Equilibrium conformations and surface charge regulation of spherical polymer brushes in stretched regimes

TL;DR

This study investigates the equilibrium shapes and surface charge regulation of spherical polymer brushes in stretched states, combining density functional theory and Monte Carlo simulations to analyze ionic and electrostatic effects.

Contribution

It introduces a comprehensive framework integrating classical DFT and Monte Carlo simulations to analyze polymer brush conformations and charge regulation mechanisms.

Findings

High ionic strength leads to polymer swelling dominated by ionic entropy.

Low ionic concentrations result in a balance between electrostatic and entropic forces.

Charge regulation effects significantly influence the surface charge distribution.

Abstract

In the present work, we study the equilibrium conformations of linear polyelectrolytes tethered onto a spherical, oppositely charged core in equilibrium with an ionic reservoir of fixed concentration. Particular focus is placed on the situation of stretched chains, where the monomer concentration is known to display an inverse square-law decay far away from the spherical surface, which is then further extrapolated all the way down to the grafting core. While the equilibrium distributions of mobile ions are computed in the framework of a classical Density Functional Theory (cDFT) that incorporates both their size and electrostatic correlations within the grafted polyelectrolyte, the equilibrium configuration of the latter is described by its averaged radius of gyration, which is taken as a variational parameter that guarantees mechanical equilibrium across the polymer-solvent interface. The averaged particle size is then analyzed over a wide range of polymerization degrees, ionic concentrations and functionality of the polymer backbones. Two distinct regimes can be identified: at high ionic strengths, swelling of the grafted polymers is dominated by ionic entropic contribution as well as polymer size effects, whereas at low ionic concentrations a balance between electrostatic and entropic effects is the main driven mechanism for particle stretching. Using Monte Carlo simulations, we then proceed to investigate the effects of charge regulation when the brush core is further decorated with active functional sites randomly distributed over its surface, which act as receptors onto which dissolved acidic ions can be adsorbed.