Comparative Study of Polymer Globules and Liquid Droplets in Poor Solvents: Effects of Cosolvents and Solvent Quality.

IF 2.8 2区 化学 Q3 CHEMISTRY, PHYSICAL The Journal of Physical Chemistry B Pub Date : 2025-01-09 DOI:10.1021/acs.jpcb.4c07137
Tushar Mahendrakar, Kaustubh Rane
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引用次数: 0

Abstract

We compare the structures of polymer globules, composed of flexible polymer chains, with liquid droplets made of nonbonded monomers of the same polymer in poor solvents. This comparison is performed in three different poor solvents, with and without the addition of cosolvents. Molecular dynamics simulations are used to analyze the properties of the polymer globules, while semigrand canonical Monte Carlo simulations are used to form metastable liquid droplets of nonbonded monomers through homogeneous nucleation in the same solvents. Our findings show that both globules and droplets are nearly spherical, although droplets display slightly more anisotropy. In the absence of cosolvents, the surrounding solvent structures are similar for both globules and droplets. However, in the presence of cosolvents, significant differences arise in the liquid structure, with the disparities increasing as the solvent quality worsens. Cosolvents tend to accumulate near the surface of globules due to the restricted movement of bonded monomers, which partially immobilizes the cosolvents. This effect becomes more pronounced as the solvent quality declines. Interfacial free energy calculations reveal that cosolvents act like surfactants, promoting larger interfacial areas for both globules and droplets. This effect is more significant for globules due to the greater accumulation of cosolvents at their surface. Therefore, modeling polymer globules as liquid droplets may underestimate the impact of cosolvents on the stability of the globule state. Additionally, the transition states involved in polymer collapse in the presence of cosolvents differ from those involved in the nucleation of liquid droplets in the same solution.

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来源期刊
CiteScore
5.80
自引率
9.10%
发文量
965
审稿时长
1.6 months
期刊介绍: An essential criterion for acceptance of research articles in the journal is that they provide new physical insight. Please refer to the New Physical Insights virtual issue on what constitutes new physical insight. Manuscripts that are essentially reporting data or applications of data are, in general, not suitable for publication in JPC B.
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