Surface localisation of photosensitisers on intraocular lens biomaterials for prevention of infectious endophthalmitis and retinal protection

Cataract surgery is one of the most commonly-practiced surgical procedures in Western medicine, and, while complications are rare, the most serious is infectious postoperative endophthalmitis. Bacteria may adhere to the implanted intraocular lens (IOL) and subsequent biofilm formation can lead to a chronic, difficult to treat infection. To date, no method to reduce the incidence of infectious endophthalmitis through bacterial elimination, while retaining optical transparency, has been reported. In this study we report a method to optimise the localisation of a cationic porphyrin at the surface of suitable acrylate copolymers, which is the first point of contact with potential pathogens. The porphyrin catalytically generates short-lived singlet oxygen, in the presence of visible light, which kills adherent bacteria indiscriminately. By restricting the photosensitiser to the surface of the biomaterial, reduction in optical transparency is minimised without affecting efficacy of singlet oxygen production. Hydrogel IOL biomaterials incorporating either methacrylic acid (MAA) or methyl methacrylate (MMA) co-monomers allow tuning of the hydrophobic and anionic properties to optimise the localisation of porphyrin. Physiochemical and antimicrobial properties of the materials have been characterised, giving candidate materials with self-generating, persistent anti-infective character against Gram-positive and Gram-negative organisms. Importantly, incorporation of porphyrin can also serve to protect the retina by filtering damaging shortwave visible light, due to the Soret absorption (?max) 430 nm). © 2012 Elsevier Ltd. All rights reserved.

Chemically blockable transformation and ultraselective low-pressure gas adsorption in a non-porous metal organic framework

Metal organic frameworks (MOFs) are among the most exciting materials discovered recently, attracting particular attention for their gas-adsorption and -storage properties. Certain MOFs show considerable structural flexibility in response to various stimuli. Although there are several examples of 'breathing' MOFs, in which structural changes occur without any bond breaking, examples of transformations in which several bonds are broken and made are much rarer. In this paper we demonstrate how a flexible MOF, Cu-2(OH)(C8H3O7S)(H2O)center dot 2H(2)O, can be synthesized by careful choice of the organic linker ligand. The flexibility can be controlled by addition of a supplementary coordinating molecule, which increases the thermal stability of the solid sufficiently for direct imaging with electron microscopy to be possible. We also demonstrate that the MOF shows unprecedented low-pressure selectivity towards nitric oxide through a coordination-driven gating mechanism. The chemical control over these behaviours offers new possibilities for the synthesis of MOFs with unusual and potentially exploitable properties.

Metal organic frameworks as NO delivery materials for biological applications

Metal organic frameworks (MOFs) are highly porous materials that can store significant amounts of gas, including nitric oxide. The chemical composition and toxicology of many (but not all) of these materials makes them potentially suitable for medical applications. In this paper, we will describe how triggered release methods can be used to deliver biologically relevant amounts of NO and then show how Ni, Co and Cu-containing MOFs are biologically active materials with potential applications in several different areas (anti-thrombosis, dermatology and wound healing, anti-bacterial, vasodilation etc.). We will also discuss the pros and cons of MOFs, including their chemical and biological stability and the toxicology of MOFs in general. (C) 2009 Elsevier Inc. All rights reserved.

Simultaneous Gas Storage and Catalytic Gas Production Using Zeolites-A New Concept for Extending Lifetime Gas Delivery

Copper containing MCM-41 materials can be used to both store gaseous nitric oxide and to catalytically produce nitric oxide from nitrite. The active species for the reaction is copper (I). Addition of cysteine to the solution in contact with the material has different effects depending on how much Cu(I) is present. This is a new method of extending the lifetime of gas delivery from a gas storage material.

Time-Resolved DRIFTS, MS, and Resistance Study of SnO2 Materials: The Role of Surface Hydroxyl Groups in Formation of Donor States

Time-resolved DRIFTS, MS, and resistance measurements were used to study the interaction of undoped and Pd-doped SnO2 with H-2 in air and argon at 300 degrees C. Using first-order kinetics, we compare the time constants for the resistance drop and its partial recovery with those of the surface hydroxyl evolution and water formation in the gas phase upon exposure to hydrogen. In the case of the undoped oxide, resistance and bridging hydroxyls (BOHs) evolve similarly, manifesting a fast main drop followed by recovery at a similar rate. The rate of water formation for this material was found to be much slower than that of the main drop in both the resistance and BOHs. In contrast, the resistance change for SnO2-Pd appeared to be similar to that of water formation, and no correlation was found between the evolution of resistance and surface OHs. Isotopic exchange on both materials revealed that water formation occurs via fast and slow hydrogen transfer to surface oxygen species. While the former originates from just-adsorbed hydrogen, the latter appears to proceed from the preadsorbed OHs. Both surfaces exhibit close interaction between chemisorbed oxygen and existing bridging OH groups, indicating that the latter is an intermediate in the hydrogen oxidation and generation of donor states on the surface.

