Effect of External Stimuli-triggered Hydrophobic-Hydrophilic Transition on the Disassembly of ABCA Tetrablock Asymmetric Vesicles: a Monte Carlo Simulation Study

Yan-Qi Zong; Jie Cui; Yuan-Yuan Han

doi:10.1007/s10118-026-3778-3

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Effect of External Stimuli-triggered Hydrophobic-Hydrophilic Transition on the Disassembly of ABCA Tetrablock Asymmetric Vesicles: a Monte Carlo Simulation Study

RESEARCH ARTICLE | Updated：2026-08-19

- Effect of External Stimuli-triggered Hydrophobic-Hydrophilic Transition on the Disassembly of ABCA Tetrablock Asymmetric Vesicles: a Monte Carlo Simulation Study
- Effect of External Stimuli-triggered Hydrophobic-Hydrophilic Transition on the Disassembly of ABCA Tetrablock Asymmetric Vesicles: a Monte Carlo Simulation Study
- Chinese Journal of Polymer Science 2026年44卷页码：1-11
- Affiliations：
  
  School of New Energy and Advanced Materials, Liaoning Petrochemical University, Fushun 113001, China
- Author bio：
  
  cuijie@lnpu.edu.cn (J.C.)
  hanyuanyuan@lnpu.edu.cn (Y.Y.H.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 52433001), the Scientific Research Fund of Liaoning Provincial Education Department (No. JYTMS20231437), the Talent Scientific Research Fund of Liaoning Petrochemical University (Nos. 2019XJJL-014 and 2019XJJL-015).;The authors declare no interest conflict.Data supporting the findings of this study can be provided by contacting the corresponding author.
- DOI：10.1007/s10118-026-3778-3
  中图分类号：
- 收稿：2026-05-07，
  
  录用：2026-06-09，
  
  网络首发：2026-08-19，
  
  纸质出版：2026-07
- Accepted：
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Zong, Y. Q.; Cui, J.; Han, Y. Y. Effect of external stimuli-triggered hydrophobic-hydrophilic transition on the disassembly of ABCA tetrablock asymmetric vesicles: a Monte Carlo simulation study. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3778-3

Yan-Qi Zong, Jie Cui, Yuan-Yuan Han. Effect of External Stimuli-triggered Hydrophobic-Hydrophilic Transition on the Disassembly of ABCA Tetrablock Asymmetric Vesicles: a Monte Carlo Simulation Study[J/OL]. Chinese Journal of Polymer Science, 2026, 441-11.
Zong, Y. Q.; Cui, J.; Han, Y. Y. Effect of external stimuli-triggered hydrophobic-hydrophilic transition on the disassembly of ABCA tetrablock asymmetric vesicles: a Monte Carlo simulation study. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3778-3 DOI：

Yan-Qi Zong, Jie Cui, Yuan-Yuan Han. Effect of External Stimuli-triggered Hydrophobic-Hydrophilic Transition on the Disassembly of ABCA Tetrablock Asymmetric Vesicles: a Monte Carlo Simulation Study[J/OL]. Chinese Journal of Polymer Science, 2026, 441-11. DOI： 10.1007/s10118-026-3778-3.

摘要

Abstract

Various external stimuli

such as pH

light

and temperature

have been widely used to trigger the hydrophobic-hydrophilic transition of a certain block in block copolymer

which has become a commonly used and effective strategy to induce the disassembly of vesicles for controlled drug release. Based on this

the disassembly behavior of the ABCA tetrablock asymmetric vesicles induced by the hydrophobic-hydrophilic transition of block C was studied using Monte Carlo simulation. In this work

the hydrophobicity of block C was tuned to mimic the hydrophobic-hydrophilic transition triggered by external stimuli. As the hydrophobicity of block C decreases

the initial ABCA asymmetric vesicles disassemble into a series of ordered aggregates such as Janus lamella

