

浏览全部资源
扫码关注微信
河南大学化学与分子科学学院 开封 475001
Received:28 February 2026,
Accepted:02 April 2026,
Online First:27 May 2026,
Published:20 July 2026
移动端阅览
段承博, 曾尚辉, 王慧, 陈永明. 基于点击化学策略的聚合物分子刷设计、合成与应用研究进展. 高分子通报, 2026, 39(7), 1128–1139.
Duan, C. B.; Zeng, S. H.; Wang, H.; Chen, Y. M. Advances in the design, synthesis, and applications of molecular bottlebrushes via click chemistry. Polym. Bull. (in Chinese), 2026, 39(7), 1128–1139.
段承博, 曾尚辉, 王慧, 陈永明. 基于点击化学策略的聚合物分子刷设计、合成与应用研究进展. 高分子通报, 2026, 39(7), 1128–1139. DOI: 10.14028/j.cnki.1003-3726.2026.26.098.
Duan, C. B.; Zeng, S. H.; Wang, H.; Chen, Y. M. Advances in the design, synthesis, and applications of molecular bottlebrushes via click chemistry. Polym. Bull. (in Chinese), 2026, 39(7), 1128–1139. DOI: 10.14028/j.cnki.1003-3726.2026.26.098.
聚合物分子刷是一种高密度接枝的单分子纳米材料,其具有独特的分子构象、可精准调控的尺寸与拓扑结构,在生物医药、弹性体、表面活性剂等领域受到广泛关注。点击化学作为一种高效、快速和条件温和的偶联反应技术,被用来精准构筑具有复杂拓扑结构的聚合物分子刷。本综述聚焦于点击化学在聚合物分子刷结构设计、精准合成及应用中的研究进展,系统总结了铜催化叠氮–炔环加成和无金属点击反应在调控聚合物分子刷拓扑结构中的应用策略。分析点击反应介导的聚合物分子刷接枝效率和接枝密度的调控机制,阐述聚合物分子刷结构与性能之间的构效关系。在此基础上,总结了聚合物分子刷在生物医药和功能材料等领域的应用进展,并对未来发展方向进行了展望。
Molecular bottlebrushes are a class of densely grafted
unimolecular nanomaterials characterized by unique molecular conformations and precisely tunable dimensions and topologies. These materials have garnered significant attention in biomedicine
elastomers
and surfactants. Click chemistry
a highly efficient
rapid
and mild conjugation technique
has emerged as a powerful tool for the precise construction of molecular bottlebrushes with complex architectures. This review focuses on recent advances in the structural design
precision synthesis
and applications of molecular bottlebrushes enabled by click chemistry. This review systematically summarizes the application strategies of copper-catalyzed azide-alkyne cycloaddition and metal-free click reactions for tailoring the topology of molecular bottlebrushes. The regulatory mechanisms governing grafting efficiency and grafting density in click-mediated molecular bottlebrush synthesis were analyzed
and the structure-property relationships of molecular bottlebrushes were elucidated. Furthermore
the progress of molecular bottlebrush applications in biomedical and functional materials is reviewed
and future directions in this rapidly evolving field are discussed.
Chen, Y. M. Shaped hairy polymer nanoobjects . Macromolecules , 2012 , 45 ( 6 ), 2619 – 2631 .
Xie, G. J. ; Martinez, M. R. ; Olszewski, M. ; Sheiko, S. S. ; Matyjaszewski, K. Molecular bottlebrushes as novel materials . Biomacromolecules , 2019 , 20 ( 1 ), 27 – 54 .
Li, Z. L. ; Tang, M. ; Liang, S. ; Zhang, M. Y. ; Biesold, G. M. ; He, Y. J. ; Hao, S. M. ; Choi, W. ; Liu, Y. J. ; Peng, J. ; Lin, Z. Q. Bottlebrush polymers: from controlled synthesis, self-assembly, properties to applications . Prog. Polym. Sci. , 2021 , 116 , 101387 .
孙子扬 , 李华安 , 黄华华 , 石毅 , 陈永明 . 聚合物分子刷在纳米载体领域的应用 . 高分子学报 , 2020 , 51 ( 6 ), 609 – 619 .
