Self-assembly of amphiphilic homopolymers grafted onto spherical nanoparticles: complete embedded minimal surfaces and a machine learning algorithm for their recognition.

By means of computer modelling, the self-assembly of amphiphilic A--B macromolecules, grafted onto a spherical nanoparticle, is studied. In a solvent, that is poor for side pendants, the macromolecules self-assemble into thin membrane-like ABBA bilayers deviated from spherical nanoparticles. The bilayers form morphological structures that depend on the grafting density and macromolecular polymerization degree and can be referred to as the classical family of complete embedded minimal surfaces.

Hedgehog, Chamomile, and Multipetal Polymeric Structures on the Nanoparticle Surface: Computer Modelling.

A single spherical nanoparticle coated with a densely grafted layer of an amphiphilic homopolymer with identical A-graft-B monomer units was studied by means of coarse-grained molecular dynamics. In solvent, selectively poor for mainchain and good for pendant groups; the grafted macromolecules self-assemble into different structures to form a complex pattern on the nanoparticle surface. We distinguish hedgehog, multipetalar, chamomile, and densely structured shells and outline the area of their stability using visual analysis and calculate aggregation numbers and specially introduced order parameters, including the branching coefficient and relative orientation of monomer units.

Self-assembly in amphiphilic spherical brushes.

The structure of amphiphilic spherical brushes, consisting of the nano-SiO core, the hyperbranched polyamidoamine subshell, and a grafted layer of long hydrophobically modified polyacrylamide (HMPAM) chains, in aqueous solution was analyzed and described in the framework of the original mean-field approach. The scaling estimations of the hydrodynamic radius of such polymer brushes as a function of the number of grafted macromolecules allow concluding that the HMPAM shells are in a globular state and that the region of the stretched chains adjacent to the grafting surface is a minor part of the grafted macromolecules and does not have a significant impact on the self-assembly of the HMPAM shell caused by the complex hydrophobic-hydrophilic composition of their monomer units. In mean-field theory, the amphiphilic nature of HMPAM was taken into account by attaching the hydrophobic side group H to some fraction of monomer units of the hydrophilic P backbone.

Lamellae and parking garage structures in amphiphilic homopolymer brushes with different grafting densities.

This article is devoted to the study of polymer layers of amphiphilic homopolymers tightly grafted to a flat surface at the nodes of a square lattice. It was shown that, due to the amphiphilicity of monomer units containing groups with different affinities, in a selective solvent, such layers form lamellae perpendicular to the grafting surface. The period of the lamellae depends on the grafting density and the quality of the solvent.

Lamellae-Parking Garage Structure-Lamellae Transition in Densely Grafted Layers of Amphiphilic Homopolymers: Impact of Polymerization Degree.

By means of computer modeling, the self-organization of densely grafted macromolecules with amphiphilic monomer units as a function of macromolecular polymerization degree and solvent quality was studied and a diagram of state was constructed. The diagram contains fields of disordered distribution of monomer units and of prolonged aggregates, regions of lamellae with small and big domain spacing, and transition region. Within the transition region, the lamellae with different spacing coexist: the lamellae with big domain spacing are on the top of the grafting layer and the lamellae with small domain spacing are close to the grafting surface.