Graphene Nanocoating: High Quality and Stability upon Several Stressors.

Titanium implants present 2 major drawbacks-namely, the long time needed for osseointegration and the lack of inherent antimicrobial properties. Surface modifications and coatings to improve biomaterials can lose their integrity and biological potential when exposed to stressful microenvironments. Graphene nanocoating (GN) can be deposited onto actual-size dental and orthopedic implants. It has antiadhesive properties and can enhance bone formation in vivo. However, its ability to maintain structural integrity and quality when challenged by biologically relevant stresses remains largely unknown. GN was produced by chemical vapor deposition and transferred to titanium via a polymer-assisted transfer technique. GN has high inertness and did not increase expression of inflammatory markers by macrophages, even in the presence of lipopolysaccharides. It kept high coverage at the top tercile of tapered dental implant collars after installation and removal from bone substitute and pig maxilla. It also resisted microbiologically influenced corrosion, and it maintained very high coverage area and quality after prolonged exposure to biofilms and their removal by different techniques. Our findings show that GN is unresponsive to harsh and inflammatory environments and that it maintains a promising level of structural integrity on the top tercile of dental implant collars, which is the area highly affected by biofilms during the onset of implant diseases. Our findings open the avenues for the clinical studies required for the use of GN in the development of implants that have higher osteogenic potential and are less prone to implant diseases.

Inhibiting Corrosion of Biomedical-Grade Ti-6Al-4V Alloys with Graphene Nanocoating.

The identification of metal ions and particles in the vicinity of failed implants has raised the concern that biomedical titanium alloys undergo corrosion in healthy and infected tissues. Various surface modifications and coatings have been investigated to prevent the deterioration and biocorrosion of titanium alloys but so far with limited success. Graphene is a cytocompatible atom-thick film made of carbon atoms. It has a very high surface area and can be deposited onto metal objects with complex shapes. As the carbon lattice has a very small pore size, graphene has promising impermeability capacity. Here, we show that graphene coating can effectively protect Ti-6Al-4V from corrosion. Graphene nanocoatings were produced on Ti-6Al-4V grade 5 and 23 discs and subjected to corrosive challenge (0.5M NaCl supplemented with 2-ppm fluoride, pH of 2.0) up to 30 d. The linear polarization resistance curves and electrochemical impedance spectroscopy analysis showed that the graphene-coated samples presented higher corrosion resistance and electrochemical stability at all time points. Moreover, the corrosion rate of the graphene-coated samples was very low and stable (~0.001 mm/y), whereas that of the uncoated controls increased up to 16 and 5 times for grade 5 and 23 (~0.091 mm/y) at the end point, respectively. The surface oxidation, degradation (e.g., crevice defects), and leaching of Ti, Al, and V ions observed in the uncoated controls were prevented by the graphene nanocoating. The Raman mappings confirmed that the graphene nanocoating presented high structural stability and resistance to mechanical stresses and chemical degradation, keeping >99% of coverage after corrosion challenge. Our findings open the avenues for the use of graphene as anticorrosion coatings for metal biomedical alloys and implantable devices.

Nanoscale dynamics and protein adhesivity of alkylamine self-assembled monolayers on graphene.

Atomic-scale molecular dynamics computer simulations are used to probe the structure, dynamics, and energetics of alkylamine self-assembled monolayer (SAM) films on graphene and to model the formation of molecular bilayers and protein complexes on the films. Routes toward the development and exploitation of functionalized graphene structures are detailed here, and we show that the SAM architecture can be tailored for use in emerging applications (e.g., electrically stimulated nerve fiber growth via the targeted binding of specific cell surface peptide sequences on the functionalized graphene scaffold). The simulations quantify the changes in film physisorption on graphene and the alkyl chain packing efficiency as the film surface is made more polar by changing the terminal groups from methyl (-CH3) to amine (-NH2) to hydroxyl (-OH). The mode of molecule packing dictates the orientation and spacing between terminal groups on the surface of the SAM, which determines the way in which successive layers build up on the surface, whether via the formation of bilayers of the molecule or the immobilization of other (macro)molecules (e.g., proteins) on the SAM. The simulations show the formation of ordered, stable assemblies of monolayers and bilayers of decylamine-based molecules on graphene. These films can serve as protein adsorption platforms, with a hydrophobin protein showing strong and selective adsorption by binding via its hydrophobic patch to methyl-terminated films and binding to amine-terminated films using its more hydrophilic surface regions. Design rules obtained from modeling the atomic-scale structure of the films and interfaces may provide input into experiments for the rational design of assemblies in which the electronic, physicochemical, and mechanical properties of the substrate, film, and protein layer can be tuned to provide the desired functionality.