具有动态共价键的两亲性嵌段共聚物的形成与自组装

张兆磊; 汤浩; 邱先灯; 张子瑄; 方舒越; 汪蓉

doi:10.11777/j.issn1000-3304.2026.26088

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具有动态共价键的两亲性嵌段共聚物的形成与自组装

研究论文 | 更新时间：2026-06-18

- 具有动态共价键的两亲性嵌段共聚物的形成与自组装
- Formation and Self-assembly of Amphiphilic Block Copolymers with Dynamic Covalent Bonds
- 高分子学报 2026年页码：1-11
- 作者机构：
  
  南京大学化学化工学院高分子科学与工程系配位化学全国重点实验室高性能高分子材料教育部重点实验室南京 210023
- 作者简介：
  
  E-mail: wangrong@nju.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 ┣92477118;52573024);22173045┫
- DOI：10.11777/j.issn1000-3304.2026.26088
  中图分类号：
- CSTR：32057.14.GFZXB.2026.7612
- 收稿：2026-03-24，
  
  录用：2026-04-21，
  
  网络首发：2026-06-18，
- 稿件说明：
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张兆磊, 汤浩, 邱先灯, 张子瑄, 方舒越, 汪蓉. 具有动态共价键的两亲性嵌段共聚物的形成与自组装. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26088.

Zhang, Z. L.; Tang, H.; Qiu, X. D.; Zhang, Z. X.; Fang, S. Y.; Wang, R. Formation and self-assembly of amphiphilic block copolymers with dynamic covalent bonds. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26088.
张兆磊, 汤浩, 邱先灯, 张子瑄, 方舒越, 汪蓉. 具有动态共价键的两亲性嵌段共聚物的形成与自组装. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26088. DOI： CSTR： 32057.14.GFZXB.2026.7612.

Zhang, Z. L.; Tang, H.; Qiu, X. D.; Zhang, Z. X.; Fang, S. Y.; Wang, R. Formation and self-assembly of amphiphilic block copolymers with dynamic covalent bonds. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26088. DOI： CSTR： 32057.14.GFZXB.2026.7612.

摘要

采用耗散粒子动力学(dissipative particle dynamics，DPD)模拟方法研究了具有动态共价键的两亲性嵌段共聚物的自组装行为. 结果表明，在动态共价键的存在下，通过调控疏水作用和嵌段间的相互作用，得到了多室囊泡、囊泡、大复合胶束和球形胶束等形态. 疏水相互作用是自组装的主要驱动力，嵌段间的相互作用可以调节界面曲率，进一步控制聚集体形态；随嵌段间排斥作用增强，聚集体从大复合胶束依次演变为多室囊泡、囊泡及胶束. 在动力学方面，体系浓度对动态键成键率呈现非单调影响，低浓度下反应受扩散控制，成键率随浓度增加而升高；当浓度进一步升高时，排斥体积效应和空间受限增强，反而抑制后续成键，从而表现出成键的最优浓度区间. 此外，对比了游离链与预连接嵌段2种初始模型的组装路径，发现初始拓扑连接性会显著影响体系的组装演化过程；与游离链体系相比，预连接嵌段体系中单室囊泡的形成区域明显扩大. 上述结果为动态共价键调控的高分子聚集体形态设计提供了理论依据.

Abstract

Dissipative particle dynamics (DPD) simulations were employed to investigate the self-assembly behavior of amphiphilic block copolymers with dynamic covalent bonds. The results showed that in the presence of dynamic covalent bonds

multicompartment vesicles

vesicles

large compound micelles

and spherical micelles can be obtained by tuning the hydrophobic interaction and the interaction between blocks. Hydrophobic interactions served as the primary driving force for self-assembly

whereas the interaction between blocks regulated the interfacial curvature

thereby further controlling the aggregate morphology. With increasing repulsion between the blocks

the aggregate morphology underwent a sequential transition from large compound micelles to multicompartment vesicles

vesicles

and micelles. From a kinetic perspective

the system concentration exerted a non-monotonic effect on the bond fraction of the dynamic bonds. At low concentrations

the reaction was diffusion-controlled

and the bond fraction increased with increasing concentration. When the concentration further increased

the enhanced excluded-volume effects and spatial confinement suppressed subsequent bond formation

resulting in an optimal concentration window for bond formation. In addition

a comparison of the assembly pathways between the free-chain and pre-connected block models revealed that the initial topological connectivity significantly affects the assembly evolution process. Compared with the free-chain system

the region for single-compartment vesicle formation was markedly enlarged in the preconnected block system. These results provide a theoretical basis for the morphological design of polymer aggregates regulated by dynamic covalent bonds.

