Advantages and limitations of the use of an extended polyelectrolyte model to describe the proton-binding process in macromolecular systems. Application to a poly(acrylic acid) and a humic acid.

A number of studies have shown the suitability of the polyelectrolyte model to describe the proton-binding behavior of macromolecules. This model, however, has two limitations associated with its theoretical approach: (1) it does not consider the possible heterogeneity of binding sites, and (2) for certain calculations, it involves the need to assume a specific molecular geometry. In this article we describe the theoretical basis of an extension of the polyelectrolyte model that removes the two limitations described above. Likewise, we discuss the advantages and limitations of the extended polyelectrolyte model (EPM) through its application to describe the proton-binding process in a well-characterized macromolecular system (a poly(acrylic acid)) and a complex molecular system (a humic acid). The results obtained showed the suitability of EPM to describe proton-binding processes in complex molecular systems without the need to assume previously a specific molecular geometry and explicitly considering the possible heterogeneity of the binding sites. The results obtained indicated that the field effects associated with the conformational structure corresponding to each ionic strength, even in the discharged state, affect the values of the intrinsic constants defining the proton-binding process using EPM. Likewise, EPM analysis reveals the significant influence of both the surface charge density and the molecular size on the value of the electrostatic effects affecting the values of the intrinsic constants in the proton-binding process.