Predictive modelling of the water contact angle of surfaces using attenuated total reflection - Fourier transform infrared (ATR-FTIR) chemical imaging and partial least squares regression (PLSR).

The static water contact angle (CA) quantifies the degree of wetting that occurs when a surface encounters a liquid, e.g. water. This property is a result of factors such as surface chemistry and local roughness and is an important analytical parameter linked to the suitability of a surface for a given bioanalytical process. Monitoring the spatial variation in wettability over surfaces is increasingly critical to analysts and manufacturers for improved quality control. However, CA acquisition is often time-consuming because it involves measurements over multiple spatial locations, independent sampling and the need for a single instrument operator. Furthermore, surfaces exposed to local environments specific to an intended application may affect the surface chemistry thereby modifying the surface properties. In this study, Attenuated Total Reflection-Fourier Transform Infrared (ATR-FTIR) chemical imaging data acquired from wet and dry polymer surfaces were used to develop multivariate predictive models for CA prediction. Partial Least Squares Regression (PLSR) models were built using IR spectra from surfaces presenting differences in the experimentally measured CA in the range 16°-141°. The best performing PLSR models were locally developed and combined to make a global model utilising wet IR spectra which performed well (R2p = 0.98, RMSECV ∼ 5°) when tested on an independent experimental set. This model was subsequently applied to IR spectra acquired from a surface exhibiting spatial differences in surface chemistry and the CA with a reasonable confidence and precision (prediction error within 10°), demonstrating the potential of this method for prediction of the spatially varying CA as a non-destructive in-line process monitoring technique.

Influence of substrate metal alloy type on the properties of hydroxyapatite coatings deposited using a novel ambient temperature deposition technique.

Hydroxyapatite (HA) coatings are applied widely to enhance the level of osteointegration onto orthopedic implants. Atmospheric plasma spray (APS) is typically used for the deposition of these coatings; however, HA crystalline changes regularly occur during this high-thermal process. This article reports on the evaluation of a novel low-temperature (<47°C) HA deposition technique, called CoBlast, for the application of crystalline HA coatings. To-date, reports on the CoBlast technique have been limited to titanium alloy substrates. This study addresses the suitability of the CoBlast technique for the deposition of HA coatings on a number of alternative metal alloys utilized in the fabrication of orthopedic devices. In addition to titanium grade 5, both cobalt chromium and stainless steel 316 were investigated. In this study, HA coatings were deposited using both the CoBlast and the plasma sprayed techniques, and the resultant HA coating and substrate properties were evaluated and compared. The CoBlast-deposited HA coatings were found to present similar surface morphologies, interfacial properties, and composition irrespective of the substrate alloy type. Coating thickness however displayed some variation with the substrate alloy, ranging from 2.0 to 3.0 µm. This perhaps is associated with the electronegativity of the metal alloys. The APS-treated samples exhibited evidence of both coating, and significantly, substrate phase alterations for two metal alloys; titanium grade 5 and cobalt chrome. Conversely, the CoBlast-processed samples exhibited no phase changes in the substrates after depositions. The APS alterations were attributed to the brief, but high-intensity temperatures experienced during processing.

Effect of doping (C or N) and co-doping (C+N) on the photoactive properties of magnetron sputtered titania coatings for the application of solar water-splitting.

The photocatalytic splitting of water into hydrogen and oxygen using a photoelectrochemical (PEC) cell containing titanium dioxide (TiO2) photoanode is a potentially renewable source of chemical fuels. However, the size of the band gap (-3.2 eV) of the TiO2 photocatalyst leads to its relatively low photoactivity toward visible light in a PEC cell. The development of materials with smaller band gaps of approximately 2.4 eV is therefore necessary to operate PEC cells efficiently. This study investigates the effect of dopant (C or N) and co-dopant (C+N) on the physical, structural and photoactivity of TiO2 nano thick coating. TiO2 nano-thick coatings were deposited using a closed field DC reactive magnetron sputtering technique, from titanium target in argon plasma with trace addition of oxygen. In order to study the influence of doping such as C, N and C+N inclusions in the TiO2 coatings, trace levels of CO2 or N2 or CO2+N2 gas were introduced into the deposition chamber respectively. The properties of the deposited nano-coatings were determined using Spectroscopic Ellipsometry, SEM, AFM, Optical profilometry, XPS, Raman, X-ray diffraction UV-Vis spectroscopy and tri-electrode potentiostat measurements. Coating growth rate, structure, surface morphology and roughness were found to be significantly influenced by the types and amount of doping. Substitutional type of doping in all doped sample were confirmed by XPS. UV-vis measurement confirmed that doping (especially for C doped sample) facilitate photoactivity of sputtered deposited titania coating toward visible light by reducing bandgap. The photocurrent density (indirect indication of water splitting performance) of the C-doped photoanode was approximately 26% higher in comparison with un-doped photoanode. However, coating doped with nitrogen (N or N+C) does not exhibit good performance in the photoelectrochemical cell due to their higher charge recombination properties.

