Citation: Hao Zha, Zuowei Wang, Chao Liu, Chunyan Hong. Preparing cyclic polymers at high concentrations via self-folding cyclization technique by adjusting the contents of hydrophilic units in linear precursors[J]. Chinese Chemical Letters, ;2024, 35(2): 108956. doi: 10.1016/j.cclet.2023.108956 shu

Preparing cyclic polymers at high concentrations via self-folding cyclization technique by adjusting the contents of hydrophilic units in linear precursors

Hao Zha ^a ,
Zuowei Wang ^a ,
Chao Liu ^{a, *,} ,
Chunyan Hong ^{a, b, *,}

a.
Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, China
b.
Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China

liuchao216@ustc.edu.cn

hongcy@ustc.edu.cn

Received Date: 9 July 2023
Revised Date: 14 August 2023
Accepted Date: 20 August 2023
Available Online: 23 August 2023

Figures(4)

Cyclic polymers are a class of polymers that feature endless topology, and the synthesis of cyclic polymers has attracted the attention of many researchers. Herein, cyclic polymers were efficiently constructed by self-folding cyclization technique at high concentrations. Linear poly((oligo(ethylene glycol)acrylate)-co-(dodecyl acrylate)) (P(OEGA-co-DDA)) precursors with different ratios of hydrophilic and hydrophobic moieties were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization using a bifunctional chain transfer agent with two anthryl end groups. The amphiphilic linear precursors underwent the self-folding process to generate polymeric nanoparticles in water. By irradiating the aqueous solution of the nanoparticles with 365 nm UV light, cyclic polymers were synthesized successfully via coupling of anthryl groups. The effects of the ratios of hydrophilic and hydrophobic moieties in linear P(OEGA-co-DDA) copolymers and polymer concentration on the purity of the obtained cyclic polymers were explored in detail via ¹H nuclear magnetic resonance (¹H NMR), dynamic light scattering (DLS), UV‒visible (vis) analysis, three-detection size exclusion chromatography (TD-SEC) and transmission electron microscopy (TEM). It was found that by adjusting the content of the hydrophilic segments in linear precursors, single chain polymeric nanoparticles (SCPNs) can be generated at high polymer concentrations. Therefore, cyclic polymers with high purity can be constructed efficiently. This method overcomes the limitation of traditional ring-closure method, which is typically conducted in highly dilute conditions, providing an efficient method for the scalable preparation of cyclic polymers.
- Cyclic polymers,
- Self-folding cyclization technique,
- Single chain polymeric nanoparticles,
- RAFT polymerization,
- Direct visualization
1. [1]
  T. McLeish, Science 297 (2002) 2005–2006. doi: 10.1126/science.1076810
2. [2]
  M. Kapnistos, M. Lang, D. Vlassopoulos, et al., Nat. Mater. 7 (2008) 997–1002. doi: 10.1038/nmat2292
3. [3]
  S.M. Grayson, J.M.J. Fréchet, Chem. Rev. 101 (2001) 3819–3868. doi: 10.1021/cr990116h
4. [4]
  Z. Lu, B. Guo, Y. Zhao, L. Hou, L. Xiao, Chin. Chem. Lett. 33 (2022) 825–829. doi: 10.1016/j.cclet.2021.07.033
5. [5]
  F.P. Seib, A.T. Jones, R. Duncan, J. Control. Release 117 (2007) 291–300. doi: 10.1016/j.jconrel.2006.10.020
6. [6]
  H. Wei, D.S.H. Chu, J. Zhao, J.A. Pahang, S.H. Pun, ACS Macro Lett. 2 (2013) 1047–1050. doi: 10.1021/mz400560y
7. [7]
  V.P. Torchilin, A.N. Lukyanov, Z. Gao, B. Papahadjopoulos-Sternberg, Proc. Natl. Acad. Sci. U. S. A. 100 (2003) 6039–6044. doi: 10.1073/pnas.0931428100