Zhang, Z. ; Li, Z. Q. ; Shi, Y. ; Chen, Y. M. Molecular bottlebrushes as emerging nanocarriers: material design and biomedical application . Langmuir , 2024 , 40 ( 14 ), 7286 – 7299 .
Shi, Y. ; Hou, W. M. ; Li, Z. Q. ; Chen, Y. M. Tailoring the architecture of molecular bottlebrushes via click grafting-onto strategy . Macromol. Rapid Commun. , 2023 , 44 ( 23 ), 2300362 .
Sheiko, S. S. ; Sumerlin, B. S. ; Matyjaszewski, K. Cylindrical molecular brushes: synthesis, characte-rization, and properties . Prog. Polym. Sci. , 2008 , 33 ( 7 ), 759 – 785 .
Wang, B. B. ; Liu, T. ; Chen, H. ; Yin, B. Q. ; Zhang, Z. ; Russell, T. P. ; Shi, S. W. Molecular brush surfactants: versatile emulsifiers for stabilizing and structuring liquids . Angew. Chem. Int. Ed. , 2021 , 60 ( 36 ), 19626 – 19630 .
Müllner, M. Molecular polymer bottlebrushes in nanomedicine: therapeutic and diagnostic applications . Chem. Commun. , 2022 , 58 ( 38 ), 5683 – 5716 .
Zeng, W. T. ; Feng, W. S. ; Zhang, X. ; Yao, Y. ; Xu, B. B. ; Lin, S. L. Insight into the solution self-assembly of amphiphili c asymmetric brush copolymers via computer simulations . Chinese J. Polym. Sci. , 2025 , 43 ( 1 ), 132 – 140 .
Guo, Q. L. ; Xue, R. Z. ; Zhao, J. ; Zhang, Y. X. ; van de Kerkhof, G. T. ; Zhang, K. Y. ; Li, Y. S. ; Vignolini, S. ; Song, D. P. Precise tailoring of polyester bottlebrush amphiphiles toward eco-friendly photonic pigments via interfacial self-assembly . Angew. Chem. Int. Ed. , 2022 , 61 ( 34 ), e202206723 .
Li, J. L. ; Ji, S. Q. ; Yu, X. L. ; Yuan, X. Y. ; Zhang, K. ; Ren, L. X. Magnetic poly(ionic liquid)s: bottlebrush versus linear structures . Macromolecules , 2022 , 55 ( 6 ), 2067 – 2074 .
Basak, S. ; Chatterjee, R. ; Bandyopadhyay, A. Beyond traditional stimuli: exploring salt-responsive bottlebrush polymers─trends, applications, and perspectives . ACS Omega , 2024 , 9 ( 31 ), 33365 – 33385 .
Yin, L. Y. ; Liu, L. ; Zhang, N. Brush-like polymers: design, synthesis and applications . Chem. Commun. , 2021 , 57 ( 81 ), 10484 – 10499 .
Verduzco, R. ; Li, X. Y. ; Pesek, S. L. ; Stein, G. E. Structure, function, self-assembly, and applications of bottlebrush copolymers . Chem. Soc. Rev. , 2015 , 44 ( 8 ), 2405 – 2420 .
Zou, H. ; Wang, S. Q. ; Han, C. F. ; Hu, M. H. ; Chu, B. F. ; Zhou, L. Helical polymer-containing bottlebrush polymers (BBPs): design, synthesis, and perspectives . Macromol. Rapid Commun. , 2025 , 46 ( 10 ), 2400985 .
Zhang, M. J. ; Wu, J. S. ; Li, Z. Q. ; Hou, W. M. ; Li, Y. C. ; Shi, Y. ; Chen, Y. M. Synthesis and visualization of bottlebrush-shaped segmented hyperbranched polymers . Polym. Chem. , 2022 , 13 ( 34 ), 4895 – 4900 .
Clarke, B. R. ; Witt, C. L. ; Ilton, M. ; Crosby, A. J. ; Watkins, J. J. ; Tew, G. N. Bottlebrush networks: a primer for advanced architectures . Angew. Chem. Int. Ed. , 2024 , 63 , e202318220 .
