Polyelectrolyte-Graphene Oxide Multilayer Composites for Array of Microchambers which are Mechanically Robust and Responsive to NIR Light.

Development of composite polymer/graphene oxide (GO) materials attracts significant attention due to their unique properties. In this work, highly ordered arrays of hollow microchambers made of composite polyelectrolyte/GO multilayers (PEGOMs) are successfully fabricated via layer-by-layer assembly on sacrificial or sustainable templates having imprinted patterns of microwells on their surface. Mechanical and optical properties of PEGOMs are studied by nanoindentation and near-infrared (NIR) absorption spectroscopy. Incorporation of three GO layers in between the polyelectrolyte multilayer stacks increases Young's modulus and critical stress of the microchambers by a factor of 5.6 and 2.6, respectively. Optical density of this PEGOM film is found to decrease gradually from 0.14 at λ = 800 nm to 0.06 at λ = 1500 nm. Remote opening of PEGOM microchambers with NIR laser beam is also demonstrated. One of the possible applications of the developed structures includes micropackaging and delivery systems in biological tissues with remote triggering.

Graphene nanocoating provides superb long-lasting corrosion protection to titanium alloy.

OBJECTIVE: The presence of metallic species around failed implants raises concerns about the stability of titanium alloy (Ti-6Al-4V). Graphene nanocoating on titanium alloy (GN) has promising anti-corrosion properties, but its long-term protective potential and structural stability remains unknown. The objective was to determine GN's anti-corrosion potential and stability over time. METHODS: GN and uncoated titanium alloy (Control) were challenged with a highly acidic fluorinated corrosive medium (pH 2.0) for up to 240 days. The samples were periodically tested using potentiodynamic polarization curves, electrochemical impedance spectroscopy and inductively coupled plasma-atomic emission spectroscopy (elemental release). The integrity of samples was determined using Raman spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy and scanning electron microscopy. Statistical analyses were performed with one-sample t-test, paired t-test and one-way ANOVA with Tukey post-hoc test with a pre-set significance level of 5%. RESULTS: There was negligible corrosion and elemental loss on GN. After 240 days of corrosion challenge, the corrosion rate and roughness increased by two and twelve times for the Control whereas remained unchanged for GN. The nanocoating presented remarkably high structural integrity and coverage area (>98%) at all time points tested. SIGNIFICANCE: Graphene nanocoating protects titanium alloy from corrosion and dissolution over a long period while maintaining high structural integrity. This coating has promising potential for persistent protection of titanium and potentially other metallic alloys against corrosion.

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.

Graphene onto medical grade titanium: an atom-thick multimodal coating that promotes osteoblast maturation and inhibits biofilm formation from distinct species.

The time needed for the osseointegration of titanium implants is deemed too long. Moreover, the bacterial colonization of their surfaces is a major cause of failure. Graphene can overcome these issues but its wet transfer onto substrates employs hazardous chemicals limiting the clinical applications. Alternatively, dry transfer technique has been developed, but the biological properties of this technique remain unexplored. Here, a dry transfer technique based on a hot-pressing method allowed to coat titanium substrates with high-quality graphene and coverage area >90% with a single transfer. The graphene-coated titanium is cytocompatible, did not induce cell membrane damage, induced human osteoblast maturation (gene and protein level), and increased the deposition of mineralized matrix compared to titanium alone. Moreover, graphene decreased the formation of biofilms from Streptococcus mutans, Enterococcus faecalis and even from whole saliva on titanium without killing the bacteria. These findings confirm that coating of titanium with graphene via a dry transfer technique is a promising strategy to improve osseointegration and prevent biofilm formation on implants and devices.