Higher surface exposure of polar functional groups correlates with higher tendency to stick to metal surfaces and AFM tips, indicating involvement of specific polar interactions in the adhesion behavior. In addition, an AFM method is identified to prospectively assess the risk of sticking during the early stages of drug development.

The phenomenon of microphase separation is an example of self-assembly in soft matter and has been observed in block copolymers (BCPs) and similar materials (i.e., supramolecular assemblies (SMAs) and homo/block copolymer blends (HBCs)). In this study, we use microphase separation to construct responsive polymer brushes that collapse to generate periodic surfaces. This is achieved by a chemical reaction between the minor block (10%, poly(4-vinylpyridine)) of the block copolymer and a substrate. The major block of polystyrene (PS) forms mosaic-like arrays of grafted patches that are 10-20 nm in size. Depending on the nature of the assembly (SMA, HBC, or neat BCP) and annealing method (exposure to vapors of different solvents or heating above the glass transition temperature), a range of "mosaic" brushes with different parameters can be obtained. Successive grafting of a secondary polymer (polyacrylamide, PAAm) results in the fabrication of binary polymer brushes (BPBs). Upon being exposed to specific selective solvents, BPBs may adopt different conformations. The surface tension and adhesion of the binary brush are governed by the polymer occupying the top stratum. The "mosaic" brush approach allows for a combination of strongly immiscible polymers in one brush. This facilitates substantial contrast in the surface properties upon switching, previously only possible for substrates composed of predetermined nanostructures. We also demonstrate a possible application of such PS/PAAm brushes in a tunable bioadhesion-bioadhesive (PS on top) or nonbioadhesive (PAAm on top) surface as revealed by Escherichia coli bacterial seeding.

Grafted polymers and polymer brushes in particular have attracted significant attention in the last 2 decades as a way to alter and control interfacial properties. In the case of polymer brushes on solid substrates, a high grafting density of polymer chains results in stretching of the polymer coils normal to the substrate surface due to the effect of excluded volume. In this study, polyacrylamide is grafted to the surface of relatively soft thin films of chitosan. The "grafting through" approach is used by introducing double C═C bonds to amino groups of chitosan. The acquired kinetic data of grafting along with AFM and ellipsometry characterization suggest that the chitosan substrate undergoes surface reconstruction during the grafting of PAAm and simultaneously induces PAAm growth inside the soft substrate. As a result, much higher amounts of grafted polymer are achieved in comparison to traditional hard substrates like silicon or glass. Additionally, selective plasma etching of PAAm reveals filament-like structures oriented normal to the surface.

The concept of co-ordinated responsive arrays of surface-linked islands (polymer CORALs) is introduced. This study targets a responsive system capable of revealing or covering the substrate surface in response to environmental changes in a reversible way. A convenient method of fabrication of polymer CORALs is proposed. It is based on microphase separation that occurs in thin films of supramolecular assemblies of block copolymers with reactive blocks. Such blocks form nanometer-size domains that may serve as anchors for surface-linked polymer islands. Two characteristics of the islands are critically important for the switching function: high grafting density within the islands and small lateral separation that allows interactions between polymer chains grafted to the neighboring islands. This combination permits complete coverage of the substrate surface upon exposure to a good solvent (relaxed state). In a weak solvent, the chains collapse within the islands, thus revealing the substrate (compact state). The morphology of the CORALs in both states and some details of the switching process were studied with atomic force microscopy, grazing incidence small-angle scattering, and coarse-grained molecular dynamic simulations.

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