reversed asymmetric vesicle

toroid micelle

ring-like micelle and cylindrical micelle. It should be noted that these aggregates disassembled from the initial vesicle state cannot be obtained through the traditional self-assembly method from homogeneous states of the ABCA tetrablock terpolymers under the same conditions. The simulation results show that the hydrophobicity changing rate of block C has a significant effect on the disassembly pathway from the initial asymmetric vesicle to the reversed asymmetric vesicle. It is found that during the disassembly from the initial to the reversed vesicles

the system will undergo an energy-driven process first

then followed by an entropy-driven process. In addition

the simulation results further indicate that the disassembly behavior of the initial ABCA asymmetric vesicles is irreversible.

关键词

Keywords

references

Zhang, Y. N.; Han, Y. L.; Li, J. W.; Shi. T. F. Perforation dynamics and directional motion of Janus vesicles under the coupled effects of flow and electric fields. Chinese J. Polym. Sci. 2025 , 43 , 1939−1949..

Xu, Q. R.; Wang, Y. W.; Zheng, Y.; Zhu, Y. L.; Li, Z. F.; Liu, Y.; Ding, M. M. Polymersomes in drug delivery-from experiment to computational modeling. Biomacromolecules 2023 , 25 , 2114−2135..

Zhou, J. W.; Zou, M. H.; Qiu, X. D.; Wang, R. Co-assembly of amphiphilic triblock copolymers with DNA-polymer targeting ligands in solution. Soft Matter 2025 , 21 , 5764−5772..

Zhou, J. W.; Tang, H.; Wang, R. Co-assembly of amphiphilic triblock copolymers with nanodrugs and drug release kinetics in solution. J. Phys. Chem. B 2024 , 128 , 2841−2852..

Gao, Y. N.; Gao, C. C.; Fan, Y. R.; Sun, H.; Du, J. Z. Physically and chemically compartmentalized polymersomes for programmed delivery and biological applications. Biomacromolecules 2023 , 24 , 5511−5538..

Xu, X. F.; Pan, C. Y.; Zhang, W. J.; Hong, C. Y. Polymerization-induced self-assembly generating vesicles with adjustable pH-responsive release performance. Macromolecules 2019 , 52 , 1965−1975..

Gong, H. Y.; Chen, Y. G.; Yu, X. S.; Xiao, H.; Xiao, J. P.; Wang, Y.; Shuai. X. T. Co-delivery of doxorubicin and afatinib with pH-responsive polymeric nanovesicle for enhanced lung cancer therapy. Chinese J. Polym. Sci. 2019 , 37 , 1224−1233..

Wang, Z. D.; Peng, C.; Zheng, Y.; Zhang, Y. W.; Xu, T. R.; Yan, J. Y.; Zhou, Y. Q.; Liu, Y.; Xie, H. X.; Wang, C.; Tan, H.; Fu, Q.; Ding, M. M. Enzyme-inspired nanoreactor containing light-controlled "trojan horse" for redox-hypersensitive drug delivery. Adv. Funct. Mater. 2023 , 33 , 2214899..

Hu, W.; Su, Y. W.; Jiang, Y. K.; Fan,W. D.; Cheng, S. Y.; Tong, Z. Z.; Cen, C.; Jiang, G. H. Polymer vesicles with upper critical solution temperature for near-infrared light-triggered transdermal delivery of metformin in diabetic rats. Chinese J. Polym. Sci. 2022 , 40 , 157−165..

Yao, C. Z.; Wang, X. R.; Liu, G. H.; Hu, J. M.; Liu, S. Y. Distinct morphological transitions of photoreactive and thermoresponsive vesicles for controlled release and nanoreactors. Macromolecules 2016 , 49 , 8282−8295..

Lee, D.; Kim, J.; Ku, K. H.; Li, S.; Shin, J. J.; Kim, B. J. Poly(vinylpyridine)-containing block copolymers for smart, multicompartment particles. Polym. Chem. 2022 , 13 , 2570−2588..