8. [8]
  X. Wan, T. Liu, S. Liu, Biomacromolecules 12 (2011) 1146–1154. doi: 10.1021/bm101463d
9. [9]
  M.A. Aboudzadeh, A. Iturrospe, A. Arbe, M. Grzelczak, F. Barroso-Bujans, ACS Macro Lett. 9 (2020) 1604–1610. doi: 10.1021/acsmacrolett.0c00730
10. [10]
  G. Morgese, B. Shirmardi Shaghasemi, V. Causin, et al., Angew. Chem. Int. Ed. 56 (2017) 4507–4511. doi: 10.1002/anie.201700196
11. [11]
  E.R. Gillies, E. Dy, J.M.J. Fréchet, F.C. Szoka, Mol. Pharmaceutics 2 (2005) 129–138. doi: 10.1021/mp049886u
12. [12]
  L. Trachsel, M. Romio, B. Grob, et al., ACS Nano 14 (2020) 10054–10067. doi: 10.1021/acsnano.0c03239
13. [13]
  W. Chen, Y. Zhou, Y. Li, et al., Polym. Chem. 7 (2016) 6789–6797. doi: 10.1039/C6PY01638C
14. [14]
  K. Zhang, G.N. Tew, React. Funct. Polym. 80 (2014) 40–47. doi: 10.1016/j.reactfunctpolym.2014.01.012
15. [15]
  T. Josse, J. De Winter, P. Gerbaux, O. Coulembier, Angew. Chem. Int. Ed. 55 (2016) 13944–13958. doi: 10.1002/anie.201601677
16. [16]
  H. Kammiyada, A. Konishi, M. Ouchi, M. Sawamoto, ACS Macro Lett. 2 (2013) 531–534. doi: 10.1021/mz400191t
17. [17]
  J. Huang, J. Li, R. Yan, et al., Chin. Chem. Lett. 35 (2024) 108643. doi: 10.1016/j.cclet.2023.108643
18. [18]
  Y. Xia, A.J. Boydston, R.H. Grubbs, Angew. Chem. Int. Ed. 50 (2011) 5882–5885. doi: 10.1002/anie.201101860
19. [19]
  A. Narumi, M. Yamada, Y. Unno, et al., ACS Macro Lett. 8 (2019) 634–638. doi: 10.1021/acsmacrolett.9b00308
20. [20]
  S.A. Gonsales, T. Kubo, M.K. Flint, et al., J. Am. Chem. Soc. 138 (2016) 4996–4999. doi: 10.1021/jacs.6b00014
21. [21]
  Y.A. Chang, R.M. Waymouth, J. Polym. Sci. A: Polym. Chem. 55 (2017) 2892–2902. doi: 10.1002/pola.28635
22. [22]
  C.D. Roland, H. Li, K.A. Abboud, K.B. Wagener, A.S. Veige, Nat. Chem. 8 (2016) 791–796. doi: 10.1038/nchem.2516
23. [23]
  Y.Y. Fei, C. Liu, G. Chen, C.Y. Hong, Polym. Chem. 10 (2019) 3895–3901. doi: 10.1039/c9py00472f
24. [24]
  C. Liu, Y.Y. Fei, H.L. Zhang, C.Y. Pan, C.Y. Hong, Macromolecules 52 (2019) 176–184. doi: 10.1021/acs.macromol.8b02192
25. [25]
  H. Jacobson, W.H. Stockmayer, J. Chem. Phys. 18 (2004) 1600–1606.
26. [26]
  M. Ouchi, N. Badi, J.F. Lutz, M. Sawamoto, Nat. Chem. 3 (2011) 917–924. doi: 10.1038/nchem.1175
27. [27]
  M. Gonzalez-Burgos, A. Latorre-Sanchez, J.A. Pomposo, Chem. Soc. Rev. 44 (2015) 6122–6142. doi: 10.1039/C5CS00209E
28. [28]
  S. Mavila, O. Eivgi, I. Berkovich, N.G. Lemcoff, Chem. Rev. 116 (2016) 878–961. doi: 10.1021/acs.chemrev.5b00290
29. [29]
  A.M. Hanlon, C.K. Lyon, E.B. Berda, Macromolecules 49 (2016) 2–14. doi: 10.1021/acs.macromol.5b01456
30. [30]
  Y. Hirai, T. Terashima, M. Takenaka, M. Sawamoto, Macromolecules 49 (2016) 5084–5091. doi: 10.1021/acs.macromol.6b01085
31. [31]
  K. Matsumoto, T. Terashima, T. Sugita, M. Takenaka, M. Sawamoto, Macromolecules 49 (2016) 7917–7927. doi: 10.1021/acs.macromol.6b01702
32. [32]
  H.L. Zhang, H. Zha, C. Liu, C.Y. Hong, Sci. China Chem. 65 (2022) 2558–2566. doi: 10.1007/s11426-022-1344-3
33. [33]
  M. Shibata, M. Matsumoto, Y. Hirai, et al., Macromolecules 51 (2018) 3738–3745. doi: 10.1021/acs.macromol.8b00570
34. [34]
  S. Imai, Y. Hirai, C. Nagao, M. Sawamoto, T. Terashima, Macromolecules 51 (2018) 398–409. doi: 10.1021/acs.macromol.7b01918
35. [35]
  Y. Jiang, Z. Zhang, D. Wang, N. Hadjichristidis, Macromolecules 51 (2018) 3193–3202. doi: 10.1021/acs.macromol.8b00333
36. [36]
  P. Sun, J.Q. Chen, J.A. Liu, K. Zhang, Macromolecules 50 (2017) 1463–1472. doi: 10.1021/acs.macromol.6b02614
37. [37]
