Oxidation of aqueous sulfur dioxide catalyzed by poly-4-vinylpyridine-Cu(II) complex. Part 1: Homogeneous phase oxidation

The oxidation of aqueous sulfur dioxide in the presence of polymer-supported copper(II) catalyst is also accompanied by homogeneous oxidation of aqueous sulfur dioxide catalyzed by leached copper(II) ions. Aqueous phase oxidation of sulfur dioxide of low concentrations by oxygen in the presence of dissolved copper(II) has therefore been studied. The solubility of SO2 in aqueous solutions is not affected by the concentration of copper(II) in the solution. In the oxidation reaction, only HSO3- is the reactive S(IV) species. Based on this observation a rate model which also incorporates the effect of sulfuric acid on the solubility of SO2 is developed. The rate model includes a power-law type term for the rate of homogeneous phase reaction obtained from a proposed free-radical chain mechanism for the oxidation. Experiments are conducted at various levels of concentrations of SO2 and O-2 in the gas phase and Cu(II) in the liquid phase. The observed orders are one in each of O-2, Cu(II) and HSO3-. This suggests a first-order termination of the free radicals of bisulfite ions.

Multiphase models for simulating hot and slightly miscible DNAPL (dense non-aqueous phase fluids) in a saturated rock fracture under deformation

In the present study a two dimensional model is first developed to show the behaviour of dense non-aqueous phase liquids (DNAPL) within a rough fracture. To consider the rough fracture, the fracture is imposed with variable apertures along its plane. It is found that DNAPL follows preferential pathways. In next part of the study the above model is further extended for non-isothermal DNAPL flow and DNAPL-water interphase mass transfer phenomenon. These two models are then coupled with joint deformation due to normal stresses. The primary focus of these models is specifically to elucidate the influence of joint alteration due to external stress and fluid pressures on flow driven energy transport and interphase mass transfer. For this, it is assumed that the critical value for joint alteration is associated with external stress and average of water and DNAPL pressures in multiphase system and the temporal and spatial evolution of joint alteration are determined for its further influence on energy transport and miscible phase transfer. The developed model has been studied to show the influence of deformation on DNAPL flow. Further this preliminary study demonstrates the influence of joint deformation on heat transport and phase miscibility via multiphase flow velocities. It is seen that the temperature profile changes and shows higher diffusivity due to deformation and although the interphase miscibility value decreases but the lateral dispersion increases to a considerably higher extent.

Cyclone-induced mixing does not cool SST in the post-monsoon north Bay of Bengal

High-resolution data from the TRMM satellite shows that sea surface temperature (SST) cools by 3 degrees C under the tracks of pre-monsoon tropical cyclones in the north Indian Ocean. However, even the strongest post-monsoon cyclones do not cool the open north Bay of Bengal. In this region, a shallow layer of freshwater from river runoff and monsoon rain caps a deep warm layer. Therefore, storm-induced mixing is not deep, and it entrains warm subsurface water. It is possible that the hydrography of the post-monsoon north Bay favours intense cyclones.

Structural and optical investigations of TiO2 films deposited on transparent substrates by sol-gel technique

An inexpensive and effective simple method for the preparation of nano-crystalline titanium oxide (anatase) thin films at room temperature on different transparent substrates is presented. This method is based on the use of peroxo-titanium complex, i.e. titanium isopropoxide as a single initiating organic precursor. Post-annealing treatment is necessary to convert the deposited amorphous film into titanium oxide (TiO2) crystalline (anatase) phase. These films have been characterized for X-ray diffraction (XRD) studies, atomic force microscopic (AFM) studies and optical measurements. The optical constants such as refractive index and extinction coefficient have been estimated by using envelope technique. Also, the energy gap values have been estimated using Tauc's formula for on glass and quartz substrates are found to be 3.35 eV and 3.39 eV, respectively.

A phase field study of morphological instabilities in multilayer thin films

We studied the microstructural evolution of multiple layers of elastically stiff films embedded in an elastically soft matrix using a phase field model. The coherent and planar film/matrix interfaces are rendered unstable by the elastic stresses due to a lattice parameter mismatch between the film and matrix phases, resulting in the break-up of the films into particles. With an increasing volume fraction of the stiff phase, the elastic interactions between neighbouring layers lead to: (i) interlayer correlations from an early stage; (ii) a longer wavelength for the maximally growing wave; and therefore (iii) a delayed break-LIP. Further, they promote a crossover in the mode of instability from a predominantly anti-symmetric (in phase) one to a symmetric (out of phase) one. We have computed a stability diagram for the most probable mode of break-up in terms of elastic modulus Mismatch and Volume fraction. We rationalize our results in terms of the initial driving force for destabilization, and corroborate our conclusions using simulations in elastically anisotropic systems.

