We report the fabrication, characterisation (SEM/EDX, TEM, XRD, XPS and Raman spectroscopy) and electrochemical properties of graphite and graphene paste electrodes with varying lateral flake sizes. The fabricated paste electrodes are electrochemically analysed using both outer-sphere and inner-sphere redox probes, namely; hexaammineruthenium(III) chloride, N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD), potassium ferrocyanide(II) and ammonium ferrous(II) sulphate. Upon comparison of different graphite paste electrodes, a clear correlation between the lateral flake sizes (L_a), ranging from 1.5 mm–0.5 μm, and electrochemical activity (heterogeneous electron transfer (HET) kinetics) is evident, where an improvement in the HET is observed at smaller lateral flake sizes. We infer that the beneficial response evident when employing laterally smaller flakes is due to an increased number of edge plane like-sites/defects available upon the electrode surface, facilitating electron transfer. Interestingly, given that the overall lateral flake sizes of the graphenes utilised (10.0–1.3 μm) were significantly smaller than those studied previously, an improvement in HET kinetics was also evident with the reduction of lateral flake size; the extent to which is redox-probe dependent. Improvements are observed up to a distinct point, termed the ‘lateral size threshold’ (ca. ≤2 μm) where the electrochemical reversible limit is approached. Further support is provided from density functional theory (DFT), exploring the electronic structure (i.e. HOMO–LUMO) as a function of flake size, which demonstrates that the coverage of edge plane like-sites/defects comprising the geometric structure of the relatively small graphene flakes is such that effectively the entire flake has become electrochemically active. In this study, the importance of lateral flake size with respect to electrochemical reactivity at carbon-based electrodes has been demonstrated alongside a structural relationship upon HET performance, a phenomenon that has not previously been described in the literature. Such work is both highly important and informative for the field of electrochemistry and electrode performance, with potential implications in a plethora of areas, ranging from novel renewable energy sources to electroanalytical sensing platforms.

Biofouling of PVAc and PVOH surfaces by fungal conidia can result in surface discolouration and subsequent biodeterioration. In order to understand the interactions of fungal conidia on polymer surfaces, the surface properties of PVAc and PVOH and the hydrophobicity, size and shape of three type of fungal conidia was determined (Aspergillus niger 1957, Aspergillus niger 1988 and Aureobasidium pullulans). Fungal conidia were used in a range of binding assays (attachment, adhesion and retention). The PVAc and PVOH demonstrated different surface topographies and the PVAc demonstrated a higher maximum height (300.6 nm) when compared to the PVOH (434.2 nm). The PVAc surfaces was less wettable (75°) than the PVOH surface (62°). The FTIR demonstrated differences in the chemistries of the two surfaces, whereby the PVOH confirmed the presence of polar moieties. Hydrophobicity assays demonstrated that both A. niger species’ were more non-wettable than the A. pullulans. Following the attachment assays, the more hydrophobic Aspergillus spp. conidia attached in greater numbers to the more wettable surface and the A. pullulans was retained in greater numbers to the less wettable PVAc surface. The adhesion and retention assays demonstrated that the more polar surface retained all the types of conidia, regardless of their surface hydrophobicities. This study demonstrated that conidial binding to the surfaces were influenced by the chemistry and physicochemistry of the surfaces and spores. However, the inclusion of a washing stage influenced the adhesion of conidia to surfaces. In environments that were indicative of a attachment or retention assay a PVAc surface would reduce the number of A. niger spp. spores whilst a PVOH surface would reduce the number of A. pullulans spores. However, in an environment similar to a adhesion assay, a PVAc surface would be most beneficial to reduce spore retention. Thus, the use of the correct methodology that reflects the environment in which the surface is to be used is important in order to accurately inform hygienic surface development.

Due to the ever-increasing rise of antimicrobial resistant (AMR) bacteria, the development of alternative antimicrobial agents is a global priority. The antimicrobial activity of ionic gold was explored against four Pseudomonas aeruginosa strains with different AMR profiles in order to determine the antimicrobial activity of ionic gold and elucidate the mechanisms of action. Disc diffusion assays (zone of inhibition: ZoI) coupled with minimum inhibitory/bactericidal concentrations (MIC/MBC) were conducted to determine the antimicrobial efficacy of ionic gold. Scanning electron microscopy (SEM) was used to visualise morphological changes to the bacterial cell ultrastructure. Strains with increased AMR were slower to grow which is likely a fitness cost due to the enhanced AMR activity. Although greater concentrations of ionic gold were required to promote antimicrobial activity, ionic gold demonstrated similar antimicrobial values against all strains tested. Lowry assay results indicated that protein leakage was apparent following incubation with ionic gold, whilst SEM revealed cellular ultrastructure damage. This study suggests that the application of ionic gold as an alternative antimicrobial is promising, particularly against AMR P. aeruginosa. The antimicrobial activity of ionic gold against P. aeruginosa could potentially be utilised as an alternative therapeutic option in wound management, an approach that could benefit healthcare systems worldwide.

Severely broken bones often require external bone fixation pins to provide support but they can become infected. In order to reduce such infections, novel solutions are required. Titanium zirconium nitride (Ti-ZrN) and Ti-ZrN silver (Ti-ZrN/Ag) coatings were deposited onto stainless steel. Surface microtopography demonstrated that on the silver containing surfaces, S _a and S _v values demonstrated similar trends whilst the R _a , average height and RMS value and S _p values increased with increasing silver concentration. On the Ti-ZrN/Ag coatings, surface hydrophobicity followed the same trend as the S _a and S _v values. An increase in dead Staphylococcus aureus and Staphylococcus epidermidis cells was observed on the coatings with a higher silver concentration. Using CTC staining, a significant increase in S. aureus respiration on the silver containing surfaces was observed in comparison to the stainless steel control whilst against S. epidermidis, no significant difference in viable cells was observed across the surfaces. Cytotoxicity testing revealed that the TiZrN coatings, both with and without varying silver concentrations, did not possess a detrimental effect to a human monocyte cell line U937. This work demonstrated that such coatings have the potential to reduce the viability of bacteria that result in pin tract infections.

External bone fixation devices provide support and rehabilitation for severely damaged/broken bones, however, this invasive procedure is prone to infection. Zirconium nitride/silver (Ti-ZrN/Ag) coatings were characterised for surface topography, chemical composition, physicochemistry and antimicrobial efficacy (against Staphylococcus aureus and Staphylococcus epidermidis), in the presence of a blood conditioning film. The conditioning film altered the width of the microtopography of the surfaces however, the depth of the features remained relatively constant. The conditioning film also altered the coatings from hydrophobic to hydrophilic/partially hydrophilic surfaces. Following the MATH assay, the presence of a conditioning film reduced affinity towards the hydrocarbons for both microorganisms. The addition of a blood conditioning film reduced the antimicrobial efficacy of the Ti-ZrN/Ag coatings but also reduced the number of retained bacteria. This study suggests that the presence of a pre-defined blood conditioning film may result in surfaces with anti-adhesive properties, potentially leading to a reduction in bacterial retention. This, combined with the antimicrobial efficacy of the coatings, could reduce the risk of infection on biomaterial surfaces.