Charge regulation mechanism in end-tethered weak polyampholytes

Prusty, D.; Nap, R. J.; Szleifer, I.; Olvera de la Cruz, M.

doi:10.1039/d0sm01323d

Title: Charge regulation mechanism in end-tethered weak polyampholytes

Journal Article · Tue Sep 01 00:00:00 EDT 2020 · Soft Matter

DOI:https://doi.org/10.1039/d0sm01323d· OSTI ID:1850628

Prusty, D. ^[1];

^[1];

^[1]

Northwestern Univ., Evanston, IL (United States)

Weak polyampholytes, containing oppositely charged dissociable groups, are expected to be responsive to changes in ionic conditions. Here, we determine structural and thermodynamic properties, including the charged groups’ degrees of dissociation, of end-tethered weak polyampholyte layers as a function of salt concentration, pH, and the solvent quality. For diblock weak polyampholytes grafted by their acidic blocks, we find that the acidic monomers increase their charge while the basic monomers decrease their charge with decreasing salt concentration for pH values less than the pK_a value of both monomers and vice versa when the pH > pK_a. This complex charge regulation occurs because the electrostatic attraction between oppositely charged blocks is stronger than the repulsion between monomers with the same charge in both good and poor solvents when the screening by salt ions is weak. This is shown by the retraction of the top block into the bottom layer. In the case of poor solvent conditions to the basic block (the top block), we find lateral segregation of basic monomers into micelles, forming a two-dimensional hexagonal pattern on the surface at intermediate and high pH values for monovalent salt concentrations from 0.01 to 0.1 M. When the solvent is poor to both blocks, we find lateral segregation of the grafted acidic block into lamellae with longitudinal undulations of low and high acidic monomer density. By exploiting weak block polyampholytes, our work expands the parameter space for creating responsive surfaces stable over a wide range of pH and salt concentration.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0000989

OSTI ID:: 1850628

Alternate ID(s):: OSTI ID: 1658978

Journal Information:: Soft Matter, Vol. 16, Issue 38; ISSN 1744-683X

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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