Controlling self-assembling co-polymer coatings of hydrophilic polysaccharide substrates via co-polymer block length ratio

A Scacchi and K Hasheminejad and SJ Nikkhah and M Sammalkorpi, JOURNAL OF COLLOID AND INTERFACE SCIENCE, 640, 809-819 (2023).

DOI: 10.1016/j.jcis.2023.02.117

Hypothesis: The degree of polymerization of amphiphilic di-block co- polymers, which can be varied with ease in computer simulations, provides a means to control self-assembling di-block co-polymer coatings on hydrophilic substrates.Simulations: We examine self-assembly of linear amphiphilic di-block co-polymers on hydrophilic sur-face via dissipative particle dynamics simulations. The system models a glucose based polysaccharide surface on which random co-polymers of styrene and n-butyl acrylate, as the hydrophobic block, and starch, as the hydrophilic block, forms a film. Such setups are common in e.g. hygiene, pharmaceutical, and paper product applications.Findings: Variation of the block length ratio (35 monomers in total) reveals that all examined composi-tions readily coat the substrate. However, strongly asymmetric block co-polymers with short hydropho-bic segments are best in wetting the surface, whereas approximately symmetric composition leads to most stable films with highest internal order and well-defined internal stratification. At intermediate asymmetries, isolated hydrophobic domains form. We map the sensitivity and stability of the assembly response for a large variety of interaction parameters. The reported response persists for a wide polymer mixing interactions range, providing general means to tune surface coating films and their internal struc-ture, including compartmentalization.(c) 2023 The Author(s). Published by Elsevier Inc. This is an open access article under the CC BY license (

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