PW376 A pilot study of a post-discharge nurse-led, educational intervention on cardiac self-efficacy and anxiety in post-PCI patients

Introduction Hospitalisation for percutaneous coronary intervention (PCI) is often short, with limited nurse-teaching time and poor information absorption. Currently, patients are discharged home only to wait up to 4-8 weeks to commence a secondary prevention program and visit their cardiologist. This wait is an anxious time for patients and confidence or self-efficacy (SE) to self-manage may be low. Objectives To determine the effects of a nurse-led, educational intervention on participant SE and anxiety in the early post-discharge period. Methods A pilot study was undertaken as a randomised controlled clinical trial. Thirty-three participants were recruited, with n=13 randomised to the intervention group. A face-to-face, nurse-led, educational intervention was undertaken within the first 5-7 days post-discharge. Intervention group participants received standard post-discharge education, physical assessment, with a strong focus on the emotional impact of cardiovascular events and PCI. Early reiteration of post-discharge education was offered, along with health professional support with the aim to increase patients’ SE and to effectively manage their post-discharge health and well being, as well as anxieties. Self-efficacy to return to normal activities was measured to gauge participants’ abilities to manage post-PCI after attending the intervention using the cardiac self-efficacy (CSE) scale. State and trait anxiety was also measured using the State-Trait Anxiety Inventory (STAI) to determine if an increase in SE would influence participant anxiety. Results There were some increases in mean CSE scores in the intervention group participants over time. Areas of increase included return to normal social activities and confidence to change diet. Although reductions were observed in mean state and trait anxiety scores in both groups, an overall larger reduction in intervention group participants was observed over time. Conclusion It is essential that patients are given the education, support, and skills to self-manage in the early post-discharge period so that they have greater SE and are less anxious. This study provides some initial evidence that nurse-led support and education during this period, particularly the first week following PCI, is beneficial and could be trialled using alternate modes of communication to support remote and rural PCI patients and extend to other cardiovascular patients.

The Post-Illumination Pupil Response (PIPR)

Purpose The post-illumination pupil response (PIPR) has been quantified using four metrics, but the spectral sensitivity of only one is known; here we determine the other three. To optimize the human PIPR measurement, we determine the protocol producing the largest PIPR, the duration of the PIPR, and the metric(s) with the lowest coefficient of variation. Methods The consensual pupil light reflex (PLR) was measured with a Maxwellian view pupillometer. - Experiment 1: Spectral sensitivity of four PIPR metrics [plateau, 6 s, area under curve (AUC) early and late recovery] was determined from a criterion PIPR to a 1s pulse and fitted with Vitamin A1 nomogram (λmax = 482nm). - Experiment 2: The PLR was measured as a function of three stimulus durations (1s, 10s, 30s), five irradiances spanning low to high melanopsin excitation levels (retinal irradiance: 9.8 to 14.8 log quanta.cm-2.s-1), and two wavelengths, one with high (465nm) and one with low (637nm) melanopsin excitation. Intra and inter-individual coefficients of variation (CV) were calculated. Results The melanopsin (opn4) photopigment nomogram adequately describes the spectral sensitivity of all four PIPR metrics. The PIPR amplitude was largest with 1s short wavelength pulses (≥ 12.8 log quanta.cm-2.s-1). The plateau and 6s PIPR showed the least intra and inter-individual CV (≤ 0.2). The maximum duration of the sustained PIPR was 83.0±48.0s (mean±SD) for 1s pulses and 180.1±106.2s for 30s pulses (465nm; 14.8 log quanta.cm-2.s-1). Conclusions All current PIPR metrics provide a direct measure of the intrinsic melanopsin photoresponse. To measure progressive changes in melanopsin function in disease, we recommend that the PIPR be measured using short duration pulses (e.g., ≤ 1s) with high melanopsin excitation and analyzed with plateau and/or 6s metrics. Our PIPR duration data provide a baseline for the selection of inter-stimulus intervals between consecutive pupil testing sequences.

