Photodynamic antimicrobial polymers for infection control

Hospital-acquired infections pose both a major risk to patient wellbeing and an economic burden on global healthcare systems, with the problem compounded by the emergence of multidrug resistant and biocide tolerant bacterial pathogens. Many inanimate surfaces can act as a reservoir for infection, and adequate disinfection is difficult to achieve and requires direct intervention. In this study we demonstrate the preparation and performance of materials with inherent photodynamic, surface-active, persistent antimicrobial properties through the incorporation of photosensitizers into high density poly(ethylene) (HDPE) using hot-melt extrusion, which require no external intervention except a source of visible light. Our aim is to prevent bacterial adherence to these surfaces and eliminate them as reservoirs of nosocomial pathogens, thus presenting a valuable advance in infection control. A two-layer system with one layer comprising photosensitizer-incorporated HDPE, and one layer comprising HDPE alone is also described to demonstrate the versatility of our approach. The photosensitizer-incorporated materials are capable of reducing the adherence of viable bacteria by up to 3.62 Log colony forming units (CFU) per square centimeter of material surface for methicillin resistant Staphylococcus aureus (MRSA), and by up to 1.51 Log CFU/cm2 for Escherichia coli. Potential applications for the technology are in antimicrobial coatings for, or materials comprising objects, such as tubing, collection bags, handrails, finger-plates on hospital doors, or medical equipment found in the healthcare setting.

Universal tight binding model for chemical reactions in solution and at surfaces. II. Water

A revised water model intended for use in condensed phase simulations in the framework of the self consistent polarizable ion tight binding theory is constructed. The model is applied to water monomer, dimer, hexamers, ice, and liquid, where it demonstrates good agreement with theoretical results obtained by more accurate methods, such as DFT and CCSD(T), and with experiment. In particular, the temperature dependence of the self diffusion coefficient in liquid water predicted by the model, closely reproduces experimental curves in the temperature interval between 230 K and 350 K. In addition, and in contrast to standard DFT, the model properly orders the relative densities of liquid water and ice. A notable, but inevitable, shortcoming of the model is underestimation of the static dielectric constant by a factor of two. We demonstrate that the description of inter and intramolecular forces embodied in the tight binding approximation in quantum mechanics leads to a number of valuable insights which can be missing from ab initio quantum chemistry and classical force fields. These include a discussion of the origin of the enhanced molecular electric dipole moment in the condensed phases, and a detailed explanation for the increase of coordination number in liquid water as a function of temperature and compared with ice-leading to insights into the anomalous expansion on freezing. The theory holds out the prospect of an understanding of the currently unexplained density maximum of water near the freezing point. 

Universal tight binding model for chemical reactions in solution and at surfaces. III. Stoichiometric and reduced surfaces of titania and the adsorption of water

We demonstrate a model for stoichiometric and reduced titanium dioxide intended for use in molecular dynamics and other atomistic simulations and based in the polarizable ion tight binding theory. This extends the model introduced in two previous papers from molecular and liquid applications into the solid state, thus completing the task of providing a comprehensive and unified scheme for studying chemical reactions, particularly aimed at problems in catalysis and electrochemistry. As before, experimental results are given priority over theoretical ones in selecting targets for model fitting, for which we used crystal parameters and band gaps of titania bulk polymorphs, rutile and anatase. The model is applied to six low index titania surfaces, with and without oxygen vacancies and adsorbed water molecules, both in dissociated and non-dissociated states. Finally, we present the results of molecular dynamics simulation of an anatase cluster with a number of adsorbed water molecules and discuss the role of edge and corner atoms of the cluster. (C) 2014 AIP Publishing LLC.