  X.Q. Xue, Y.J. Chen, K. Liang, et al., Polym. Chem. 11 (2020) 6529–6538. doi: 10.1039/d0py01116a
38. [38]
  B.A. Laurent, S.M. Grayson, J. Am. Chem. Soc. 133 (2011) 13421–13429. doi: 10.1021/ja2024355
39. [39]
  V.V. Varadaiah, V.S.R. Rao, J. Polym. Sci. 50 (1961) 31–34. doi: 10.1002/pol.1961.1205015304
40. [40]
  H.L. Zhang, W. Xu, C. Liu, C.Y. Hong, Polym. Chem. 12 (2021) 5357–5363. doi: 10.1039/d1py00341k
41. [41]
  M.L. McGraw, R.W. Clarke, E.Y.X. Chen, J. Am. Chem. Soc. 143 (2021) 3318–3322. doi: 10.1021/jacs.1c00561
42. [42]
  Y. Muramatsu, A. Takasu, M. Higuchi, M. Hayashi, J. Polym. Sci. 58 (2020) 2936–2942. doi: 10.1002/pol.20200587
43. [43]
  Z. Zhang, X. Nie, F. Wang, et al., Nat. Commun. 11 (2020) 3654. doi: 10.1038/s41467-020-17474-0
44. [44]
  K. Zhang, M.A. Lackey, Y. Wu, G.N. Tew, J. Am. Chem. Soc. 133 (2011) 6906–6909. doi: 10.1021/ja2007559
45. [45]
  C.H. Ma, Y. Quan, R.Y. Sun, et al., Chem. Commun. 58 (2022) 4340–4343. doi: 10.1039/d1cc07223d
46. [46]
  M. Schappacher, A. Deffieux, Angew. Chem. Int. Ed. 48 (2009) 5930–5933. doi: 10.1002/anie.200900704
47. [47]
  M. Schappacher, A. Deffieux, Science 319 (2008) 1512–1515. doi: 10.1126/science.1153848
1. [1]
  Bing Niu , Honggao Huang , Liwei Luo , Li Zhang , Jianbo Tan . Coating colloidal particles with a well-defined polymer layer by surface-initiated photoinduced polymerization-induced self-assembly and the subsequent seeded polymerization. Chinese Chemical Letters, 2025, 36(2): 110431-. doi: 10.1016/j.cclet.2024.110431
2. [2]
  Wenjian Zhang , Mengxin Fan , Wenwen Fei , Wei Bai . Cultivation of Critical Thinking Ability: Based on RAFT Polymerization-Induced Self-Assembly. University Chemistry, 2025, 40(4): 108-112. doi: 10.12461/PKU.DXHX202406099
3. [3]
  Huiju Cao , Lei Shi . sp¹-Hybridized linear and cyclic carbon chain. Chinese Chemical Letters, 2025, 36(4): 110466-. doi: 10.1016/j.cclet.2024.110466
4. [4]
  Yi Liu , Peng Lei , Yang Feng , Shiwei Fu , Xiaoqing Liu , Siqi Zhang , Bin Tu , Chen Chen , Yifan Li , Lei Wang , Qing-Dao Zeng . Topologically engineering of π-conjugated macrocycles: Tunable emission and photochemical reaction toward multi-cyclic polymers. Chinese Chemical Letters, 2024, 35(10): 109571-. doi: 10.1016/j.cclet.2024.109571
5. [5]
  Yifei Zhang , Yuncong Xue , Laiwei Gao , Rui Liao , Feng Wang , Fei Wang . Merging non-covalent and covalent crosslinking: En route to single chain nanoparticles. Chinese Chemical Letters, 2024, 35(6): 109217-. doi: 10.1016/j.cclet.2023.109217
6. [6]
  Zhenzhu Wang , Chenglong Liu , Yunpeng Ge , Wencan Li , Chenyang Zhang , Bing Yang , Shizhong Mao , Zeyuan Dong . Differentiated self-assembly through orthogonal noncovalent interactions towards the synthesis of two-dimensional woven supramolecular polymers. Chinese Chemical Letters, 2024, 35(5): 109127-. doi: 10.1016/j.cclet.2023.109127
7. [7]
  Yikun Wang , Qiaomei Chen , Shijie Liang , Dongdong Xia , Chaowei Zhao , Christopher R. McNeill , Weiwei Li . Near-infrared double-cable conjugated polymers based on alkyl linkers with tunable length for single-component organic solar cells. Chinese Chemical Letters, 2024, 35(4): 109164-. doi: 10.1016/j.cclet.2023.109164
8. [8]
  Yiran Tao , Chunlei Dai , Zhaoxiang Xie , Xinru You , Kaiwen Li , Jun Wu , Hai Huang . Redox responsive polymeric nanoparticles enhance the efficacy of cyclin dependent kinase 7 inhibitor for enhanced treatment of prostate cancer. Chinese Chemical Letters, 2024, 35(8): 109170-. doi: 10.1016/j.cclet.2023.109170
