A generic electrochemical method of "bioreceptor" antibody attachment to phenyl amine functionalised graphitic surfaces is demonstrated. Micro-channels of chemically modified multi-layer epitaxial graphene (MLEG) have been used to provide a repeatable and reliable response to nano molar (nM) concentrations of the cancer risk (oxidative stress) biomarker 8hydroxydeoxyguanosine (8-OHdG). X-ray photoelectron spectroscopy, Raman spectroscopy are used to characterize the functionalised MLEG. Confocal fluorescence microscopy using fluorescent-labelled antibodies indicates that the anti-8-OHdG antibody selectively binds to the phenyl amine-functionalised MLEG's channel. Current-voltage measurements on functionalised channels showed repeatable current responses from antibody-biomarker binding events. This technique is scalable, reliable, and capable of providing a rapid, quantitative, label-free assessment of biomarkers at nano-Molar (less than 20 nM) concentrations in analyte solutions. The sensitivity of the sensor device was investigated using varying concentrations of 8-OHdG, with changes in the sensor's channel resistance observed upon exposure to 8-OHdG. Detection of 8-OHdG concentrations as low as 0.1ng/ml

Understanding the role of defects in graphene is the key to tailoring the properties of graphene and promoting the development of graphene-based devices. Defects can affect the electronic properties of a device while also offering a means by which to functionalize the local properties. Using tip-enhanced Raman spectroscopy (TERS), heightened defect sensitivity was demonstrated on graphene edges, folds, and overlapping regions. Measurements confirm that TERS can provide simultaneous structural and spectral information on a localized scale, hence offering defect characterization on a scale that is not obtainable using conventional Raman spectroscopy. This study observed preferential enhancement of the D band signal on multilayered graphene and ultrathin graphite; in addition, other key defect signatures were also enhanced and detected. We present our findings in relation to theoretical predictions of graphene defect signatures and an analysis of the sensitivity of TERS in measuring two-dimensional structures.

Single-walled carbon nanotubes (SWCNTs) have recently attracted great attention because of their fibrous structure and high aspect ratio. Here the genotoxic potential of 400-800 nm, 1-3 μm and 5-30 μm SWCNT with respect to their geometry and surface characteristics was studied. Following thorough physico-chemical characterisation, human bronchial epithelial (BEAS-2B) and lymphoblastoid (MCL-5) cells were treated with SWCNT for 24 or 48 h. This showed significant increases in micronucleus frequency in a time- and dose-dependent manner in both cell types in the absence of cytotoxicity. Over the same dose range, only 1-3 μm SWCNT gave rise to significant increases in hprt point mutations at doses ≥25 μg/ml. Cellular 2,7-dichlorodihydrofluoresceindiacetate (DCFH-DA) fluorescence assay and RT-PCR for oxidative pathway gene profiling revealed a possible oxidative mechanism for the genotoxicity observed in the 1-3 μm SWCNT. Consequently, this study has demonstrated that SWCNT genotoxicity is dependent on its secondary structure under experimental conditions and oxidative stress alone cannot account for the observed damage.

The performance of tip-enhanced Raman spectroscopy (TERS) largely depends on probe optimisation. An electrochemical etch using nitric acid and ethanol produces sharp silver probes with radius of curvature between 20 and 60 nm. Optimisation also identified controllable tapers; rough or smooth. Boundary element method simulations comparing the response to 532 nm excitation of silver and gold probes reveal no discernable field enhancement at the gold apex, but strong localised enhancement is observed at the silver apex. The motivation for employing this method of etching silver probes can also be seen in the signal enhancement observed in preliminary TERS data presented.