Wu, Y. Q.; Wang, K.; Tan, H. Y.; Xu, J. P.; Zhu, J. T. Emulsion solvent e vaporation-induced self-assembly of block copolymers containing pH-sensitive block. Langmuir 2017 , 33 , 9889−9896..

[Ji, D.; Wang, Y. P.; Luo, M. Q.; Zhang, Z. H.; Chang, X. H.; Zhu, Y. T. pH and light-triggered shape transformation of block copolymer particles in emulsion droplets. Eur. Polym. J . 2024 , 221 , 113561..

[Chen, M.; Li, J. W.; Zhang, W. J.; Hong, C. Y.; Pan, C. Y. pH-and reductant-responsive polymeric vesicles with robust membrane-cross-linked structures: In situ cross-linking in polymerization-induced self-assembly. Macromolecules 2019 , 52 , 1140-1149..

Lomas, H.; Canton, I.; MacNeil, S.; Du, J.; Armes, S. P.; Ryan, A. J.; Lewis, A. L.; Battaglia, G. Biomimetic pH sensitive polymersomes for efficient DNA encapsulation and delivery. Adv. Mater. 2007 , 19 , 4238−4243..

Japir, A.; Lu, N. N.; Wang, Y. H.; Mukerabigwi, J. F.; Zhou, Q. H.; Ge, Z. S. Membrane-cross-linked polymersomes with tumor ph-tunable selective permeability as intelligent nanoreactors and drug delivery vehicles. Eur. Polym. J. 2020 , 138 , 109982..

Li, J. J.; Li, Y. F.; Wang, Y. H.; Ke, W. D.; Chen, W. J.; Wang, W. P.; Ge, Z. S. Polymer prodrug-based nanoreactors activated by tumor acidity for orchestrated oxidation/chemotherapy. Nano Lett. 2017 , 17 , 6983−6990..

He, J.; Cao, J. P.; Chen, Y.; Zhang, L.; Tan, J. B. Thermoresponsive block copolymer vesicles by visible light-initiated seeded polymerization-induced self-assembly for temperature-regulated enzymatic nanoreactors. ACS Macro Lett. 2020 , 9 , 533−539..

Zhang, Y.; Uthaman, S.; Song, W.; Eom, K. H.; Jeon, S. H.; Huh, K. M.; Babu, A.; Park, I. K.; Kim, I. Multistimuli-responsive polymeric vesicles for accelerated drug release in chemo-photothermal therapy. ACS Biomater. Sci. Eng. 2020 , 6 , 5012−5023..

Nishimura, T.; Shishi, S.; Sasaki, Y.; Akiyoshi, K. Thermoresponsive polysaccharide graft polymer vesicles with tunable size and structural memory. J. Am. Chem. Soc. 2020 , 142 , 11784−11790..

Liu, F.; Kozlovskaya, V.; Medipelli, S.; Xue, B.; Ahmad, F.; Saeed, M.; Cropek, D.; Kharlampieva, E. Temperature-sensitive polymersomes for controlled delivery of anticancer drugs. Chem. Mater. 2015 , 27 , 7945−7956..

Halperin, A.; Kröger, M.; Winnik, F. M. Poly(N-isopropylacrylamide) phase diagrams: Fifty years of research. Angew. Chem. Int. Ed. 2015 , 54 , 15342−15367..

Beauté, L.; McClenaghan, N.; Lecommandoux, S. Photo-triggered polymer nanomedicines: From molecular mechanisms to therapeutic applications. Adv. Drug Deliv. Rev. 2019 , 138 , 148−166..

Wang, D. R.; Wang, X. G. Amphiphilic azo polymers: Molecular engineering, self-assembly and photoresponsive properties. Prog. Polym. Sci. 2013 , 38 , 271−301..

Ye, Q. Q.; Huo, M.; Zeng, M.; Liu, L.; Peng, L.; Wang, X. S.; Yuan, J. Y. Photoinduced reversible worm-to-vesicle transformation of azo-containing block copolymer assemblies prepared by polymerization-induced self-assembly. Macromolecules 2018 , 51 , 3308−3314..