关键词

Keywords

references

Bates F. S. ; Fredrickson G. H. Block copolymer thermodynamics: theory and experiment . Annu. Rev. Phys. Chem. , 1990 , 41 , 525 - 557 . doi: 10.1146/annurev.pc.41.100190.002521 http://dx.doi.org/10.1146/annurev.pc.41.100190.002521

Blanazs A. ; Armes S. P. ; Ryan A. J. Self-assembled block copolymer aggregates: from micelles to vesicles and their biological applications . Macromol. Rapid Commun. , 2009 , 30 ( 4-5 ), 267 - 277 . doi: 10.1002/marc.200800713 http://dx.doi.org/10.1002/marc.200800713

Discher D. E. ; Eisenberg A. Polymer vesicles . Science , 2002 , 297 ( 5583 ), 967 - 973 . doi: 10.1126/science.1074972 http://dx.doi.org/10.1126/science.1074972

Mai Y. Y. ; Eisenberg A. Self-assembly of block copolymers . Chem. Soc. Rev. , 2012 , 41 ( 18 ), 5969 - 5985 . doi: 10.1039/c2cs35115c http://dx.doi.org/10.1039/c2cs35115c

Zhang L. F. ; Eisenberg A. Multiple morphologies of "crew-cut" aggregates of polystyrene- b -poly(acrylic acid) block copolymers . Science , 1995 , 268 ( 5218 ), 1728 - 1731 . doi: 10.1126/science.268.5218.1728 http://dx.doi.org/10.1126/science.268.5218.1728

Bae Y. ; Fukushima S. ; Harada A. ; Kataoka K. Design of environment-sensitive supramolecular assemblies for intracellular drug delivery: polymeric micelles that are responsive to intracellular pH change . Angew. Chem. Int. Ed. , 2003 , 42 ( 38 ), 4640 - 4643 . doi: 10.1002/anie.200250653 http://dx.doi.org/10.1002/anie.200250653

Napoli A. ; Valentini M. ; Tirelli N. ; Müller M. ; Hubbell J. A. Oxidation-responsive polymeric vesicles . Nat. Mater. , 2004 , 3 ( 3 ), 183 - 189 . doi: 10.1038/nmat1081 http://dx.doi.org/10.1038/nmat1081

Vriezema D. ; Garcia P. ; Sancho Oltra N. ; Hatzakis N. ; Kuiper S. ; Nolte R. ; Rowan A. ; van Hest J. C. M. Positional assembly of enzymes in polymersome nanoreactors for cascade reactions . Angew. Chem. Int. Ed. , 2007 , 46 ( 39 ), 7378 - 7382 . doi: 10.1002/anie.200701125 http://dx.doi.org/10.1002/anie.200701125

Du J. Z. ; Tang Y. Q. ; Lewis A. L. ; Armes S. P. pH-sensitive biocompatible block copolymer vesicles for drug delivery . J. Control. Release , 2011 , 152 , e16 - e17 . doi: 10.1016/j.jconrel.2011.08.094 http://dx.doi.org/10.1016/j.jconrel.2011.08.094

Elsabahy M. ; Wooley K. L. Design of polymeric nanoparticles for biomedical delivery applications . Chem. Soc. Rev. , 2012 , 41 ( 7 ), 2545 - 2561 . doi: 10.1039/c2cs15327k http://dx.doi.org/10.1039/c2cs15327k

Peters R. J. R. W. ; Marguet M. ; Marais S. ; Fraaije M. W. ; van Hest J. C. M. ; Lecommandoux S. Cascade reactions in multicompartmentalized polymersomes . Angew. Chem. Int. Ed. , 2014 , 53 ( 1 ), 146 - 150 . doi: 10.1002/anie.201308141 http://dx.doi.org/10.1002/anie.201308141

