 2723–2750.
3. [3]
  Y.M. Zhang, Y.H. Liu, Y. Liu, Adv. Mater. 32 (2020) 1806158.
4. [4]
  Y. Razuvayeva, R. Kashapov, L. Zakharova, Supramol. Chem. 32 (2020) 178–206. doi: 10.1080/10610278.2020.1725515
5. [5]
  R.C. Mutihac, A.A. Bunaciu, H.J. Buschmann, et al., J. Incl. Phenom. Macrocycl. 98 (2020) 137–148. doi: 10.1007/s10847-020-01019-5
6. [6]
  T. Ogoshi, S. Kanai, S. Fujinami, et al., J. Am. Chem. Soc. 130 (2008) 5022–5023. doi: 10.1021/ja711260m
7. [7]
  K. Wang, J.H. Jordan, V. Krishnasamy, et al., Angew. Chem. Int. Ed. 60 (2020) 9205–9214.
8. [8]
  S. Mosca, Y. Yu, J. Rebek Jr., Nat. Protoc. 11 (2016) 1371–1387. doi: 10.1038/nprot.2016.078
9. [9]
  J. Murray, K. Kim, T. Ogoshi, et al., Chem. Soc. Rev. 46 (2017) 2479–2496.
10. [10]
  H. Takezawa, K. Iizuka, M. Fujita, Angew. Chem. Int. Ed. 63 (2024) e202319140.
11. [11]
  Q. Zhang, K. Tiefenbacher, Nat. Chem. 7 (2015) 197–202. doi: 10.1038/nchem.2181
12. [12]
  K. Wang, J.H. Jordan, X.Y. Hu, et al., Angew. Chem. Int. Ed. 59 (2020) 13712–13721. doi: 10.1002/anie.202000045
13. [13]
  M. Morimoto, S.M. Bierschenk, K.T. Xia, et al., Nat. Catal. 3 (2020) 969–984. doi: 10.1038/s41929-020-00528-3
14. [14]
  K. Wang, X. Tian, J.H. Jordan, et al., Chin. Chem. Lett. 33 (2022) 89–96.
15. [15]
  Q. Liu, M. Zuo, K. Wang, et al., Chem. Commun. 59 (2023) 13707–13710. doi: 10.1039/d3cc04040b
16. [16]
  K. Wang, Y. Shen, P. Jeyakkumar, et al., Curr. Opin. Green Sustain. Chem. 41 (2023) 100823.
17. [17]
  K. Wang, M. Zuo, T. Zhang, et al., Chin. Chem. Lett. 34 (2023) 107848.
18. [18]
  C. Wang, L. Xu, Z. Jia, et al., Chin. Chem. Lett. 35 (2024) 109075.
19. [19]
  J.R. Moran, S. Karbach, D.J. Cram, J. Am. Chem. Soc. 104 (1982) 5826–5828. doi: 10.1021/ja00385a064
20. [20]
  K. Wang, Q. Liu, L. Zhou, et al., Chin. Chem. Lett. 34 (2023) 108559.
21. [21]
  K. Wang, K. Yan, Q. Liu, et al., Molecules 29 (2024) 5854–5871. doi: 10.3390/molecules29245854
22. [22]
  R. Eelkema, K. Maeda, B. Odell, et al., J. Am. Chem. Soc. 129 (2007) 12384–12385. doi: 10.1021/ja074997i
23. [23]
  Y. Gao, X. Tian, X. Xiong, et al., Int. J. Biol. Macromol. 265 (2024) 130680–130689.
24. [24]
  X.Q. Xu, X.Q. Wang, W. Wang, Chin. Chem. Lett. 34 (2023) 107665.
25. [25]
  F.U. Rahman, J.M. Yang, Y.H. Wan, et al., Chem. Commun. 56 (2020) 6945–6948. doi: 10.1039/d0cc02778b
26. [26]
  N.W. Wu, J. Rebek Jr., J. Am. Chem. Soc. 138 (2016) 7512–7515. doi: 10.1021/jacs.6b04278
27. [27]
  I. Martin-Torres, G. Ogalla, J.M. Yang, et al., Angew. Chem. Int. Ed. 60 (2021) 9339–9344. doi: 10.1002/anie.202017035
28. [28]
  Q. Shi, D. Masseroni, J. Rebek Jr., J. Am. Chem. Soc. 138 (2016) 10846–10848. doi: 10.1021/jacs.6b06950
29. [29]
  J.M. Yang, Y. Yu, J. Rebek Jr., J. Am. Chem. Soc. 143 (2021) 2190–2193. doi: 10.1021/jacs.0c12302
30. [30]
  W. Yao, K. Wang, Y.A. Ismaiel, et al., J. Phys. Chem. B 125 (2021) 9333–9340. doi: 10.1021/acs.jpcb.1c05238
31. [31]
  M.B. Hillyer, C.L.D. Gibb, P. Sokkalingam, et al., Org. Lett. 18 (2016) 4048–4051. doi: 10.1021/acs.orglett.6b01903
32. [32]
  J. Kiruthika, S. Srividhya, M. Arunachalam, Org. Lett. 22 (2020) 7831–7836. doi: 10.1021/acs.orglett.0c02710
33. [33]