Universal tight binding model for chemical reactions in solution and at surfaces. I. Organic molecules

As is now well established, a first order expansion of the Hohenberg-Kohn total energy density functional about a trial input density, namely, the Harris-Foulkes functional, can be used to rationalize a non self consistent tight binding model. If the expansion is taken to second order then the energy and electron density matrix need to be calculated self consistently and from this functional one can derive a charge self consistent tight binding theory. In this paper we have used this to describe a polarizable ion tight binding model which has the benefit of treating charge transfer in point multipoles. This admits a ready description of ionic polarizability and crystal field splitting. It is necessary in constructing such a model to find a number of parameters that mimic their more exact counterparts in the density functional theory. We describe in detail how this is done using a combination of intuition, exact analytical fitting, and a genetic optimization algorithm. Having obtained model parameters we show that this constitutes a transferable scheme that can be applied rather universally to small and medium sized organic molecules. We have shown that the model gives a good account of static structural and dynamic vibrational properties of a library of molecules, and finally we demonstrate the model's capability by showing a real time simulation of an enolization reaction in aqueous solution. In two subsequent papers, we show that the model is a great deal more general in that it will describe solvents and solid substrates and that therefore we have created a self consistent quantum mechanical scheme that may be applied to simulations in heterogeneous catalysis.

Photosensitisers - the progression from photodynamic therapy to anti-infective surfaces

Introduction: The application of light as a stimulus in pharmaceutical systems and the associated ability to provide precise spatiotemporal control over location, wavelength and intensity, allowing ease of external control independent of environmental conditionals, has led to its increased use. Of particular note is the use of light with photosensitisers.

Areas covered: Photosensitisers are widely used in photodynamic therapy to cause a cidal effect towards cells on irradiation due to the generation of reactive oxygen species. These cidal effects have also been used to treat infectious diseases. The effects and benefits of photosensitisers in the treatment of such conditions are still being developed and further realised, with the design of novel delivery strategies. This review provides an overview of the realisation of the pharmaceutically relevant uses of photosensitisers, both in the context of current research and in terms of current clinical application, and looks to the future direction of research.

Expert opinion: Substantial advances have been and are being made in the use of photosensitisers. Of particular note are their antimicrobial applications, due to absence of resistance that is so frequently associated with conventional treatments. Their potency of action and the ability to immobilise to polymeric supports is opening a wide range of possibilities with great potential for use in healthcare infection prevention strategies.

A carefully curated collection: female figures as sites of inscription in Gautier’s Émaux et Camées

This article examines the ways in which female figures function as additional sites for poetic inscription in Gautier's Émaux et Camées. Although considerable attention has already been paid to the numerous and varied objects catalogued in the collection and, indeed, to the notion of the poems themselves as objects, the present study aims to expand upon such interpretations of the work by focusing on three texts, "Le Poëme de la femme", "Étude de mains : Impéria" and "La fellah". In these poems, female figures who, while they may at first be granted some agency (and be represented going about the business of daily, if highly stylized, life), are finally immobilized within the verse as their bodies, and particularly their pristine skin, ultimately function as an additional paper-like surface for the poet, permitting their assimilation into Gautier's diminutive private collection.

Reconfigurable frequency selective surfaces with interleaved spiral slots

A new type of active frequency selective surface (AFSS) is proposed to realise a voltage controlled bi-state (transparent and reflecting) response at the specified frequencies. The bi-state switching is achieved by combining a passive array of interleaved spiral slots in conducting screens and active dipole arrays with integrated pin diodes at the opposite sides of a thin dielectric substrate. Simulation results show that such active surfaces have high isolation between the transparency and reflection states, while retaining the merits of substantially sub-wavelength response of the unit cell and large fractional bandwidths (FBWs) inherent to the original passive interwoven spiral arrays. Potential applications include reconfigurable and controllable electromagnetic architecture of buildings.

Active singly and dual polarised interwoven spiral frequency selective surfaces

Reconfigurable bi-state interwoven spiral FSSs are explored in this work. Their switching capability is realized by pin diodes that enable the change of the electromagnetic response between transparent and reflecting modes at the specified frequencies in both singly and dual polarised unit cell configurations. The proposed topologies are single layer FSS with their elements acting also as dc current carrying conductors supplying the bias signal for switching pin diodes between the on and off states, thus avoiding the need of external bias lines that can cause parasitic resonances and affect the response at oblique incidence. The presented simulation results show that such active FSSs have potentially good isolation between the transmission and reflection states, while retaining the substantially subwavelength response of the unit cell with large fractional bandwidths (FBWs) inherent to the original passive FSSs.