Zhao J. Y. ; Peng Y. Y. ; Diaz-Dussan D. ; White J. ; Duan W. ; Kong L. X. ; Narain R. ; Hao X. J. Zwitterionic block copolymer prodrug micelles for pH responsive drug delivery and hypoxia-specific chemotherapy . Mol. Pharmaceutics , 2022 , 19 ( 6 ), 1766 - 1777 . doi: 10.1021/acs.molpharmaceut.1c00518 http://dx.doi.org/10.1021/acs.molpharmaceut.1c00518

Kumar S. ; Dory Y. L. ; Lepage M. ; Zhao Y. Surface-grafted stimuli-responsive block copolymer brushes for the thermo-, photo- and pH-sensitive release of dye molecules . Macromolecules , 2011 , 44 ( 18 ), 7385 - 7393 . doi: 10.1021/ma2010102 http://dx.doi.org/10.1021/ma2010102

Kim S. ; Park S. ; Kim M. S. ; Lee H. ; Lee H. ; Lee K. H. ; Kim M. Supramolecular association of a block copolymer via strong hydrogen bonding to form self-healable ionogels . ACS Appl. Mater. Interfaces , 2024 , 16 ( 38 ), 51459 - 51468 . doi: 10.1021/acsami.4c09988 http://dx.doi.org/10.1021/acsami.4c09988

Sun Y. T. ; Deming T. J. Self-healing multiblock copolypeptide hydrogels via polyion complexation . ACS Macro Lett. , 2019 , 8 ( 5 ), 553 - 557 . doi: 10.1021/acsmacrolett.9b00269 http://dx.doi.org/10.1021/acsmacrolett.9b00269

Deng R. H. ; Derry M. J. ; Mable C. J. ; Ning Y. ; Armes S. P. Using dynamic covalent chemistry to drive morphological transitions: controlled release of encapsulated nanoparticles from block copolymer vesicles . J. Am. Chem. Soc. , 2017 , 139 ( 22 ), 7616 - 7623 . doi: 10.1021/jacs.7b02642 http://dx.doi.org/10.1021/jacs.7b02642

Zhang, X. Y.; Waymouth, R. M. 1,2-dithiolane-derived dynamic, covalent materials: cooperative self-assembly and reversible cross-linking . J. Am. Chem. Soc. , 2017 , 139 ( 10 ), 3822 - 3833 . doi: 10.1021/jacs.7b00039 http://dx.doi.org/10.1021/jacs.7b00039

Yi Y. ; Xu H. P. ; Wang L. ; Cao W. ; Zhang X. A new dynamic covalent bond of Se-N: towards controlled self-assembly and disassembly . Chem. Eur. J. , 2013 , 19 ( 29 ), 9506 - 9510 . doi: 10.1002/chem.201301446 http://dx.doi.org/10.1002/chem.201301446

Jackson A. W. ; Fulton D. A. Triggering polymeric nanoparticle disassembly through the simultaneous application of two different stimuli . Macromolecules , 2012 , 45 ( 6 ), 2699 - 2708 . doi: 10.1021/ma202721s http://dx.doi.org/10.1021/ma202721s

Chakma P. ; Konkolewicz D. Dynamic covalent bonds in polymeric materials . Angew. Chem. Int. Ed. , 2019 , 58 ( 29 ), 9682 - 9695 . doi: 10.1002/anie.201813525 http://dx.doi.org/10.1002/anie.201813525

Lei Z. Q. ; Xiang H. P. ; Yuan Y. J. ; Rong M. Z. ; Zhang M. Q. Room-temperature self-healable and remoldable cross-linked polymer based on the dynamic exchange of disulfide bonds . Chem. Mater. , 2014 , 26 ( 6 ), 2038 - 2046 . doi: 10.1021/cm4040616 http://dx.doi.org/10.1021/cm4040616

Cromwell O. R. ; Chung J. ; Guan Z. B. Malleable and self-healing covalent polymer networks through tunable dynamic boronic ester bonds . J. Am. Chem. Soc. , 2015 , 137 ( 20 ), 6492 - 6495 . doi: 10.1021/jacs.5b03551 http://dx.doi.org/10.1021/jacs.5b03551

