Surface-assisted assembly of a histidine-rich lipidated peptide for simultaneous exfoliation of graphite and functionalization of graphene nanosheets.

Biological molecules have promising potential to exfoliate graphite and produce biocompatible graphene nano-materials for biomedical applications. Here, a systematic design of a histidine-rich lipidated peptide sequence is presented that simultaneously exfoliates graphite flakes and functionalizes the resulting graphene nanosheets (∼150 nm lateral size) with long-term dispersion stability in aqueous solution (>8 months). The details of peptide/peptide and peptide/graphite interactions are probed using various microscopy, spectroscopy and molecular dynamics simulation methods. The results show that histidine and stearic acid interact with the graphite surface through π-π stacking and hydrophobic forces, respectively. Surface-assisted assembly of peptide molecules is then initiated via hydrogen bonds between deprotonated histidine segments, and a textured peptide nano-structure is formed. The work of adhesion between the peptide and graphite is found to be high enough to promote exfoliation of graphite flakes through layer-by-layer peeling of graphene nanosheets. The positively charged arginine in the peptide is exposed outward, and is responsible for the stable dispersion. The peptide molecules are sufficiently small, presenting the possibility to insert into and increase the spacing between the graphitic layers for enhanced exfoliation. The peptide-functionalized graphene nanosheets not only show great biocompatibility with cells in vitro, but also enhance cancer drug uptake by the cells.

Instabilities of Teflon AF thin films in alumina nanochannels and adhesion of bi-level Teflon AF nanopillars.

In this paper, a novel replica-molding technique for fabrication of bi-level Teflon AF nanopillars, as an electrostatic-based dry adhesive, is reported. The technique reported herein relies on the concurrent heating and cooling of the Teflon AF melt which filled vertically aligned alumina nanochannels as the mold. Unlike conventional polymer infiltration methods which consist of filling the mold by only heating the polymer above its glass transition temperature, in the current method, the polymer melt was also simultaneously cooled down during the infiltration process. Concurrent cooling of the Teflon AF melt allowed control over the interfacial instabilities of the polymer thin film, which formed ahead of the polymer melt upon its infiltration into the alumina nanochannels. By doing so, the geometrical properties of the peculiar fluffy nanostructure which was subsequently developed-after removal of the mold-on top of the extremely high aspect-ratio Teflon AF nanopillars (200 nm in diameter, ~25 µm tall) were modified. The height of the base nanopillars was measured and the structural properties (i.e., surface area fraction and roughness) of the fluffy nanostructure terminating the base nanopillars at the tip were quantified. Next, the effects of the topographical properties of the bi-level Teflon AF nanopillars on their adhesion, in both the normal and shear directions, were investigated. Tribological results were discussed in detail to clarify the contribution of the structural properties of the fabricated dry adhesive toward its remarkable adhesion and friction forces generated via contact electrification. It is worthwhile to mention that bi-level Teflon AF nanopillars with these specific structural properties have generated enhanced adhesion and friction strengths, up to ~2.1 and 13 N cm(-2), respectively.