Porous organic-inorganic hybrid aerogels based on Cr3+/Fe3+ and rigid bridging carboxylates

A general method to prepare organic-inorganic hybrid aerogels has been presented. A series of organic-inorganic hybrid aerogels were successfully produced from 3d trivalent transition metals (Cr3+, Fe3+) and bridging carboxylic acids. Gelation of the Cr(III) gels was achieved by heating the precursor solution to temperatures above 80 degrees C, which is in sharp contrast to usual supramolecular gels. Among a range of ligands used, highly porous aerogels could be prepared from rigid carboxylate, e.g. 1,4-benzenedicarboxylate and 1,3,5-benzenetricarboxylate. The porous aerogels can be described as a coherent, rigid spongy network of continuous nanometre-sized particles, which is significantly different from the usual fibrous network of supramolecular gels. The aerogels have tunable porous structures with micro-and mesoporosity depending on their reactant concentrations. Their surface areas, pore volumes, and average pore sizes were analysed by using nitrogen sorption, and the accessibility of the pores to bulky molecules was also evaluated. It represents a strategy to prepare hybrid materials with large porosity utilising structurally simple building blocks as precursors.

A low temperature, isothermal gas-phase system for conversion of methane to methanol over Cu-ZSM-5

A low temperature, isothermal, gas-phase, recyclable process is described for the partial oxidation of methane to methanol over Cu–ZSM-5. Activation in NO at 150 °C followed by methane reaction and steam extraction (both at 150 °C) allowed direct observation of methanol at the reactor outlet.

Impact of sample preparation on mineralogical analysis of zero-valent iron reactive barrier materials

Permeable reactive barriers (PRBs) of zero-valent iron (Fe⁰) are increasingly being used to remediate contaminated ground water. Corrosion of Fe⁰ filings and tbe formation of precipitates can occur when the PRB material comes in contact with ground water and may reduce the lifespan and effectiveness of the barrier. At present, there are no routine procedures for preparing and analyzing the mineral precipitates from Fe⁰ PRB material. These procedures are needed because mineralogical composition of corrosion products used to interpret the barrier processes can change with iron oxidation and sample preparation. The objectives of this study were (i) to investigate a method of preparing Fe⁰ reactive barrier material for mineralogical analysis by X-ray diffraction (XRD), and (ii) to identify Fe mineral phases and rates of transformations induced by different mineralogical preparation techniques. Materials from an in situ Fe⁰ PRB were collected by undisturbed coring and processed for XRD analysis after different times since sampling for three size fractions and by various drying treatments. We found that whole-sample preparation for analysis was necessary because mineral precipitates occurred within the PRB material in different size fractions of the samples. Green rusts quickly disappeared from acetone-dried samples and were not present in air-dried and oven-dried samples Maghemite/magnetite content increased over time and in oven-dried samples, especially after heating to 105°C. We conclude that care must be taken during sample preparation of Fe⁰ PRB material, especially for detection of green rusts, to ensure accurate identification of minerals present within the barrier system.

Electromagnetic Focusing and Imaging in Stratified Media Using Gradient Phase Profiled Conjugating Lens

High-resolution imaging of a dipole source in stratified medium based on negative refraction is presented in this paper. Compensation of the material parameter contrast at the stratified media interface is achieved using a gradient phase profiled conjugating lens (GPCL). It is shown both analytically and numerically that the phase gradient applied across the GPCL positioned at the interface of vertically stratified media enables a high-quality image of a dipole source in a mirror symmetric position with respect to the lens plane. The analytical closed form expression of the phase gradient function is derived using Huygens-Kirchhoff principle. The result is applicable to media with arbitrary stratification and material parameters, including lossy materials. The mechanism for formation of the dipole image in the stratified medium and aberration due to the dielectric contrast at the interface, particularly electromagnetic loss, is discussed in detail. The efficacy of gradient phase and amplitude aberration compensations mechanisms available through the GPCL is articulated. The results of the study are of importance in a wide range of imaging problems in stratified media for medical, civil, and military applications.

In situ preparation of 3D graphene aerogels@hierarchical Fe3O4 nanoclusters as high rate and long cycle anode materials for lithium ion batteries

We describe a novel strategy for in situ fabrication of hierarchical Fe₃O₄ nanoclusters-GAs. Fe₃O₄ NCs-GAs deliver excellent rate capability (the reversible capacities obtained were 1442, 392 and 118 mA h g^-1 at 0.1C, 12C and 35C rates), and a high reversible capacity of 577 mA h g^-1 over 300 cycles at the current density of 5.2 A g^-1 (6C).

