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聚电解质在具有低介电常数内部的补丁颗粒上的临界吸附。

Critical Adsorption of Polyelectrolytes onto Patchy Particles with a Low-Dielectric Interior.

作者信息

Anhesini Dante A, Caetano Daniel L Z, Caruso Icaro P, Cherstvy Andrey G, de Carvalho Sidney J

机构信息

Institute of Biosciences, Humanities and Exact Sciences, São Paulo State University (UNESP), São José do Rio Preto 15054-000, Brazil.

Institute for Physics & Astronomy, University of Potsdam, D-14476 Potsdam-Golm, Germany.

出版信息

Polymers (Basel). 2025 Aug 12;17(16):2205. doi: 10.3390/polym17162205.

Abstract

A polyelectrolyte (PE) chain in the vicinity of an oppositely charged surface can exhibit a discontinuous transition from the adsorbed to the desorbed state once the electrostatic attractive interactions are not strong enough to overcome the entropic losses caused by the PE-surface adsorption. In the context of PE-protein interactions, the heterogeneity of the charge distribution and the effects of a low dielectric permittivity underneath the surface are crucial. Studies of the combined effects of these two properties are very sparse, especially in the spherical geometry; we thus fill this gap here. We study the adsorption of PE chains onto spherical particles with heterogeneously charged surfaces, with the main focus on the critical-adsorption conditions and the effects of a low-dielectric core. Metropolis Monte Carlo simulations are employed, with the PE exploring the phase-space around the binding particle in the canonical ensemble. Two adsorption-desorption transitions are observed when the particle possesses a net charge of the as that of the PE, resulting in behavior of the critical charge density required for the PE-particle electrostatically driven adsorption. An increased affinity between the PEs and low-dielectric particles with variable heterogeneous charge distributions is observed, in contrast to the behavior detected for homogeneous low-dielectric particles. This higher affinity occurs when the Debye screening length in the solution becomes comparable to the dimensions of a patch of the opposite sign to the PE. A number of real-life applications of the considered PE-particle system is presented in the discussion, in particular regarding the properties of the complex formation between various PEs and globular proteins featuring a dipolar-type distribution of electric charges on their surfaces, such as insulin and bovine serum albumin.

摘要

一旦静电吸引相互作用不足以克服聚电解质(PE)-表面吸附所导致的熵损失,靠近带相反电荷表面的聚电解质链会呈现从吸附态到解吸态的不连续转变。在PE-蛋白质相互作用的背景下,电荷分布的不均匀性以及表面下方低介电常数的影响至关重要。对这两种性质综合影响的研究非常稀少,尤其是在球形几何结构中;因此我们在此填补这一空白。我们研究PE链在具有不均匀带电表面的球形颗粒上的吸附,主要关注临界吸附条件和低介电核心的影响。采用 metropolis 蒙特卡罗模拟,PE在正则系综中探索围绕结合颗粒的相空间。当颗粒的净电荷与PE的净电荷相同时,观察到两个吸附-解吸转变,导致PE-颗粒静电驱动吸附所需的临界电荷密度呈现特定行为。与均匀低介电颗粒的行为相反,观察到PE与具有可变不均匀电荷分布的低介电颗粒之间的亲和力增加。当溶液中的德拜屏蔽长度与PE相反符号的斑块尺寸可比时,会出现这种更高的亲和力。讨论中介绍了所考虑的PE-颗粒系统的许多实际应用,特别是关于各种PE与表面具有偶极型电荷分布的球状蛋白质(如胰岛素和牛血清白蛋白)之间形成复合物的性质。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5294/12390199/a68506f60d1d/polymers-17-02205-g001.jpg

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