Surface Characterization and in situ Protein Adsorption Studies on Carbene-Modified Polymers.

Polystyrene thin films were functionalized using a facile two-step chemical protocol involving carbene insertion followed by azo-coupling, permitting the introduction of a range of chemical functional groups, including aniline, hexyl, amine, carboxyl, phenyl, phosphonate diester, and ethylene glycol. X-ray photoelectron spectroscopy (XPS) confirmed the success of the two-step chemical modification with a grafting density of at least 1/10th of the typical loading density (10(14)-10(15)) of a self-assembled monolayer (SAM). In situ, real-time quartz crystal microbalance with dissipation (QCM-D) studies show that the dynamics of binding of bovine serum albumin (BSA) are different at each modified surface. Mass, viscoelastic, and kinetic data were analyzed, and compared to cheminformatic descriptors (i.e., c log P, polar surface area) typically used for drug discovery. Results show that functionalities may either resist or adsorb BSA, and uniquely influence its adsorption dynamics. It is concluded that carbene-based surface modification can usefully influence BSA binding dynamics in a manner consistent with, and more robust than, traditional systems based on SAM chemistry.

Instructive electroactive electrospun silk fibroin-based biomaterials for peripheral nerve tissue engineering.

Aligned sub-micron fibres are an outstanding surface for orienting and promoting neurite outgrowth; therefore, attractive features to include in peripheral nerve tissue scaffolds. A new generation of peripheral nerve tissue scaffolds is under development incorporating electroactive materials and electrical regimes as instructive cues in order to facilitate fully functional regeneration. Herein, electroactive fibres composed of silk fibroin (SF) and poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) were developed as a novel peripheral nerve tissue scaffold. Mats of SF with sub-micron fibre diameters of 190 ± 50 nm were fabricated by double layer electrospinning with thicknesses of ∼100 µm (∼70-80 µm random fibres and ∼20-30 µm aligned fibres). Electrospun SF mats were modified with interpenetrating polymer networks (IPN) of PEDOT:PSS in various ratios of PSS/EDOT (α) and the polymerisation was assessed by hard X-ray photoelectron spectroscopy (HAXPES). The mechanical properties of electrospun SF and IPNs mats were characterised in the wet state tensile and the electrical properties were examined by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The cytotoxicity and biocompatibility of the optimal IPNs (α = 2.3 and 3.3) mats were ascertained via the growth and neurite extension of mouse neuroblastoma x rat glioma hybrid cells (NG108-15) for 7 days. The longest neurite outgrowth of 300 µm was observed in the parallel direction of fibre alignment on laminin-coated electrospun SF and IPN (α = 2.3) mats which is the material with the lowest electron transfer resistance (Ret, ca. 330 Ω). These electrically conductive composites with aligned sub-micron fibres exhibit promise for axon guidance and also have the potential to be combined with electrical stimulation treatment as a further step for the effective regeneration of nerves.

A stable electrode for high-potential, electrocatalytic O(2) reduction based on rational attachment of a blue copper oxidase to a graphite surface.

Attachment of substrate-like anthracene based units to the surface of pyrolytic graphite greatly enhances the adsorption of high-potential fungal laccases, 'blue' Cu enzymes that catalyse the four-electron reduction of O(2), providing a stable cathode for enzymatic biological fuel cells and electrochemical studies.