Adsorption-active polydisperse brush with tunable molecular mass distribution

Abstract

Recently, a novel class of responsive uncharged polymer brushes has been proposed [Klushin et al., J. Chem. Phys. 154(7), 074904 (2021)] where the brush-forming chains have an affinity to the substrate. For sufficiently strong surface interactions, a fraction of chains condenses into a near-surface layer, while the remaining ones form the outer brush with a reduced grafting density. The dense layer and the more tenuous outer brush can be seen as coexisting microphases. The effective grafting density of the outer brush is controlled by the adsorption strength and can be changed reversibly as a response to changes in environmental parameters. In this paper, we use numerical self-consistent field calculations to study this phenomenon in polydisperse brushes. Our results reveal an unexpected effect: Although all chains are chemically identical, shorter chains are adsorbed preferentially. Hence, with the increase in the surface affinity parameter, a reduction in the surface grafting density of the residual brush is accompanied by a change in the shape of its molecular mass distribution (MMD). In particular, an originally bidisperse brush can be effectively transformed into a nearly monodisperse one containing only the longer chain fraction. We introduce a method of assigning different chain conformations to one or the other microphase, based on analyzing tail length distributions. In a polydisperse brush with a uniform MMD, short chains are relegated to the adsorbed phase, leading to a narrower effective MMD in the residual brush. Preferential adsorption is not absolute, and longer chains are also partially involved in adsorption. As a result, not only the width of the distribution decreases but also its shape evolves away from the initial uniform distribution. We believe that the effect of preferential adsorption stems from a fundamental property of a polydisperse brush, which is characterized by a spectrum of chemical potential values for monomers belonging to chains of different lengths. Hence, preferential adsorption is also expected in polyelectrolyte brushes; moreover, brush polydispersity would affect coexistence with any other condensed phase, not necessarily related to adsorption.