Marine Structural Protein Stability Induced by Hofmeister Salt Annealing and Enzymatic Cross-Linking.

The Humboldt squid is one of the fiercest marine predators thanks in part to its sucker ring teeth that are biopolymer blends of a protein isoform family called suckerin with compression strength that rivals silkworm silk. Here, we focus on the popular suckerin-12 isoform to understand what makes the secondary structure of this biopolymer different in water and the potential role of diverse physical and chemical cross-linkings. By choosing a salt post-treatment, in accordance with the Hofmeister series, we achieved film stability with salt annealing that is comparable to chemical cross-links. By correlating the film morphology with the protein secondary structure changes, suckerin-12 films were shown to contract upon treatment with kosmotropic salts and exhibited increased stability in water. These changes are related to the rearrangement of suckerin-12 secondary structure from random coils and helices to ß-sheets. Overall, understanding secondary structure changes caused by aqueous and ionic environments can be instructive for the tuning of the suckerin film sclerotization, its conversion to a tough biological material, and to ultimately produce the natural squid sucker ring teeth.

Attainment of Water and Oil Repellency for Engineering Thermoplastics without Long-Chain Perfluoroalkyls: Perfluoropolyether-Based Triblock Polyester Additives.

For decades, water and oil repellency of engineering thermoplastics has been achieved with introduction of long-chain perfluoroalkyl substances and moieties (C nF2 n+1, n ≥ 7). However, their bioaccumulative and toxicological impact is now widely recognized and, consequently, the substances have been phased out of industrial production and applications. To this end, we have synthesized fluorinated oligomeric triblock polyesters (FOPBs), which do not possess the long-chain perfluoroalkyl segments and serve as effective low-surface-energy additives to engineering thermoplastics. More specifically, we obtained original perfluoropolyether (PFPE)-based triblock copolymers, in which two identical fluorinated blocks were separated by a short nonfluorinated polyester block made of poly(ethylene isophthalate) (PEI). It was found that when FOPBs were added to poly(ethylene terephthalate), nylon-6, and poly(methyl methacrylate) films they readily migrate to the film surface and in doing so imparted significant water and oil repellency to the thermoplastic boundary. The water/oil wettability of the films modified with FOPB is considerably lower than the wettability of the films modified with an analogous PFPE-based polyester, which differs from FOPB only by the absence of the short nonfluorinated PEI middle block. We associate the superiority of the triblock copolymers in terms of water and oil repellency with their ability to form brushlike structures on polymer film surfaces.

Highly Conductive and Transparent Reduced Graphene Oxide Nanoscale Films via Thermal Conversion of Polymer-Encapsulated Graphene Oxide Sheets.

Despite noteworthy progress in the fabrication of large-area graphene sheetlike nanomaterials, the vapor-based processing still requires sophisticated equipment and a multistage handling of the material. An alternative approach to manufacturing functional graphene-based films includes the employment of graphene oxide (GO) micrometer-scale sheets as precursors. However, search for a scalable manufacturing technique for the production of high-quality GO nanoscale films with high uniformity and high electrical conductivity is still continuing. Here we show that conventional dip-coating technique can offer fabrication of high quality mono- and bilayered films made of GO sheets. The method is based on our recent discovery that encapsulating individual GO sheets in a nanometer thick molecular brush copolymer layer allows for the nearly perfect formation of the GO layers via dip coating from water. By thermal reduction the bilayers (cemented by a carbon-forming polymer linker) are converted into highly conductive and transparent reduced GO films with a high conductivity up to 104 S/cm and optical transparency on the level of 90%. The value is the highest electrical conductivity reported for thermally reduced nanoscale GO films and is close to the conductivity of indium tin oxide currently in use for transparent electronic devices, thus making these layers intriguing candidates for replacement of ITO films.

Ultrarobust Transparent Cellulose Nanocrystal-Graphene Membranes with High Electrical Conductivity.

Ultra-robust nanomembranes possessing high mechanical strength combined with excellent stiffness and toughness rarely achieved in nanocomposite materials are presented. These are fabricated by alternately depositing 1D cellulose nanocrystals and 2D graphene oxide nanosheets by using a spin assisted layer-by-layer assembly technique. Such a unique combination of 1D and 2D reinforcing nanostructures results in layered nanomaterials.

Biopolymeric nanocomposites with enhanced interphases.

Ultrathin and robust nanocomposite membranes were fabricated by incorporating graphene oxide (GO) sheets into a silk fibroin (SF) matrix by a dynamic spin-assisted layer-by-layer assembly (dSA-LbL). We observed that in contrast to traditional SA-LbL reported earlier fast solution removal during dropping of solution on constantly spinning substrates resulted in largely unfolded biomacromolecules with enhanced surface interactions and suppressed nanofibril formation. The resulting laminated nanocomposites possess outstanding mechanical properties, significantly exceeding those previously reported for conventional LbL films with similar composition. The tensile modulus reached extremely high values of 170 GPa, which have never been reported for graphene oxide-based nanocomposites, the ultimate strength was close to 300 MPa, and the toughness was above 3.4 MJ m(-3). The failure modes observed for these membranes suggested the self-reinforcing mechanism of adjacent graphene oxide sheets with strong 2 nm thick silk interphase composed mostly from individual backbones. This interphase reinforcement leads to the effective load transfer between the graphene oxide components in reinforced laminated nanocomposite materials with excellent mechanical strength that surpasses those known today for conventional flexible laminated carbon nanocomposites from graphene oxide and biopolymer components.