Guilherme Volpe Bossa*, Erik Hobbie and Sylvio May,
{"title":"Counterion Release from Macroion Assemblies of Planar Geometry","authors":"Guilherme Volpe Bossa*, Erik Hobbie and Sylvio May, ","doi":"10.1021/acs.jpcb.4c03222","DOIUrl":null,"url":null,"abstract":"<p >Macroions such as nanoparticles, polyelectrolytes, ionic gels, and amphiphiles can form condensed, often self-assembled, phases that are embedded in a solvent region. The condensed phase contains not only the partially or fully immobile charges of their macroions but also corresponding counterions that are mobile and thus free to migrate out of their confinement into the solvent region where they benefit from high translational entropy. Based on the nonlinear Poisson–Boltzmann model for monovalent ions, we quantify the corresponding fraction of released counterions for a planar slab geometry of the macroion phase. Slab thickness, extension of the solvent phase, fixed background charge density provided by the macroions, and dielectric constants inside slab and solvent combine into three dimensionless parameters that the fraction of released counterions depends on. We calculate that fraction and analyze the limits of a thin macroion phase, a large solvent phase, and linearized theory, where simple analytic results become available. Of particular interest is the presence of a single-planar interface that separates a bulk macroion phase from an extended solvent region. We calculate the apparent surface charge density that emerges due to the released counterions. Our model yields a comprehensive description of counterion partitioning between a planar macroion phase and a solvent region on the level of mean-field electrostatics in the absence of added salt ions.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":null,"pages":null},"PeriodicalIF":2.8000,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry B","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jpcb.4c03222","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Macroions such as nanoparticles, polyelectrolytes, ionic gels, and amphiphiles can form condensed, often self-assembled, phases that are embedded in a solvent region. The condensed phase contains not only the partially or fully immobile charges of their macroions but also corresponding counterions that are mobile and thus free to migrate out of their confinement into the solvent region where they benefit from high translational entropy. Based on the nonlinear Poisson–Boltzmann model for monovalent ions, we quantify the corresponding fraction of released counterions for a planar slab geometry of the macroion phase. Slab thickness, extension of the solvent phase, fixed background charge density provided by the macroions, and dielectric constants inside slab and solvent combine into three dimensionless parameters that the fraction of released counterions depends on. We calculate that fraction and analyze the limits of a thin macroion phase, a large solvent phase, and linearized theory, where simple analytic results become available. Of particular interest is the presence of a single-planar interface that separates a bulk macroion phase from an extended solvent region. We calculate the apparent surface charge density that emerges due to the released counterions. Our model yields a comprehensive description of counterion partitioning between a planar macroion phase and a solvent region on the level of mean-field electrostatics in the absence of added salt ions.
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.