Abstract

The spontaneous formation and fusion of raspberry vesicles was studied using the dissipative particle dynamics (DPD) method. The vesicles were formed through the self-assembly of amphiphilic E12O6F2 star terpolymers in selective solvent. E and F blocks are solvophobic and the O block is solvophilic. The shortest F block plays a major role in the formation of raspberry vesicles. Distinct vesicle formation mechanisms were observed at different polymer concentrations. At higher concentrations, vesicles form via the bending and closure of an oblate F-bump-E bilayer. At lower concentrations, the formation pathway contains: the initial formation of a vesicle with a core, the combination of such vesicles into cylindrical micelles, and the bending of the cylindrical micelles to form a hollow vesicle. In addition, raspberry vesicle fusion is regulated by F bumps through the continuous coalescence of them from apposed vesicle membranes. The contact area bends, followed by the formation of a fusion pore and a tilted inner layer. As the pore sealed, the hemifusion structure appears, which further restructures to form a vesicle. Our results provide guidance on understanding the dynamic processes of complex vesicles and biological membrane fusion.

Highlights

  • Micelles, whose surfaces are composed of physically or chemically distinct domains, are regarded as soft patchy micelles [1,2]

  • In Mechanism II, vesicles form through the diffusion of the solvent into semivesicles, and a cavity is formed as a result

  • Controlling the vesicle formation path is of great importance to improving encapsulation efficiency

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Summary

Introduction

Micelles, whose surfaces are composed of physically or chemically distinct domains, are regarded as soft patchy micelles [1,2]. Studies [7,9,10,11] have revealed that by manipulating conditions such as solvent addition rate, polymer concentration, block ratio, polymer–solvent interaction, or heating rate, the formation mechanism can be tuned Fusion behavior is another important feature of vesicles [12,13,14]. Since many functions of vesicles are related to their fusion behavior [23], investigating the fusion process can help us understand the relationship between structures and the design of potential applications [13,27] As reported from both experiments and simulations, patchy hollow capsules can be obtained from the self-assembly of amphiphilic block copolymers in selective solvent [25,28,29,30]. The fusion path of the patchy vesicle was studied for further understanding of the dynamic processes of complex vesicles

Simulation Methods
Effect of Block Solvophobicity on Vesicle Formation
Vesicle Formation Mechanism
Findings
Vesicle Fusion
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