Roman Sheparovych

Chemical Gating with Nanostructured Responsive Polymer Brushes: Mixed Brush versus Homopolymer Brush

In this report, we describe a novel approach to create an electrochemical gating system using mixed polymer brushes grafted to an electrode surface, and we explore the switchable properties of these mixed polymer brushes. The morphological transitions in the mixed polymer brushes associated with the electrode surface result in the opening, closing, or precise tuning of their permeability for ion transport through the channels formed in the nanostructured thin film in response to an external stimulus (pH change). The gating mechanism was studied by atomic force microscopy, ellipsometry, contact angle measurements, force-distance measurements, and electrochemical impedance spectroscopy. In comparison to a homopolymer brush system, the mixed brush demonstrates much broader variation of ion transport through the thin film. We suggest that this approach could find important applications in electrochemical sensors and devices with tunable/switchable access to the electrode surface.

Adapting low-adhesive thin films from mixed polymer brushes.

The concept of the responsive/adaptive mixed polymer brushes was applied to the development of the thin film coatings possessing low adhesive properties that were evaluated with AFM probes in different media. Mixed brushes composed of polydimethylsiloxane (PDMS) and polyethyleneoxide (PEO) revealed a selective layered segregation in air and water. Immersion of the sample into an aqueous environment drove PEO chains to the brush-water interface while upon drying the surface undergoing reconstruction and was occupied with PDMS. Low interfacial energies of PDMS in air and PEO in water provided low-adhesive properties of the PDMS-PEO brushes to the probes in both media due to the spontaneous and rapid reconstruction of the mixed brush.

Stimuli-responsive properties of peptide-based copolymers studied via directional growth of self-assembled patterns on solid substrate

We studied the self-assembly of peptide-based ABA and CBC triblock-copolymers (obtained by bacterial expression) containing random coiled hydrophilic central B blocks flanked with helical A or C blocks. The A and C blocks were of different compositions with respect to the fraction of lysine residues which provided a higher pH sensitivity of the copolymer solutions. The interchain interactions of the copolymers driven by external stimuli (pH and temperature) were explored in the process of macromolecular self-assembling in the thin films of the copolymer solutions deposited on the solid substrate. The interactions involved in the macromolecular association affected the morphology of the developed patterns. The polypeptide of the B block was not involved in the formation of the secondary structures, while the A and C blocks demonstrated helical folding responsible for the intermolecular association. The mechanism of the responsive behavior of the copolymers is based on the reversible assembling of the helices into coiled-coil structures upon the change of pH or temperature. It was found that at low pH values, when electrostatic repulsion was strong and the A/C blocks unfolded, assembling yielded fractal dendrites. Increasing the pH resulted in the recovery of the helical conformation of the A/C blocks and caused a transition from the fractal to compact structures. An elevation of temperature resulted in the disruption of the dendritic structures. The reported here approach to the evaluation of the intermolecular interactions, based on the analysis of the dendritic patterns, provides a rapid and simple method for the characterization of complex processes of self-assembling biomacromolecules.