SURFACE ENHANCED RAMAN-SCATTERING FROM MILDLY ROUGHENED SURFACES - VARIATION OF SIGNAL WITH METAL GRAIN-SIZE

The intensity of surface enhanced Raman scattering from benzoic acid derivatives on mildly roughened, thermally evaporated Ag films shows a remarkably strong dependence on metal grain size. Large grained (slowly deposited) films give a superior response, by up to a factor of 10, to small grained (quickly deposited) films, with films of intermediate grain size yielding intermediate results. The optical field amplification underlying the enhancement mechanism is due to the excitation of surface plasmon polaritons (SPPs). Since surface roughness characteristics, as determined by STM, remain relatively constant as a function of deposition rate, it is argued that the contrast in Raman scattering is due to differences in elastic grain boundary scattering of SPPs (leading to different degrees of internal SPP damping), rather than differences in the interaction of SPPs with surface inhomogeneities.

Near-monochromatic high-harmonic radiation from relativistic laser-plasma interactions with blazed grating surfaces

Intense, femtosecond laser interactions with blazed grating targets are studied through experiment and particle-in-cell (PIC) simulations. The high harmonic spectrum produced by the laser is angularly dispersed by the grating leading to near-monochromatic spectra emitted at different angles, each dominated by a single harmonic and its integer-multiples. The spectrum emitted in the direction of the third-harmonic diffraction order is measured to contain distinct peaks at the 9th and 12th harmonics which agree well with two-dimensional PIC simulations using the same grating geometry. This confirms that surface smoothing effects do not dominate the far-field distributions for surface features with sizes on the order of the grating grooves whilst also showing this to be a viable method of producing near-monochromatic, short-pulsed extreme-ultraviolet radiation.

Harmonic Generation from Relativistic Plasma Surfaces in Ultrasteep Plasma Density Gradients

Harmonic generation in the limit of ultrasteep density gradients is studied experimentally. Observations reveal that, while the efficient generation of high order harmonics from relativistic surfaces requires steep plasma density scale lengths (L-p/lambda <1), the absolute efficiency of the harmonics declines for the steepest plasma density scale length L-p -> 0, thus demonstrating that near-steplike density gradients can be achieved for interactions using high-contrast high-intensity laser pulses. Absolute photon yields are obtained using a calibrated detection system. The efficiency of harmonics reflected from the laser driven plasma surface via the relativistic oscillating mirror was estimated to be in the range of 10(-4)-10(-6) of the laser pulse energy for photon energies ranging from 20-40 eV, with the best results being obtained for an intermediate density scale length.

Broadband XUV polarimetry of high harmonics from plasma surfaces using multiple Fresnel reflections

High-harmonic generation (HHG) by nonlinear interaction of intense laser pulses with gases or plasma surfaces is the most prominent way of creating highly coherent extreme ultraviolet (EUV/XUV) pulses. In the last years, several scientific applications have been found which require the measurement of the polarization of the harmonic radiation. We present a broadband XUV polarimeter based on multiple Fresnel reflections providing an extinction rate of 5-25 for 17-45 nm which is particularly suited for surface harmonics. The device has first been tested at a gas harmonic source providing linearly polarized XUV radiation. In a further experiment using HHG from plasma surfaces, the XUV polarimeter allowed a polarization measurement of high harmonic radiation from plasma surfaces for the first time which reveals a linear polarization state as predicted for our generation parameters. The generation and control of intense polarized XUV pulses-together with the availability of broadband polarizers in the XUV-open the way for a series of new experiments. For instance, dichroism in the XUV, elliptically polarized harmonics from aligned molecules, or the selection rules of relativistic surface harmonics can be studied with the broadband XUV polarimeter.