Hou, W. M. ; Yin, X. Z. ; Zhou, Y. Q. ; Shi, Y. ; Chen, Y. M. Ring-opening metathesis polymerization for synthesizing molecular bottlebrushes via the grafting-through strategy . J. Polym. Sci. , 2024 , 62 ( 21 ), 4835 – 4850 .
Gao, H. F. ; Matyjaszewski, K. Synthesis of molecular brushes by “grafting onto” method: combination of ATRP and click reactions . J. Am. Chem. Soc. , 2007 , 129 ( 20 ), 6633 – 6639 .
Hou, W. M. ; Li, Z. Q. ; Xu, L. ; Li, Y. C. ; Shi, Y. ; Chen, Y. M. High-yield synthesis of molecular bottlebrushes via PISA-assisted grafting-from strategy . ACS Macro Lett. , 2021 , 10 ( 10 ), 1260 – 1265 .
Messina, M. S. ; Messina, K. M. M. ; Bhattacharya, A. ; Montgomery, H. R. ; Maynard, H. D. Preparation of biomolecule-polymer conjugates by grafting-from using ATRP, RAFT, or ROMP . Prog. Polym. Sci. , 2020 , 100 , 101186 .
Hou, W. M. ; Wu, J. S. ; Li, Z. Q. ; Zhang, Z. ; Shi, Y. ; Chen, Y. M. Efficient synthesis and PISA behavior of molecular bottlebrush block copolymers via a grafting-from strategy through RAFT dispersion polymerization . Macromolecules , 2023 , 56 ( 3 ), 824 – 832 .
Gan, W. P. ; Shi, Y. ; Jing, B. X. ; Cao, X. S. ; Zhu, Y. X. ; Gao, H. F. Produce molecular brushes with ultrahigh grafting density using accelerated CuAAC grafting-onto strategy . Macromolecules , 2017 , 50 ( 1 ), 215 – 222 .
Wilk, J. T. ; Furner, C. T. ; Kent, E. W. ; Kelly, M. T. ; Zhao, B. ; Li, C. Y. Effect of grafting density on the crystallization behavior of molecular bottlebrushes . Macromolecules , 2024 , 57 ( 17 ), 8487 – 8497 .
Xiao, L. F. ; Chen, Y. M. ; Zhang, K. Efficient metal-free “grafting onto” method for bottlebrush polymers by combining RAFT and triazolinedione–diene click reaction . Macromolecules , 2016 , 49 ( 12 ), 4452 – 4461 .
Zhou, Y. Q. ; Xu, Y. P. ; Yin, X. Z. ; Hou, W. M. ; Liu, Z. J. ; Shi, Y. ; Chen, Y. M. Synthesis of dendronized polymers via a “m+n” grafting-onto strategy with reaction-enhanced reactivity of intermediates (RERI) mechanism . Chinese J. Chem. , 2025 , 43 ( 7 ), 805 – 813 .
Shi, Y. ; Cao, X. S. ; Gao, H. F. The use of azide-alkyne click chemistry in recent syntheses and applications of polytriazole-based nanostructured polymers . Nanoscale , 2016 , 8 ( 9 ), 4864 – 4881 .
St Amant, A. ; Discekici, E. H. ; Bailey, S. J. ; Zayas, M. S. ; Song, J. A. ; Shankel, S. L. ; Nguyen, S. N. ; Bates, M. W. ; Anastasaki, A. ; Hawker, C. J. ; Read de Alaniz, J. Norbornadienes: robust and scalable building blocks for cascade “click” coupling of high molecular weight polymers . J. Am. Chem. Soc. , 2019 , 141 ( 34 ), 13619 – 13624 .
Li, Z. Q. ; Hou, W. M. ; Li, Y. C. ; Xu, J. X. ; Shi, Y. ; Chen, Y. M. Efficient metal-free norbornadiene-maleimide click reaction for the formation of molecular bottlebrushes . Macromolecules , 2021 , 54 ( 21 ), 10031 – 10039 .
Briou, B. ; Améduri, B. ; Boutevin, B. Trends in the Diels-Alder reaction in polymer chemistry . Chem. Soc. Rev. , 2021 , 50 ( 19 ), 11055 – 11097 .