  H. Sun, S. Li, Q. Liu, et al., Chin. Chem. Lett. 36 (2025) 109999.
34. [34]
  K. Wang, X. Cai, W. Yao, et al., J. Am. Chem. Soc. 141 (2019) 6740–6747. doi: 10.1021/jacs.9b02287
35. [35]
  M. Zarska, F. Novotny, F. Havel, et al., Bioconjugate Chem. 27 (2016) 2558–2574. doi: 10.1021/acs.bioconjchem.6b00491
36. [36]
  S. Liu, D.H. Russell, N.F. Zinnel, et al., J. Am. Chem. Soc. 135 (2013) 4314–4324. doi: 10.1021/ja310741q
37. [37]
  J.W. Barnett, B.C. Gibb, H.S. Ashbaugh, J. Phys. Chem. B 120 (2016) 10394–10402. doi: 10.1021/acs.jpcb.6b06496
1. [1]
  Hao Sun , Shengke Li , Qian Liu , Minzan Zuo , Xueqi Tian , Kaiya Wang , Xiao-Yu Hu . Supramolecular prodrug vesicles for selective antimicrobial therapy employing a chemo-photodynamic strategy. Chinese Chemical Letters, 2025, 36(3): 109999-. doi: 10.1016/j.cclet.2024.109999
2. [2]
  Hong-Jin Liao , Zhu Zhuo , Qing Li , Yoshihito Shiota , Jonathan P. Hill , Katsuhiko Ariga , Zi-Xiu Lu , Lu-Yao Liu , Zi-Ang Nan , Wei Wang , You-Gui Huang . A new class of crystalline X-ray induced photochromic materials assembled from anion-directed folding of a flexible cation. Chinese Chemical Letters, 2024, 35(8): 109052-. doi: 10.1016/j.cclet.2023.109052
3. [3]
  Zhikang Wu , Guoyong Dai , Qi Li , Zheyu Wei , Shi Ru , Jianda Li , Hongli Jia , Dejin Zang , Mirjana Čolović , Yongge Wei . POV-based molecular catalysts for highly efficient esterification of alcohols with aldehydes as acylating agents. Chinese Chemical Letters, 2024, 35(8): 109061-. doi: 10.1016/j.cclet.2023.109061
4. [4]
  Rui Wang , Yang Liang , Julius Rebek Jr. , Yang Yu . Stabilization and detection of labile reaction intermediates in supramolecular containers. Chinese Chemical Letters, 2024, 35(6): 109228-. doi: 10.1016/j.cclet.2023.109228
5. [5]
  Ji-Jia Zhou , Li-Gao Liu , Zhen-Tao Zhang , Hao-Xuan Dong , Xin Lu , Zhou Xu , Xin-Qi Zhu , Bo Zhou , Long-Wu Ye . Copper-catalyzed asymmetric cascade diyne cyclization/Meinwald rearrangement. Chinese Chemical Letters, 2025, 36(9): 110870-. doi: 10.1016/j.cclet.2025.110870
6. [6]
  Zhibin Ren , Shan Li , Xiaoying Liu , Guanghao Lv , Lei Chen , Jingli Wang , Xingyi Li , Jiaqing Wang . Penetrating efficiency of supramolecular hydrogel eye drops: Electrostatic interaction surpasses ligand-receptor interaction. Chinese Chemical Letters, 2024, 35(11): 109629-. doi: 10.1016/j.cclet.2024.109629
7. [7]
  Xuanyu Wang , Zhao Gao , Wei Tian . Supramolecular confinement effect enabling light-harvesting system for photocatalytic α-oxyamination reaction. Chinese Chemical Letters, 2024, 35(11): 109757-. doi: 10.1016/j.cclet.2024.109757
8. [8]
  Kebo Xie , Qian Zhang , Fei Ye , Jungui Dai . A multi-enzymatic cascade reaction for the synthesis of bioactive C-oligosaccharides. Chinese Chemical Letters, 2024, 35(6): 109028-. doi: 10.1016/j.cclet.2023.109028
9. [9]
  Yi-Fan Wang , Hao-Yun Yu , Hao Xu , Ya-Jie Wang , Xiaodi Yang , Yu-Hui Wang , Ping Tian , Guo-Qiang Lin . Rhodium(Ⅲ)-catalyzed diastereo- and enantioselective hydrosilylation/cyclization reaction of cyclohexadienone-tethered α, β-unsaturated aldehydes. Chinese Chemical Letters, 2024, 35(9): 109520-. doi: 10.1016/j.cclet.2024.109520