Evaluation of microwave plasma sintering for the fabrication of dye sensitized solar cell (DSSC) electrodes.

Dye-sensitized solar cells (DSSCs) have demonstrated considerable potential due to their solar energy conversion efficiency and their fabrication from relatively low cost materials. Titanium dioxide (TiO2) nanoparticles are widely used in the fabrication of the DSSC electrodes. There is a considerable energy requirement however required for the sintering of the TiO2 particles during the fabrication of the mesoporous electrodes. This study investigates the use of microwave (MW) plasma treatments as a rapid, energy efficient processing technique for the sintering of the metal oxide particles. A comparison is made with conventional furnace treatments for the sintering of TiO2 nanoparticles (Degussa P25), deposited onto fluorine doped tin oxide (FTO) coated glass substrates. Subsequent to the TiO2 sintering, ruthenium based dye (N719) adsorption studies were carried out for coatings heated using both sintering techniques. Based on UV/Vis absorption spectra measurements of 5 mins plasma and 30 mins furnace sintering, it was observed that both sintering techniques exhibited similar levels of dye adsorption. A decrease in the level of dye adsorption was observed for the TiO2 coatings sintered for longer periods (up to 10 mins in this study). This change with longer plasma treatment times was associated with rutile grain growth and a decrease in surface roughness, possibly due to a densification of the mesoporous structure. The effect of TiO2 coating plasma treatment times on the conversion efficiency of the dye sensitised electrodes was also evaluated. Plasma treatments of 5 mins were found to yield the highest conversion efficiency of 6.4%.

Evaluation of protein adsorption on atmospheric plasma deposited coatings exhibiting superhydrophilic to superhydrophobic properties.

Protein adsorption is one of the key parameters influencing the biocompatibility of medical device materials. This study investigates serum protein adsorption and bacterial attachment on polymer coatings deposited using an atmospheric pressure plasma jet system. The adsorption of bovine serum albumin and bovine fibrinogen (Fg) onto siloxane and fluorinated siloxane elastomeric coatings that exhibit water contact angles (θ) ranging from superhydrophilic (θ < 5°) to superhydrophobic (θ > 150°) were investigated. Protein interactions were evaluated in situ under dynamic flow conditions by spectroscopic ellipsometry. Superhydrophilic coatings showed lower levels of protein adsorption when compared with hydrophobic siloxane coatings, where preferential adsorption was shown to occur. Reduced levels of protein adsorption were also observed on fluorinated siloxane copolymer coatings exhibiting hydrophobic wetting behaviour. The lower levels of protein adsorption observed on these surfaces indicated that the presence of fluorocarbon groups have the effect of reducing surface affinity for protein attachment. Analysis of superhydrophobic siloxane and fluorosiloxane surfaces showed minimal indication of protein adsorption. This was confirmed by bacterial attachment studies using a Staphylococcus aureus strain known to bind specifically to Fg, which showed almost no attachment to the superhydrophobic coating after protein adsorption experiments. These results showed the superhydrophobic surfaces to exhibit antimicrobial properties and significantly reduce protein adsorption.

Influence of the physical, structural and chemical properties on the photoresponse property of magnetron sputtered TiO2 for the application of water splitting.