Brevé, T. G. ; Filius, M. ; Araman, C. ; van der Helm, M. P. ; Hagedoorn, P. L. ; Joo, C. ; van Kasteren, S. I. ; Eelkema, R. Conditional copper-catalyzed azide-alkyne cycloaddition by catalyst encapsulation . Angew. Chem. Int. Ed. , 2020 , 59 ( 24 ), 9340 – 9344 .
Wiest, A. ; Kielkowski, P. Cu-catalyzed azide-alkyne-thiol reaction forms ubiquitous background in chemical proteomic studies . J. Am. Chem. Soc. , 2024 , 146 ( 3 ), 2151 – 2159 .
Ornelas, C. ; Broichhagen, J. ; Weck, M. Strain-promoted alkyne azide cycloaddition for the functionalization of poly(amide)-based dendrons and dendrimers . J. Am. Chem. Soc. , 2010 , 132 ( 11 ), 3923 – 3931 .
Zhao, P. ; Liu, L. X. ; Feng, X. Q. ; Wang, C. ; Shuai, X. T. ; Chen, Y. M. Molecular nanoworm with PCL core and PEO shell as a non-spherical carrier for drug delivery . Macromol. Rapid Commun. , 2012 , 33 ( 16 ), 1351 – 1355 .
Zou, L. ; Zhu, W. ; Chen, Y. M. ; Xi, F. Modification of side chain terminals of PEGylated molecular bottle brushes: a toolbar of molecular nanoobjects . Polymer , 2013 , 54 ( 2 ), 481 – 484 .
Yan, Y. C. ; Shi, Y. ; Zhu, W. ; Chen, Y. M. Highly efficient synthesis of cylindrical polymer brushes with various side chains via click grafting-onto approach . Polymer , 2013 , 54 ( 21 ), 5634 – 5642 .
Shi, Y. ; Zhu, W. ; Yao, D. D. ; Long, M. L. ; Peng, B. ; Zhang, K. ; Chen, Y. M. Disk-like micelles with a highly ordered pattern from molecular bottlebrushes . ACS Macro Lett. , 2014 , 3 ( 1 ), 70 – 73 .
Zhu, W. ; Zhang, L. C. ; Chen, Y. M. ; Zhang, K. A UV-cleavable bottlebrush polymer with o-nitrobenzyl-linked side chains . Macromol. Rapid Commun. , 2017 , 38 ( 11 ), 1700007 .
Yin, X. Z. ; Song, Q. L. ; Hou, W. M. ; Zhou, Y. Q. ; Liu, Z. J. ; Li, W. H. ; Du, J. Z. ; Shi, Y. ; Chen, Y. M. Realignment of bottlebrush segments induces the contraction of individual polymer vesicles . Macromolecules , 2025 , 58 ( 2 ), 989 – 999 .
Yin, X. Z. ; Zhou, Y. Q. ; Hou, W. M. ; Liu, Z. J. ; Shi, Y. ; Chen, Y. M. Molecular bottlebrushes with programmable grafting densities . Macromolecules , 2025 , 58 ( 15 ), 8217 – 8224 .
Chen, Y. ; Sun, Z. Y. ; Li, H. A. ; Dai, Y. K. ; Hu, Z. T. ; Huang, H. H. ; Shi, Y. ; Li, Y. C. ; Chen, Y. M. Molecular bottlebrushes featuring brush-on-brush architecture . ACS Macro Lett. , 2019 , 8 ( 6 ), 749 – 753 .
Nguyen, H. V. T. ; Gallagher, N. M. ; Vohidov, F. ; Jiang, Y. ; Kawamoto, K. ; Zhang, H. ; Park, J. V. ; Huang, Z. H. ; Ottaviani, M. F. ; Rajca, A. ; Johnson, J. A. Scalable synthesis of multivalent macromonomers for ROMP . ACS Macro Lett. , 2018 , 7 ( 4 ), 472 – 476 .
Shi, Y. ; Zhu, W. ; Chen, Y. M. Synthesis of cylindrical polymer brushes with umbrella-like side chains via a combination of grafting-from and grafting-onto methods . Macromolecules , 2013 , 46 ( 6 ), 2391 – 2398 .
