Charles W. Dunnill

Band alignment of rutile and anatase TiO2

The most widely used oxide for photocatalytic applications owing to its low cost and high activity is TiO₂. The discovery of the photolysis of water on the surface of TiO₂ in 1972 launched four decades of intensive research into the underlying chemical and physical processes involved. Despite much collected evidence, a thoroughly convincing explanation of why mixed-phase samples of anatase and rutile outperform the individual polymorphs has remained elusive. One long-standing controversy is the energetic alignment of the band edges of the rutile and anatase polymorphs of TiO₂ (ref. ). We demonstrate, through a combination of state-of-the-art materials simulation techniques and X-ray photoemission experiments, that a type-II, staggered, band alignment of ~ 0.4 eV exists between anatase and rutile with anatase possessing the higher electron affinity, or work function. Our results help to explain the robust separation of photoexcited charge carriers between the two phases and highlight a route to improved photocatalysts.

The role of surfaces in catheter-associated infections

In this critical review the biocidal efficacies of a variety of antimicrobial coatings currently in use for catheter surfaces are discussed to formulate the best strategy for decreasing the risk of catheter-associated infections. The development of new coatings containing antimicrobial chemicals and light-activated antimicrobial agents, and their applicability for use in catheters are summarised (132 references).

The interaction between gold nanoparticles and cationic and anionic dyes: enhanced UV-visible absorption.

The interactions of charge stabilised gold nanoparticles with cationic and anionic dyes are reported. The nanoparticles were synthesised by the Turkevich citrate reduction method. It was found that when a solution of thiazine dye is titrated against gold citrate hydrosol, at a critical concentration of dye there is an enhanced maximum absorption in the dye. The extinction coefficient is increased up to ten-fold. This enhancement was observed for a number of cationic thiazine dyes, of which methylene blue and toluidine blue are established light-activated antimicrobial agents. The same enhancement was not observed for anionic, acidic dyes such as rose bengal which showed no communication with the gold nanoparticles and showed UV-visible titration experiments with well formed isosbestic points. By studying the interaction of the dye and gold nanoparticles under conditions of different ionic strength and by using a zetasizer and TEM to measure the gold nanoparticle size it was demonstrated that the cause of enhancement was not due to nanoparticle aggregation. It is proposed that thiazine cationic dyes coordinate around a gold nanoparticle and give significantly enhanced UV-visible absorptions.

Incorporation of methylene blue and nanogold into polyvinyl chloride catheters; a new approach for light-activated disinfection of surfaces

Methylene blue and 2 nm gold nanoparticles were incorporated into commercial PVC catheters by use of a simple “swell–encapsulation–shrink” method using acetone–water mixtures. Neither the methylene blue nor the nanogold leached into aqueous solution and the assemblage was stable to photodegradation upon laser irradiation. Exposure of the modified catheters to red laser light for 4–8 minutes induced the lethal photosensitisation of Staphylococcus epidermidis and Escherichia coli. Results from time-resolved EPR spectroscopy suggested that enhanced methylene blue triplet state production occurs in the presence of 2 nm gold nanoparticles. The implication being that the levels of reactive oxygen species are higher in these co-doped materials than with methylene blue alone.

Calcium phosphate-based materials of natural origin showing photocatalytic activity

Calcium phosphate based materials of natural origin with photocatalytic properties were produced. Bones of Atlantic cod fish were treated in appropriate solutions (either Ca- or Ti-containing salts) and successively annealed. Results showed multiphasic materials (hydroxyapatite, β-tricalcium phosphate and anatase titania) with excellent photocatalytic performance under both UV and visible light, with an anatase concentration of only about 2 mol%. Results with such a low amount of anatase have never been reported before for a calcium phosphate-based material; this is attributed to the presence of anatase being mainly on the surface. Single-phase hydroxyapatite (Ca10(PO4)6(OH)2 or HAp) also showed some photocatalytic properties and antibacterial activity.