The production of hydrogen from water (called "water splitting"), utilises sunlight as an energy source (solar-hydrogen) in a photoelectrochemical (PEC) solar cell, is a promising source of green energy. In this work, a PEC was used, for evaluating the photoactivity of a thin film TiO2 based photoanode by measuring photocurrent (which is comparable to hydrogen production rate by water splitting process in PEC). The main focus of this work is to study the effect of the TiO2 nanosurface and bulk properties on the photoresponse properties of the photoanode. The TiO2 coatings (360-400 nm) were deposited using a closed field reactive magnetron sputtering system. The structure and morphology of the TiO2 coatings were systematically altered by varying the deposition pressure between 5 x 10(-4) to 1 x 10(-2) mbar. The properties of the deposited nano-coatings were determined using Ellipsometry, SEM, AFM, profilometry, XPS, Raman and X-ray diffraction (XRD). Coating properties were correlated with the light absorption and photocurrent performance which were evaluated using UV-Vis spectroscopy and tri-electrode potentiostat measurements respectively. It was concluded from this study that the coating deposition pressure has a pronounced effect on the TiO2 photoanode properties leading to a significant enhancement in the photoactivity in PEC cell. Over a six fold increase in photocurrent at applied potential 0 V was observed for TiO2 photoanode prepared at 4 x 10(-3) mbar as compared to 5 x 10(-4) mbar. A correlation has been established between the deposition pressure, nano surface morphology and bulk properties, UV-Vis light absorbance and bandgap value, and the consequently higher (i) photocurrent density, (ii) negative flat band, and (iii) open circuit potential measured in Photoelectrochemical (PEC) cell.

Effect of process parameters on chemistry, growth rate and nano-sized particulate formation of atmospheric plasma deposited, nm thick siloxane coatings.

Nano-thick siloxane coatings with thickness in the range 1-33 nm were deposited using a reel-to-reel atmospheric plasma coating system. The coatings were deposited from a tetraethoxysilane (TEOS) precursor which was nebulised into a helium plasma. An issue influencing coating performance is the incorporation of particulates, which are formed during the deposition process. By systematically varying the process parameters such as plasma power, TEOS flow rate, gas flow rates (He, O2, and N2), a correlation was obtained between the deposition conditions and particulate formation. The effect of process parameters on growth rate, changes in coating chemistry and particulate formation on the deposited nm-thick films were studied by spectroscopic ellipsometry, contact angle/surface energy measurements, optical profilometry, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray reflectometry (XRR), Scanning electron microscopy (SEM) and Atomic force microscopy (AFM). Larger numbers of particulates were formed under the conditions of higher plasma power, with the addition of O2 or N2 into the He plasma and also at both very low and high TEOS flow rates in the range 10-200 microl/min. Low plasma input power and moderate precursor flow rates (approx. 25 microl/min) significantly reduced particulate formation.

Evolution of the arginase fold and functional diversity.

Novel structural superfamilies can be identified among the large number of protein structures deposited in the Protein Data Bank based on conservation of fold in addition to conservation of amino acid sequence. Since sequence diverges more rapidly than fold in protein Evolution, proteins with little or no significant sequence identity are occasionally observed to adopt similar folds, thereby reflecting unanticipated evolutionary relationships. Here, we review the unique alpha/beta fold first observed in the manganese metalloenzyme rat liver arginase, consisting of a parallel eight-stranded beta-sheet surrounded by several helices, and its evolutionary relationship with the zinc-requiring and/or iron-requiring histone deacetylases and acetylpolyamine amidohydrolases. Structural comparisons reveal key features of the core alpha/beta fold that contribute to the divergent metal ion specificity and stoichiometry required for the chemical and biological functions of these enzymes.

Adhesion of slime producing Staphylococcus epidermidis strains to PVC and diamond-like carbon/silver/fluorinated coatings.

Staphylococcus epidermidis has emerged as a pathogen associated with infections of implanted medical devices. Bacterial adhesion is a crucial step in infection on biomaterial surfaces. To quantitatively determine the relationship between poly (vinyl chloride) (PVC) surface properties and bacterial adhesion, we have compared attachment of slime-producing S. epidermidis strains on PVC and various coatings under flow conditions. Bacterial adhesion and colonization was quantified by counting the viable organisms on the adherent surface as well as by scanning electron microscopy, epifluorescence microscopy and atomic force microscopy. Fluorination of the PVC surface encourages S. epidermidis adhesion whereas; diamond-like carbon (DLC) and especially silver (Ag) coatings seem to inhibit its adhesion. In most materials, the number of adherent bacteria decreased with the increase of shear rate. These results indicate that bacterial adhesion is influenced by the chemical properties of the polymeric surfaces, the surface roughness and the associated flow conditions.