Yin, C. F. ; Wang, R. N. ; Sun, Y. ; Li, S. ; Zhang, X. K. ; Gu, J. ; Wu, W. ; Jiang, X. Q. The in vitro and in vivo properties of ringlike polymer brushes . Nano Today , 2021 , 41 , 101293 .
Wang, S. S. ; Yang, X. K. ; Zhu, W. ; Zou, L. ; Zhang, K. ; Chen, Y. M. ; Xi, F. Strain-promoted azide-alkyne cycloaddition “click” as a conjugation tool for building topological polymers . Polymer , 2014 , 55 ( 19 ), 4812 – 4819 .
Liu, Y. L. ; Ke, F. F. ; Li, Y. C. ; Shi, Y. ; Zhang, Z. ; Chen, Y. M. Emulsion confined block copolymer self-assembly: recent progress and prospect . Nano Res. , 2023 , 16 ( 1 ), 564 – 582 .
Lee, J. ; Toujani, C. ; Tang, Y. ; Lee, R. ; Cureño Hernandez, K. E. ; Guilliams, B. F. ; Pochan, D. J. ; Ramírez-Hernández, A. ; Herrera-Alonso, M. Nonequilibrium solution-based assemblies from bottlebrush block copolymers for drug delivery . ACS Nano , 2025 , 19 ( 19 ), 18556 – 18569 .
Li, H. A. ; Liu, H. ; Nie, T. Q. ; Chen, Y. ; Wang, Z. Y. ; Huang, H. H. ; Liu, L. X. ; Chen, Y. M. Molecular bottlebrush as a unimolecular vehicle with tunable shape for photothermal cancer therapy . Biomaterials , 2018 , 178 , 620 – 629 .
Li, H. A. ; Sun, Z. Y. ; Jiang, S. Q. ; Lai, X. Y. ; Böckler, A. ; Huang, H. H. ; Peng, F. ; Liu, L. X. ; Chen, Y. M. Tadpole-like unimolecular nanomotor with sub-100 nm size swims in a tumor microenvironment model . Nano Lett. , 2019 , 19 ( 12 ), 8749 – 8757 .
Wang, R. N. ; Yang, S. ; Xiao, P. P. ; Sun, Y. ; Li, J. ; Jiang, X. Q. ; Wu, W. Fluorination and betaine modification augment the blood–brain barrier-crossing ability of cylindrical polymer brushes . Angew. Chem. Int. Ed. , 2022 , 61 ( 19 ), e202201390 .
Xu, L. ; Zhang, Q. Y. ; Lu, L. J. ; Shi, Y. ; Liu, L. X. ; Shen, J. ; Chen, Y. M. Unimolecular nano-contrast agent with ultrahigh relaxivity and very long retention for magnetic resonance lymphography . Nano Lett. , 2022 , 22 ( 10 ), 4090 – 4096 .
Yang, H. Y. ; Li, J. Q. ; Yao, S. L. ; Fan, Z. W. ; Jin, X. L. ; Cui, S. M. ; Yin, P. C. ; Zhang, W. ; Tang, L. Q. ; Wang, J. L. ; Sun, T. L. Thermal switching of polymer topology enables programmable mechanical properties in soft materials . Adv. Mater. , 2026 , 38 ( 9 ), e18403 .
Seong, H. G. ; Fink, Z. ; Chen, Z. ; Emrick, T. ; Russell, T. P. Bottlebrush polymers at liquid interfaces: assembly dynamics, mechanical properties, and all-liquid printed constructs . ACS Nano , 2023 , 17 ( 15 ), 14731 – 14741 .
Wu, L. ; Glebe, U. ; Kwok, K. T. K. ; Sun, J. W. ; Lam, J. W. Y. ; Tang, B. Z. AIE bottlebrush polymers: verification of internal crowdedness in bottlebrush polymers using the AIE effect . Angew. Chem. Int. Ed. , 2025 , 64 ( 19 ), e202500850 .
0
Views
55
下载量
0
CSCD
Publicity Resources
Related Articles
Related Author
Related Institution
京公网安备11010802046898号