The relationship between photocatalytic activity and photochromic state of nanoparticulate silver surface loaded titanium dioxide thin-films

Anatase titania thin-films were prepared by a modified spray-pyrolysis method. Glass substrates were coated at room temperature with an aerosol-spray of a titania sol-gel solution and then annealed at 500 °C to form rough, transparent, crystalline thin-films of anatase TiO(2). Silver nanoparticles were deposited on the surface of these films by a photo-assisted deposition method; films were dip-coated in methanolic solutions of silver nitrate salt and then photo-irradiated for 5 h with UVC light. The AgNO(3) concentration was adjusted to create an array of films with varying silver loadings. The films displayed photochromism; changing colour to orange-brown in UV-light to colourless under white light. The rates of photochromic change, when subjected to four different lighting conditions (UVC, UVA, white light and dark), were analysed by UV-visible spectroscopy. By assessing the photocatalytic activity to these light sources it was found that the initial photochromic state of the material had a profound effect on the films photocatalytic ability. This effect was more pronounced in the more concentrated silver loaded films; where significant enhancements in photoactivity occurred when reactions were initiated from the photo-reduced state. The mode of improved photocatalysis was attributed to the photo-generated electron trapping by silver nanoparticles, which stabilised photo-generated holes and drove photo-oxidation processes. We believe this is the first study in which the relationship between the photochromic state of a thin-film and its subsequent photocatalytic activity is reported.

Enhanced purification of carbon nanotubes by microwave and chlorine cleaning procedures

A new two-step purification method of carbon nanotubes (CNTs) involving a microwave treatment followed by a gas-phase chlorination process is reported. The significant advantage of this method over conventional cleaning carbon nanotubes procedures is that under microwave treatment in air, the carbon shells that encase the residual metal catalyst particles are removed and the metallic iron is exposed and subsequently oxidized making it accessible for chemical removal. The products from microwave and chlorine treatment have been characterized by TG/DTA, SEM, TEM, EDX, XPS, and Raman spectroscopy. The oxidation state of the iron residue is observed to change from Fe(0) to Fe(II)/Fe(III) after microwave treatment and atmospheric exposure. The effects of the duration and number of microwave exposures has been investigated. This rapid and effective microwave step favours the subsequent chlorination treatment enabling a more effective cleaning procedure to take place, yielding higher purity single- and multi-walled CNTs.

pH-responsive octylamine coupling modification of carboxylated aluminium oxide surfaces

The formation of a pH-sensitive coupling layer, through both physisorption and chemisorption, provides a responsive surface that can be assembled and disassembled in relation to external stimuli. Contact angle measurements, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and Fourier transform IR-attenuated reflectance spectroscopy (FTIR-ATR) have been used to characterize a series of bi-functionalized self-assembled monolayers (SAMs) grown on aluminium oxide wafers/nanoparticles and investigate the reaction nature of pH-responsive coupling layer (octylamine) with the SAMs. Contact angle, XPS, and AFM analyses indicate that the surface of native aluminium oxide was covered considerably as the contact angle of the surfaces decreased, carbon atomic % and roughness of the surfaces increased.

Nanoparticle–sulphur “inverse vulcanisation” polymer composites

Composites of sulphur polymers with nanoparticles such as PbS, with tunable optical properties are reported. A hydrothermal route incorporating pre-formed nanoparticles was used, and their physical and chemical properties evaluated by transmission and scanning electron microscopy, thermogravimetric and elemental analyses. These polymers are easily synthesised from an industrial waste material, elemental sulphur, can be cast into virtually any form and as such represent a new class of materials designed for a responsible energy future.

The effect of glove material upon the transfer of methicillin-resistant Staphylococcus aureus to and from a gloved hand

BACKGROUND Although disposable gloves can protect the hands of a health care worker from acquiring bacteria, during patient care the glove surface itself can become heavily contaminated making cross transmission via contaminated gloved hands likely. The aim of this study was to determine whether the type of glove worn by health care workers could influence the spread of methicillin-resistant Staphylococcus aureus (MRSA). METHODS Laboratory studies were conducted to assess the ease with which MRSA was transferred between different types of glove and surfaces likely to be found within the ward environment. RESULTS In the absence of simulated body fluid, mean bacterial transfer to and from the different gloves ranged from 0.1% to 16% and from 0.01% to 19.5%, respectively. Glove material and glove hydrophobicity were identified as the 2 most important factors influencing bacterial transfer. Nitrile gloves were associated with the lowest transfer rates. The highest numbers of bacteria were transferred to and from the most hydrophilic and most hydrophobic glove, respectively. The adsorption of simulated body fluids altered the physiochemical properties of the gloves. Bacterial transfer significantly increased and was similar to and from all glove types. CONCLUSION Disposable glove type can affect cross-contamination rates among patient, health care worker, and environment. Nonetheless, choice of glove should be considered less important than the correct use of gloves and proper hand hygiene.