9. [9]
  Tingting Hu , Chao Shen , Xueyan Wang , Fengbo Wu , Zhiyao He . Tumor microenvironment-sensitive polymeric nanoparticles for synergetic chemo-photo therapy. Chinese Chemical Letters, 2024, 35(11): 109562-. doi: 10.1016/j.cclet.2024.109562
10. [10]
  Shuang Liang , Jianjun Yao , Dan Liu , Mengli Zhou , Yong Cui , Zhaohui Wang . Tumor-responsive covalent organic polymeric nanoparticles enhancing STING activation for cancer immunotherapy. Chinese Chemical Letters, 2025, 36(3): 109856-. doi: 10.1016/j.cclet.2024.109856
11. [11]
  Jiale Zheng , Mei Chen , Huadong Yuan , Jianmin Luo , Yao Wang , Jianwei Nai , Xinyong Tao , Yujing Liu . Electron-microscopical visualization on the interfacial and crystallographic structures of lithium metal anode. Chinese Chemical Letters, 2024, 35(6): 108812-. doi: 10.1016/j.cclet.2023.108812
12. [12]
  Wei Su , Xiaoyan Luo , Peiyuan Li , Ying Zhang , Chenxiang Lin , Kang Wang , Jianzhuang Jiang . Phthalocyanine self-assembled nanoparticles for type Ⅰ photodynamic antibacterial therapy. Chinese Chemical Letters, 2024, 35(12): 109522-. doi: 10.1016/j.cclet.2024.109522
13. [13]
  Hailong He , Wenbing Wang , Wenmin Pang , Chen Zou , Dan Peng . Double stimulus-responsive palladium catalysts for ethylene polymerization and copolymerization. Chinese Chemical Letters, 2024, 35(7): 109534-. doi: 10.1016/j.cclet.2024.109534
14. [14]
  Zixu Xie , Pengfei Zhang , Ziyao Zhang , Chen Chen , Xing Wang . The choice of antimicrobial polymers: Hydrophilic or hydrophobic?. Chinese Chemical Letters, 2024, 35(9): 109768-. doi: 10.1016/j.cclet.2024.109768
15. [15]
  Hanying Li , Wee-Liat Ong . “Super-heterojunctioned” thermoelectric polymers. Chinese Chemical Letters, 2025, 36(2): 110523-. doi: 10.1016/j.cclet.2024.110523
16. [16]
  Shiqi Peng , Yongfang Rao , Tan Li , Yufei Zhang , Jun-ji Cao , Shuncheng Lee , Yu Huang . Regulating the electronic structure of Ir single atoms by ZrO₂ nanoparticles for enhanced catalytic oxidation of formaldehyde at room temperature. Chinese Chemical Letters, 2024, 35(7): 109219-. doi: 10.1016/j.cclet.2023.109219
17. [17]
  Jiajia Lv , Jie Gao , Hongyu Li , Zeli Yuan , Nan Dong . Rational design of hydroxytricyanopyrrole-based probes with high affinity and rapid visualization for amyloid-β aggregates in vitro and in vivo. Chinese Chemical Letters, 2024, 35(5): 108940-. doi: 10.1016/j.cclet.2023.108940
18. [18]
  Peide Zhu , Yangjia Liu , Yaoyao Tang , Siqi Zhu , Xinyang Liu , Lei Yin , Quan Liu , Zhiqiang Yu , Quan Xu , Dixian Luo , Juncheng Wang . Bi-doped carbon quantum dots functionalized liposomes with fluorescence visualization imaging for tumor diagnosis and treatment. Chinese Chemical Letters, 2024, 35(4): 108689-. doi: 10.1016/j.cclet.2023.108689
19. [19]
  Fan Zheng , Runsha Xiao , Shuai Huang , Zhikang Chen , Chen Lai , Anyao Bi , Heying Yao , Xueping Feng , Zihua Chen , Wenbin Zeng . Accurate visualization colorectal cancer by monitoring viscosity variations with a novel mitochondria-targeted fluorescent probe. Chinese Chemical Letters, 2025, 36(2): 109876-. doi: 10.1016/j.cclet.2024.109876
20. [20]
  Yuchen Zhang , Lifeng Ding , Zhenghe Xie , Xin Zhang , Xiaofeng Sui , Jian-Rong Li . Porous sorbents for direct capture of carbon dioxide from ambient air. Chinese Chemical Letters, 2025, 36(3): 109676-. doi: 10.1016/j.cclet.2024.109676

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(461)
HTML views(13)

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