Charge regulation with fixed and mobile charged macromolecules

Uncompensated charges do not usually 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., atomically smooth mica surfaces and soft phospholipid membranes), or free and mobile, as in the case of charged macroions (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 is derived, and is shown to combine the concept of intrinsic capacitance (introduced by Lund and Jonsson) with 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.