Effect of age and refractive error on the melanopsin mediated Post-Illumination Pupil Response (PIPR)

Melanopsin containing intrinsically photosensitive Retinal Ganglion cells (ipRGCs) mediate the pupil light reflex (PLR) during light onset and at light offset (the post-illumination pupil response, PIPR). Recent evidence shows that the PLR and PIPR can provide non-invasive, objective markers of age-related retinal and optic nerve disease, however there is no consensus on the effects of healthy ageing or refractive error on the ipRGC mediated pupil function. Here we isolated melanopsin contributions to the pupil control pathway in 59 human participants with no ocular pathology across a range of ages and refractive errors. We show that there is no effect of age or refractive error on ipRGC inputs to the human pupil control pathway. The stability of the ipRGC mediated pupil response across the human lifespan provides a functional correlate of their robustness observed during ageing in rodent models.

The post-illumination pupil response of melanopsin expressing retinal ganglion cells

Purpose The post-illumination pupil response (PIPR) has been quantified in the literature by four metrics. The spectral sensitivity of only one metric is known and this study quantifies the other three. To optimize the measurement of the PIPR in humans, we also determine the stimulus protocol producing the largest PIPR, the duration of the PIPR, and the metric(s) with the lowest coefficient of variation. Methods The consensual pupil light reflex (PLR) was measured with a Maxwellian view pupillometer (35.6° diameter stimulus). - Experiment 1: Spectral sensitivity of four PIPR metrics [plateau, 6 s, area under curve (AUC) early and late recovery] was determined from a criterion PIPR (n = 2 participants) to a 1 s pulse at five wavelengths (409-592nm) and fitted with Vitamin A nomogram (ƛmax = 482 nm). - Experiment 2: The PLR was measured in five healthy participants [29 to 42 years (mean = 32.6 years)] as a function of three stimulus durations (1 s, 10 s, 30 s), five irradiances spanning low to high melanopsin excitation levels (retinal irradiance: 9.8 to 14.8 log quanta.cm-2.s-1), and two wavelengths, one with high (465 nm) and one with low (637 nm) melanopsin excitation. Intra and inter-individual coefficients of variation (CV) were calculated. Results The melanopsin (opn4) photopigment nomogram adequately described the spectral sensitivity derived from all four PIPR metrics. The largest PIPR amplitude was observed with 1 s short wavelength pulses (retinal irradiance ≥ 12.8 log quanta.cm-2.s-1). Of the 4 PIPR metrics, the plateau and 6 s PIPR showed the least intra and inter-individual CV (≤ 0.2). The maximum duration of the sustained PIPR was 83.4 ± 48.0 s (mean ± SD) for 1 s pulses and 180.1 ± 106.2 s for 30 s pulses (465 nm; 14.8 log quanta.cm-2.s-1). Conclusions All current PIPR metrics provide a direct measure of intrinsic melanopsin retinal ganglion cell function. To measure progressive changes in melanopsin function in disease, we recommend that the intrinsic melanopsin response should be measured using a 1 s pulse with high melanopsin excitation and the PIPR should be analyzed with the plateau and/or 6 s metrics. That the PIPR can have a sustained constriction for as long as 3 minutes, our PIPR duration data provide a baseline for the selection of inter-stimulus intervals between consecutive pupil testing sequences.

Standardised antibacterial Manuka honey in the management of persistent post-operative corneal oedema: A case series

Background Corneal oedema is a common post-operative problem that delays or prevents visual recovery from ocular surgery. Honey is a supersaturated solution of sugars with an acidic pH, high osmolarity and low water content. These characteristics inhibit the growth of micro-organisms, reduce oedema and promote epithelialisation. This clinical case series describes the use of a regulatory approved Leptospermum species honey ophthalmic product, in the management of post-operative corneal oedema and bullous keratopathy. Methods A retrospective review of 18 consecutive cases (30 eyes) with corneal oedema persisting beyond one month after single or multiple ocular surgical procedures (phacoemulsification cataract surgery and additional procedures) treated with Optimel Antibacterial Manuka Eye Drops twice to three times daily as an adjunctive therapy to conventional topical management with corticosteroid, aqueous suppressants, hypertonic sodium chloride five per cent, eyelid hygiene and artificial tears. Visual acuity and central corneal thickness were measured before and at the conclusion of Optimel treatment. Results A temporary reduction in corneal epithelial oedema lasting up to several hours was observed after the initial Optimel instillation and was associated with a reduction in central corneal thickness, resolution of epithelial microcysts, collapse of epithelial bullae, improved corneal clarity, improved visualisation of the intraocular structures and improved visual acuity. Additionally, with chronic use, reduction in punctate epitheliopathy, reduction in central corneal thickness and improvement in visual acuity were achieved. Temporary stinging after Optimel instillation was experienced. No adverse infectious or inflammatory events occurred during treatment with Optimel. Conclusions Optimel was a safe and effective adjunctive therapeutic strategy in the management of persistent post-operative corneal oedema and warrants further investigation in clinical trials.

