Theoretical Study of Comb-Polymers Adsorption on Solid Surfaces

TL;DR

This paper provides a theoretical analysis of neutral comb-polymer adsorption on surfaces, identifying different regimes and deriving scaling laws for layer properties, with implications for bio-separation technologies.

Contribution

It introduces a comprehensive theoretical framework for comb-polymer adsorption, detailing regimes and deriving explicit asymptotic and scaling laws for layer characteristics.

Findings

Identified three adsorption regimes: mushroom, brush, and non-adsorbed.

Derived asymptotic forms for monomer concentration and layer thickness.

Predicted scaling laws for transitions between regimes.

Abstract

We propose a theoretical investigation of the physical adsorption of neutral comb-polymers with an adsorbing skeleton and non-adsorbing side-chains on a flat surface. Such polymers are particularly interesting as "dynamic coating" matrices for bio-separations, especially for DNA sequencing, capillary electrophoresis and lab-on-chips. Separation performances are increased by coating the inner surface of the capillaries with neutral polymers. This method allows to screen the surface charges, thus to prevent electro-osmosis flow and adhesion of charged macromolecules (e.g. proteins) on the capillary walls. We identify three adsorption regimes: a "mushroom" regime, in which the coating is formed by strongly adsorbed skeleton loops and the side-chains anchored on the skeleton are in a swollen state, a "brush" regime, characterized by a uniform multi-chains coating with an extended layer of non-adsorbing side-chains and a non-adsorbed regime. By using a combination of mean field and scaling approaches, we explicitly derive asymptotic forms for the monomer concentration profiles, for the adsorption free energy and for the thickness of the adsorbed layer as a function of the skeleton and side-chains sizes and of the adsorption parameters. Moreover, we obtain the scaling laws for the transitions between the different regimes. These predictions can be checked by performing experiments aimed at investigating polymer adsorption, such as Neutron or X-ray Reflectometry, Ellipsometry, Quartz Microbalance, or Surface Force Apparatus.