Nanoengineering Spikey Surfaces: Investigation of Reversible Organizational Control of Surface-Tethered Polypeptide Brushes.

Nature serves as an important source of inspiration for the innovation and development of micro- and nanostructures for advanced functional surfaces and substrates. One example used in nature is a spikey surface ranging from micrometer-sized spikes on pollen grains down to the nanometer-scale protein spikes found on viruses. This study explored the realization of such highly textured surfaces via the nanoengineering of self-assembled poly(γ-benzyl-l-glutamate) "nanospikes", exploiting solvent-induced chain organization, controlled surface chemical functionality, and enhanced stability in the form of polymer brushes. The reversible solvent-responsive behavior of these polymer chains and the aggregation behavior of the chain-ends were investigated via fluorescence characterization and studied through molecular simulations. Vapor-based solvent treatments were developed for orientation control with in situ analysis to understand film response and brush organizational behavior under different selected conditions. The effect of sub-100 nm nanopatterning on surface morphology and chain organization was examined via an integrated approach of experimental and computational studies. The methodologies established in this study present opportunities for engineering sophisticated nanoscale spikey surfaces with high customizability by means of nanolithography combined with solvent-assisted treatments.