Design and results of a dual-gas Quasi-Phase matching (QPM) foil target

Quasi-phase matching (QPM) can be used to increase the conversion efficiency of the high harmonic generation (HHG) process. We observed QPM with an improved dual-gas foil target with a 1 kHz, 10 mJ, 30 fs laser system. Phase tuning and enhancement were possible within a spectral range from 17 nm to 30 nm. Furthermore analytical calculations and numerical simulations were carried out to distinguish QPM from other effects, such as the influence of adjacent jets on each other or the laser gas interaction. The simulations were performed with a 3 dimensional code to investigate the phase matching of the short and long trajectories individually over a large spectral range.

TAP Reactor Development and Application in the Kinetic Characterization of Catalysts for Heterogeneously Catalyzed Gas Phase Reactions

This manuscript describes the application and further development of the TAP technique in kinetic characterization of heterogeneous catalysis. The major application of TAP systems is to study mechanisms, kinetics and transport phenomena in heterogeneous catalysis, all of which is made possible by the sub-millisecond time resolution. Furthermore, the kinetic information obtained can be used to gain an insight into the mechanism occurring over the catalyst system. This is advantageous as heterogeneous catalysts with an improved efficiency can be developed as a result. TAP kinetic studies are carried out at low pressure (~1x10-7 mbar) and TAP pulses are sufficiently small (1013-1015 molecules) so as to maintain this low pressure. The use of a small number of molecules in comparison to the total number of active sites means the state of the catalyst remains relatively unchanged. The use of the low intensity pulses also makes the pressure gradient negligible and so allows the TAP reactor system to operate in the Knudsen Diffusion regime, where gas-gas reactions are eliminated. Hence only gas-catalyst reactions are investigated and, by the use of moment analysis of observed exit flow, rate constants of elementary steps of the reaction can be obtained.

In this manuscript, two attempts to further the TAP technique are reported. Firstly, the work undertaken at QUB to attempt to control the number of molecules of condensable reagents that can be pulsed during a TAP pulse experiment is disclosed. Secondly, a collaborative project with SAI Ltd Manchester is discussed in a separate chapter, where technical details and validation of a customised time of flight mass spectrometer (ToF MS) for the QUB TAP-1 system are reported. A collaborative project with Cardiff Catalysis Institute focusing on the study of CO oxidation over hopcalite catalysts is also reported. The analysis of the experimental results has provided an insight into the possible mechanism of the oxidation of CO over these catalysts. A correction function has also been derived which accounts for the adsorption of reactant molecules over inert materials that are used for the reactor packing in TAP experiments. This function was then applied to the selective reduction of O2 in a H2 rich ethene feed, so that more accurate TAP moment based analysis could be conducted.

Photon nanojet lens: Design, fabrication and characterization

In this paper, a novel nanolens with super resolution, based on the photon nanojet effect through dielectric nanostructures in visible wavelengths, is proposed. The nanolens is made from plastic SU-8, consisting of parallel semi-cylinders in an array. This paper focuses on the lens designed by numerical simulation with the finite-difference time domain method and nanofabrication of the lens by grayscale electron beam lithography combined with a casting/bonding/lift-off transfer process. Monte Carlo simulation for injected charge distribution and development modeling was applied to define the resultant 3D profile in PMMA as the template for the lens shape. After the casting/bonding/lift-off process, the fabricated nanolens in SU-8 has the desired lens shape, very close to that of PMMA, indicating that the pattern transfer process developed in this work can be reliably applied not only for the fabrication of the lens but also for other 3D nanopatterns in general. The light distribution through the lens near its surface was initially characterized by a scanning near-field optical microscope, showing a well defined focusing image of designed grating lines. Such focusing function supports the great prospects of developing a novel nanolithography based on the photon nanojet effect.

Multiscale Analysis for Field-Effect Penetration through Two-Dimensional Materials

Gate-tunable two-dimensional (2D) materials-based quantum capacitors (QCs) and van der Waals heterostructures involve tuning transport or optoelectronic characteristics by the field effect. Recent studies have attributed the observed gate-tunable characteristics to the change of the Fermi level in the first 2D layer adjacent to the dielectrics, whereas the penetration of the field effect through the one-molecule-thick material is often ignored or oversimplified. Here, we present a multiscale theoretical approach that combines first-principles electronic structure calculations and the Poisson–Boltzmann equation methods to model penetration of the field effect through graphene in a metal–oxide–graphene–semiconductor (MOGS) QC, including quantifying the degree of “transparency” for graphene two-dimensional electron gas (2DEG) to an electric displacement field. We find that the space charge density in the semiconductor layer can be modulated by gating in a nonlinear manner, forming an accumulation or inversion layer at the semiconductor/graphene interface. The degree of transparency is determined by the combined effect of graphene quantum capacitance and the semiconductor capacitance, which allows us to predict the ranking for a variety of monolayer 2D materials according to their transparency to an electric displacement field as follows: graphene > silicene > germanene > WS2 > WTe2 > WSe2 > MoS2 > phosphorene > MoSe2 > MoTe2, when the majority carrier is electron. Our findings reveal a general picture of operation modes and design rules for the 2D-materials-based QCs.