10. [10]
  Yi-Kao Xu , Guo-Ping Luo , Liang-Bin Hu , Wei-Min He . Asymmetric Büchner reaction and arene cyclopropanation via copper-catalyzed controllable cyclization of diynes. Chinese Chemical Letters, 2025, 36(8): 111226-. doi: 10.1016/j.cclet.2025.111226
11. [11]
  Yue Sun , Yingnan Zhu , Jiahang Si , Ruikang Zhang , Yalan Ji , Jinjie Fan , Yuze Dong . Glucose-activated nanozyme hydrogels for microenvironment modulation via cascade reaction in diabetic wound. Chinese Chemical Letters, 2025, 36(4): 110012-. doi: 10.1016/j.cclet.2024.110012
12. [12]
  Xinghui Yao , Zhouyu Wang , Da-Gang Yu . Sustainable electrosynthesis: Enantioselective electrochemical Rh(III)/chiral carboxylic acid-catalyzed oxidative CH cyclization coupled with hydrogen evolution reaction. Chinese Chemical Letters, 2024, 35(9): 109916-. doi: 10.1016/j.cclet.2024.109916
13. [13]
  Conghui Wang , Lei Xu , Zhenhua Jia , Teck-Peng Loh . Recent applications of macrocycles in supramolecular catalysis. Chinese Chemical Letters, 2024, 35(4): 109075-. doi: 10.1016/j.cclet.2023.109075
14. [14]
  Xiangjun Zhang , Xiaodi Yang , Yan Wang , Zhongping Xu , Sisi Yi , Tao Guo , Yue Liao , Xiyu Tang , Jianxiang Zhang , Ruibing Wang . A supramolecular nanoprodrug for prevention of gallstone formation. Chinese Chemical Letters, 2025, 36(2): 109854-. doi: 10.1016/j.cclet.2024.109854
15. [15]
  Xiaoman Dang , Zhiying Wu , Tangxin Xiao , Zhouyu Wang , Leyong Wang . Highly robust supramolecular polymer networks crosslinked by metallacycles. Chinese Chemical Letters, 2024, 35(12): 110208-. doi: 10.1016/j.cclet.2024.110208
16. [16]
  Xinguo Mao , Shuo Zhang , Qiang Shi , Hua Cheng , Leyong Wang . Macrocyclic host molecules: Rising as a promising supramolecular material. Chinese Chemical Letters, 2025, 36(6): 110950-. doi: 10.1016/j.cclet.2025.110950
17. [17]
  Wenlong Li , Feishi Shan , Qingdong Bao , Qinghua Li , Hua Gao , Leyong Wang . Supramolecular assembly nanoparticle for trans-epithelial treatment of keratoconus. Chinese Chemical Letters, 2024, 35(10): 110060-. doi: 10.1016/j.cclet.2024.110060
18. [18]
  Chao Zhang , Ai-Feng Liu , Shihui Li , Fang-Yuan Chen , Jun-Tao Zhang , Fang-Xing Zeng , Hui-Chuan Feng , Ping Wang , Wen-Chao Geng , Chuan-Rui Ma , Dong-Sheng Guo . A supramolecular formulation of icariin@sulfonatoazocalixarene for hypoxia-targeted osteoarthritis therapy. Chinese Chemical Letters, 2025, 36(1): 109752-. doi: 10.1016/j.cclet.2024.109752
19. [19]
  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
20. [20]
  Pan-Pan Hua , Hui-Jun Feng , Shu-Ning Lan , Francisco Aznarez , Li-Fang Zhang . Post-modification-induced supramolecular transformation of Hopf link to macrocycle. Chinese Chemical Letters, 2025, 36(6): 110684-. doi: 10.1016/j.cclet.2024.110684

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(16)
HTML views(6)

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