Charge Regulation with Fixed and Mobile Charges

TL;DR

This paper reviews the mean-field modeling of charge regulation phenomena at interfaces, emphasizing recent advances in understanding mobile macro-ions and their impact on screening length and capacitance in ionic solutions.

Contribution

It introduces a unified formalism for charge regulation involving fixed and mobile charges, highlighting recent developments in modeling mobile macro-ions and their effects on electrostatic screening.

Findings

Derived a general screening length combining intrinsic and bulk capacitance.

Compared different modeling approaches like cell model and collective approach.

Discussed advantages and limitations of various charge regulation models.

Abstract

Uncompensated charges do not occur in Nature and any local charge should be a result of charge separation. Dissociable chemical groups at interfaces in contact with ions in solution, whose chemical equilibrium depends both on short-range non-electrostatic and long-range electrostatic interactions, are the physical basis of this charge separation, known as charge regulation phenomena. The charged groups can be either fixed and immobile, as in the case of solvent-exposed solid substrate and soft bounding surfaces, (e.g., molecularly smooth mica surfaces and soft phospholipid membranes), or free and mobile, as in the case of charged macro-ions, (e.g., protein or other biomolecules). Here, we review the mean-field formalism used to describe both cases, with a focus on recent advances in the modeling of mobile charge-regulated macro-ions in an ionic solution. The general form of the screening length in such a solution is derived, and is shown to combine the concept of intrinsic capacitance, introduced by Lund and J\"{o}nsson, and bulk capacitance, resulting from the mobility of small ions and macro-ions. The advantages and disadvantages of different formulations, such as the cell model vs. the collective approach, are discussed, along with several suggestions for future experiments and modeling.