Deng G. H. ; Tang C. M. ; Li F. Y. ; Jiang H. F. ; Chen Y. M. Covalent cross-linked polymer gels with reversible sol-gel transition and self-healing properties . Macromolecules , 2010 , 43 ( 3 ), 1191 - 1194 . doi: 10.1021/ma9022197 http://dx.doi.org/10.1021/ma9022197

Rekondo A. ; Martin R. ; Ruiz de Luzuriaga A. ; Cabañero G. ; Grande H. J. ; Odriozola I. Catalyst-free room-temperature self-healing elastomers based on aromatic disulfide metathesis . Mater. Horiz. , 2014 , 1 ( 2 ), 237 - 240 . doi: 10.1039/c3mh00061c http://dx.doi.org/10.1039/c3mh00061c

吴思武 , 唐征海 , 郭宝春 . 动态共价键交联橡胶的设计和性能 . 高分子学报 , 2019 , 50 ( 5 ), 442 - 450 .

陈巧梅 , 杨洋 , 危岩 , 吉岩 . 含可交换动态共价键的液晶聚合物驱动器 . 高分子学报 , 2019 , 50 ( 5 ), 451 - 468 .

陈兴幸 , 钟倩云 , 王淑娟 , 吴宥伸 , 谭继东 , 雷恒鑫 , 黄绍永 , 张彦峰 . 动态共价键高分子材料的研究进展 . 高分子学报 , 2019 , 50 ( 5 ), 469 - 484 . doi: 10.11777/j.issn1000-3304.2019.18277 http://dx.doi.org/10.11777/j.issn1000-3304.2019.18277

Tsao Y. H. ; Chen Y. J. ; Sing C. E. ; Evans C. M. Dynamic covalent bond exchange at block copolymer junctions impacts self-assembly kinetics . Macromolecules , 2025 , 58 ( 6 ), 2947 - 2957 . doi: 10.1021/acs.macromol.4c02984 http://dx.doi.org/10.1021/acs.macromol.4c02984

Chakma P. ; Morley C. N. ; Sparks J. L. ; Konkolewicz D. Exploring how vitrimer-like properties can be achieved from dissociative exchange in anilinium salts . Macromolecules , 2020 , 53 ( 4 ), 1233 - 1244 . doi: 10.1021/acs.macromol.0c00120 http://dx.doi.org/10.1021/acs.macromol.0c00120

Huang Z. X. ; Zhang J. M. ; Qian Y. Y. ; Liu H. X. ; Xiao Y. F. ; Du J. Z. Antioxidant glycopolymersomes with dynamic covalent glucose regulation for synergistic pancreatitis-diabetes therapy . Nano Today , 2025 , 65 , 102871 . doi: 10.1016/j.nantod.2025.102871 http://dx.doi.org/10.1016/j.nantod.2025.102871

Tena-Solsona M. ; Rieß B. ; Grötsch R. K. ; Löhrer F. C. ; Wanzke C. ; Käsdorf B. ; Bausch A. R. ; Müller-Buschbaum P. ; Lieleg O. ; Boekhoven J. Non-equilibrium dissipative supramolecular materials with a tunable lifetime . Nat. Commun. , 2017 , 8 , 15895 . doi: 10.1038/ncomms15895 http://dx.doi.org/10.1038/ncomms15895

Carnall J. M. A. ; Waudby C. A. ; Belenguer A. M. ; Stuart M. C. A. ; Peyralans J. J. ; Otto S. Mechanosensitive self-replication driven by self-organization . Science , 2010 , 327 ( 5972 ), 1502 - 1506 . doi: 10.1126/science.1182767 http://dx.doi.org/10.1126/science.1182767

Montarnal D. ; Capelot M. ; Tournilhac F. ; Leibler L. Silica-like malleable materials from permanent organic networks . Science , 2011 , 334 ( 6058 ), 965 - 968 . doi: 10.1126/science.1212648 http://dx.doi.org/10.1126/science.1212648