Yu, X.; Li, J. L.; Zhang, J. N.; Jin, J.; Pan, Y. X.; Ji, X. L.; Jiang, W. Pathway-dependent shape transformation of polymeric vesicles under UV l ight and the assembly of UV-irradiated polymer. Langmuir 2024 , 40 , 17630−17637..

Wang, X. R.; Hu, J. M.; Liu, G. H.; Tian, J.; Wang, H. J.; Gong, M.; Liu, S. Y. Reversibly switching bilayer permeability and release modules of photochromic polymersomes stabilized by cooperative noncovalent interactions. J. Am. Chem. Soc. 2015 , 137 , 15262−15275..

Sun, Z. C.; Xu, Z. J.; Ding, M. Y.; Wang, L. Q.; Zhao, L.; Sui, P. L.; Li, G. D.; Jin, H. B.; Zhou, Y. F.; Lin, S. L. Ultrathin polymersomes with controllable light-responsivity via adjusting the electronic effect from para -substituents of azobenzene. Angew. Chem. Int. Ed. 2025 , 64 , e202503104..

Arai, N.; Yasuoka, K.; Zeng, X. C. Self-assembly of janusoligomers into onion-like vesicles with layer-by-layer water discharging capability: A minimalist model. ACS Nano 2016 , 10 , 8026−8037..

Liu, D.; Zhang, Z. H.; Wang, R.; Hu, J. L. Stability and deformation of vesicles in a cylindrical flow. Langmuir 2022 , 38 , 629−637..

Wu, F. S.; Lin, J. P.; Wang, L. Q.; Lin, S. L. Polymer vesicles in a nanochannel under flow fields: a DPD simulation study. Macromol. Theory Simul. 2022 , 31 , 2200027..

Tseng, Y. C.; Chang, H. Y.; Sheng, Y. J.; Tsao, H. K. Atypical vesicles and membranes with monolayer and multilayer structures formed by graft copolymers with diblock side-chains: Nonlamellar structures and curvature-enhanced permeability. Soft Matter 2022 , 18 , 7559−7568..

Wang, T. Y.; Tsao, H. K.; Sheng, Y. J. Perforated vesicles of ABA triblock copolymers with on/off-switchable nanopores. Macromolecules 2020 , 53 , 10582−10590..

Jia, L.; Wang, R.; Fan, Y. N. Encapsulation and release of drug nanoparticles in functional polymeric vesicles. Soft Matter 2020 , 16 , 3088−3095..

[Luo, Z. L.; Jiang, J. W. pH-sensitive drug loading/releasing in amphiphilic copolymer PAE-PEG: Integrating molecular dynamics and dissipative particle dynamics simulations. J. Control. Release 2012 , 162 , 185−193..

[Luo, Z. L.; Li, Y.; Wang, B. B.; Jiang, J. W. pH-sensitive vesicles formed by amphiphilic grafted copolymers with tunable membrane permeability for drug loading/release: a multiscale simulation study. Macromolecules 2016 , 49 , 6084−6094..

Ma, S. Y.; Xiao, M. Y.; Wang, R. Formation and structural characteristics of thermosensitive multiblock copolymer vesicles. Langmuir 2013 , 29 , 16010−16017..

Feng, X.; Yan, N.; Jin, J.; Jiang, W. Disassembly of amphiphilic AB block copolymer vesicles in selective solvents: A molecular dynamics simulation study. Macromolecules 2023 , 56 , 2560−2567..

Zong, Y. Q.; Cui, J.; Han, Y. Y. Composition conversion-induced disassembly of amphiphilic ABA triblock copolymer vesicles: a Monte Carlo study. Langmuir 2025 , 41 , 3434−3443..

