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

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Title: Critical Adsorption of Polyelectrolytes onto Patchy Particles with a Low-Dielectric Interior.
Authors: Anhesini, Dante A.1 (AUTHOR), Caetano, Daniel L. Z.1,2 (AUTHOR), Caruso, Icaro P.1 (AUTHOR), Cherstvy, Andrey G.2 (AUTHOR), de Carvalho, Sidney J.1 (AUTHOR) sidney.carvalho@unesp.br
Source: Polymers (20734360). Aug2025, Vol. 17 Issue 16, p2205. 24p.
Subjects: Polyelectrolytes, Electrostatic interaction, Electric charge, Protein-protein interactions, Physisorption, Monte Carlo method, Colloids, Dielectric materials
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 same sign as that of the PE, resulting in nonmonotonic 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. [ABSTRACT FROM AUTHOR]
Copyright of Polymers (20734360) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Critical Adsorption of Polyelectrolytes onto Patchy Particles with a Low-Dielectric Interior.
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  Data: <searchLink fieldCode="JN" term="%22Polymers+%2820734360%29%22">Polymers (20734360)</searchLink>. Aug2025, Vol. 17 Issue 16, p2205. 24p.
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  Data: <searchLink fieldCode="DE" term="%22Polyelectrolytes%22">Polyelectrolytes</searchLink><br /><searchLink fieldCode="DE" term="%22Electrostatic+interaction%22">Electrostatic interaction</searchLink><br /><searchLink fieldCode="DE" term="%22Electric+charge%22">Electric charge</searchLink><br /><searchLink fieldCode="DE" term="%22Protein-protein+interactions%22">Protein-protein interactions</searchLink><br /><searchLink fieldCode="DE" term="%22Physisorption%22">Physisorption</searchLink><br /><searchLink fieldCode="DE" term="%22Monte+Carlo+method%22">Monte Carlo method</searchLink><br /><searchLink fieldCode="DE" term="%22Colloids%22">Colloids</searchLink><br /><searchLink fieldCode="DE" term="%22Dielectric+materials%22">Dielectric materials</searchLink>
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  Data: 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 same sign as that of the PE, resulting in nonmonotonic 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. [ABSTRACT FROM AUTHOR]
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  Label:
  Group: Ab
  Data: <i>Copyright of Polymers (20734360) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.3390/polym17162205
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        Text: English
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      – SubjectFull: Electrostatic interaction
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      – SubjectFull: Monte Carlo method
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      – SubjectFull: Colloids
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      – SubjectFull: Dielectric materials
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              Text: Aug2025
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