Sood A. ; Mandal P. K. ; Ottelé J. ; Wu J. T. ; Eleveld M. ; Hatai J. ; Pappas C. G. ; Huc I. ; Otto S. Simultaneous formation of a foldamer and a self-replicator by out-of-equilibrium dynamic covalent chemistry . J. Am. Chem. Soc. , 2024 , 146 ( 49 ), 33386 - 33394 . doi: 10.1021/jacs.4c09111 http://dx.doi.org/10.1021/jacs.4c09111

Zhang G. G. ; Peng W. J. ; Wu J. J. ; Zhao Q. ; Xie T. Digital coding of mechanical stress in a dynamic covalent shape memory polymer network . Nat. Commun. , 2018 , 9 , 4002 . doi: 10.1038/s41467-018-06420-w http://dx.doi.org/10.1038/s41467-018-06420-w

Bai J. L. ; Liu D. ; Wang R. Self-assembly of amphiphilic diblock copolymers induced by liquid-liquid phase separation . Chinese J. Polym. Sci. , 2021 , 39 ( 9 ), 1217 - 1224 . doi: 10.1007/s10118-021-2563-6 http://dx.doi.org/10.1007/s10118-021-2563-6

Hoogerbrugge P. J. ; Koelman J. M. V. A. Simulating microscopic hydrodynamic phenomena with dissipative particle dynamics . Europhys. Lett. , 1992 , 19 ( 3 ), 155 - 160 . doi: 10.1209/0295-5075/19/3/001 http://dx.doi.org/10.1209/0295-5075/19/3/001

Svaneborg C. LAMMPS framework for dynamic bonding and an application modeling DNA . Comput. Phys. Commun. , 2012 , 183 ( 8 ), 1793 - 1802 . doi: 10.1016/j.cpc.2012.03.005 http://dx.doi.org/10.1016/j.cpc.2012.03.005

Gioldasis C. ; Gkamas A. ; Moultos O. A. ; Vlahos C. H. Chemical feedback in templated reaction-assembly of polyelectrolyte complex micelles: a molecular simulation study of the kinetics and clustering . Polymers , 2023 , 15 ( 14 ), 3024 . doi: 10.3390/polym15143024 http://dx.doi.org/10.3390/polym15143024

Lei J. C. ; Xu S. ; Li Z. Q. ; Liu Z. S. Study on large deformation behavior of polyacrylamide hydrogel using dissipative particle dynamics . Front. Chem. , 2020 , 8 , 115 . doi: 10.3389/fchem.2020.00115 http://dx.doi.org/10.3389/fchem.2020.00115

Groot R. D. ; Warren P. B. Dissipative particle dynamics: bridging the gap between atomistic and mesoscopic simulation . J. Chem. Phys. , 1997 , 107 ( 11 ), 4423 - 4435 . doi: 10.1063/1.474784 http://dx.doi.org/10.1063/1.474784

Plimpton S. Fast parallel algorithms for short-range molecular dynamics . J. Comput. Phys. , 1995 , 117 ( 1 ), 1 - 19 . doi: 10.1006/jcph.1995.1039 http://dx.doi.org/10.1006/jcph.1995.1039

Stukowski A. Visualization and analysis of atomistic simulation data with OVITO-the Open Visualization Tool . Model. Simul. Mater. Sci. Eng. , 2010 , 18 ( 1 ), 015012 . doi: 10.1088/0965-0393/18/1/015012 http://dx.doi.org/10.1088/0965-0393/18/1/015012

Byard S. J. ; O'Brien C. T. ; Derry M. J. ; Williams M. ; Mykhaylyk O. O. ; Blanazs A. ; Armes S. P. Unique aqueous self-assembly behavior of a thermoresponsive diblock copolymer . Chem. Sci. , 2020 , 11 ( 2 ), 396 - 402 . doi: 10.1039/c9sc04197d http://dx.doi.org/10.1039/c9sc04197d

Warren N. J. ; Armes S. P. Polymerization-induced self-assembly of block copolymer nano-objects via RAFT aqueous dispersion polymerization . J. Am. Chem. Soc. , 2014 , 136 ( 29 ), 10174 - 10185 . doi: 10.1021/ja502843f http://dx.doi.org/10.1021/ja502843f

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