Zhao, R. X.; Zhou, W. T.; Zong, Y. Q.; Han, Y. Y.; Cui, J. Composition conversion-induced formation of multicompartment structures in the ordered aggregates of ABA triblock copolymers: a Monte Carlo study. Acta Polymerica Sinica (in Chinese) 2026 , 57 , 998−1010..

Zhou, W. T.; Zhao, R. X.; Zong, Y. Q.; Yan, C. X.; Han, Y. Y.; Cui, J. Monte Carlo simulation of chain architecture transition induced morphological transformation of diblock copolymer vesicle. Polym. Bull. (in Chinese) 2026 , 39 , 438−446..

Brannan, A. K.; Bates, F. S. ABCA tetrablock copolymer vesicles. Macromolecules 2004 , 37 , 8816−8819..

Stoenescu, R.; Graff, A.; Meier, W. Asymmetric ABC-triblock copolymer membranes induce a directed insertion of membrane proteins. Macromol. Biosci. 2004 , 4 , 930−935..

Carmesin, I.; Kremer, K. The bond fluctuation method: A new effective algorithm for the dynamics of polymers in all spatial dimensions. Macromolecules 1988 , 21 , 2819−2823..

Larson, R. Monte Carlo lattice simulation of amphiphilic systems in two and three dimensions. J. Chem. Phys. 1988 , 89 , 1642..

Larson, R. Monte Carlo simulation of microstructural transi tions in surfactant systems. J. Chem. Phys. 1992 , 96 , 7904..

Hu, W. Structural transformation in the collapse transition of the single flexible homopolymer model. J. Chem. Phys. 1998 , 109 , 3686..

Haire, K.; Carver, T.; Windle, A. A Monte Carlo lattice model for chain diffusion in dense polymer systems and its interlocking with molecular dynamics simulation. Comput. Theor. Polym. Sci. 2001 , 11 , 17−28..

Ji, S.; Ding, J. Spontaneous formation of vesicles from mixed amphiphiles with dispersed molecular weight: Monte Carlo simulation. Langmuir 2006 , 22 , 553−559..

Metropolis, N.; Rosenbluth, A. W.; Rosenbluth, M. N.; Teller, A. H.; Teller, E. Equation of state calculations by fast computing machines. J. Chem. Phys. 1953 , 21 , 1087..

Cui, J.; Jiang, W. Structure of ABCA tetrablock copolymer vesicles and their formation in selective solvents: A Monte Carlo study. Langmuir 2011 , 27 , 10141−10147..

Ma, J. N.; Cui, J.; Han, Y. Y.; Jiang, W.; Sun, Y. C. Monte Carlo study of the micelles constructed by ABCA tetrablock copolymers and their formation in A-selective solvents. RSC Adv. 2015 , 5 , 86473−86484..

Uddin, M. A.; Yu, H. J.; Wang, L.; Ul Amin, B.; Mehmood, S.; Liang, R. X.; Haq, F.; Hu, J.; Xu, J. M. Dynamics in controllable stimuli-responsive self-assembly of polymer vesicles with stable radical functionality. ACS Appl. Mater. Interfaces 2021 , 13 , 61693−61706..

Tan, H. Y.; Liu, Y. Y.; Xie, J.; Gao, Y. J.; Li, Y. C.; Ma, L.; Zhang, L. B.; Tang, T.; Zhu, J. T. Light-triggered disassembly of photo-responsive gold nanovesicles for controlled drug release. Mater. Chem. Front 2020 , 4 , 2805−2811..

[Tan, M.; Sun, F.; Zhao, X. Y.; Zhao, Z. B.; Zhang, S. R.; Xu, X. N.; Adijiang, A.; Zhang, W.; Wang, H. Y.; Wang, C. K.; Li, Z.; Scheer, E.; Xiang, D. Conductance evolution of photoisomeric single-molecule junctions under ultraviolet irradiation and mechanical stretching. J . Am . Chem . Soc . 2024 , 146 , 6856−6865..

Discher, D. E.; Eisenberg, A. Polymer vesicles. Science 2002 , 297 , 967−973..

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