Influence of Martensite Content and Morphology on Tensile and Impact Properties of High-Martensite Dual-Phase Steels

A series of dual-phase (DP) steels containing finely dispersed martensite with different volume fractions of martensite (V-m) were produced by intermediate quenching of a boron- and vanadium-containing microalloyed steel. The volume fraction of martensite was varied from 0.3 to 0.8 by changing the intercritical annealing temperature. The tensile and impact properties of these steels were studied and compared to those of step-quenched steels, which showed banded microstructures. The experimental results show that DP steels with finely dispersed microstructures have excellent mechanical properties, including high impact toughness values, with an optimum in properties obtained at similar to 0.55 V-m. A further increase in V-m was found to decrease the yield and tensile strengths as well as the impact properties. It was shown that models developed on the basis of a rule of mixtures are inadequate in capturing the tensile properties of DP steels with V-m > 0.55. Jaoul-Crussard analyses of the work-hardening behavior of the high-martensite volume fraction DP steels show three distinct stages of plastic deformation.

Structural and optical investigations of TiO2 films deposited on transparent substrates by sol-gel technique

An inexpensive and effective simple method for the preparation of nano-crystalline titanium oxide (anatase) thin films at room temperature on different transparent substrates is presented. This method is based on the use of peroxo-titanium complex, i.e. titanium isopropoxide as a single initiating organic precursor. Post-annealing treatment is necessary to convert the deposited amorphous film into titanium oxide (TiO2) crystalline (anatase) phase. These films have been characterized for X-ray diffraction (XRD) studies, atomic force microscopic (AFM) studies and optical measurements. The optical constants such as refractive index and extinction coefficient have been estimated by using envelope technique. Also, the energy gap values have been estimated using Tauc's formula for on glass and quartz substrates are found to be 3.35 eV and 3.39 eV, respectively. (C) 2008 Elsevier B.V. All rights reserved.

Detection of the protein dimers, multiple monomeric states and hydrated forms of Plasmodium falciparum triosephosphate isomerase in the gas phase

Dimeric and monomeric forms of the enzyme triosephosphate isomerase (TIM) from Plasmodium falciparum (Pf) have been detected under conditions of nanoflow by electrospray mass spectrometry. The dimer (M = 55 663 Da) exhibits a narrow charge state distribution with intense peaks limited to values of 18(+) to 21(+), maximal intensity being observed for charge states 19(+) and 20(+). A monomeric species with a charge state distribution ranging from 11(+) to 16(+) is also observed, which may be assigned to folded dissociated subunits. Complete dimer dissociation results under normal electrospray condition. The effects of solution pH and source temperature have been investigated. The observation of four distinct charge state distributions which may be assigned to a dimer, folded monomer, partially folded monomer and unfolded monomer is reported. Circular dichromism and fluorescence studies of Pf TIM at low pH support the retention of substantial secondary and tertiary structures. Satellite peaks in mass spectra corresponding to hydrated species are also observed and isotope shift upon deuteration is demonstrated. The analysis of all available independent crystal structures of Pf TIM and TIMs from other organisms permits identification of structurally conserved water molecules. Hydration observed in the dimer and folded monomeric forms in the gas phase may correspond to these conserved sites.

Dipolar reorientation and phase-transition in mixed alkali-halide crystals

We show that the results of Lüty and Ortiz-Lopez relating the cyanide reorientation rates to the high-temperature phase diagrams of alkali-halide-alkali-cyanide mixed crystals can be understood within simple mean-field theory.

Electrochemical phase formation (ECPF): Nucleation growth vis-a-vis adsorption models

The nucleataon growth model of electrochemical phase formation is analysed for the hnear potential sweep input Apart from deducing diagnostic criteria and method~ of estimating model parameters, the predictions of the nucleation growth model are compared and contrasted with those of a sample adsorption model A dastlnCtlOn is made possible between adsorption and phase transition, which seems useful for understanding the nature of ECPF phenomena, especially underpotentlal deposition (UPD).