Free radical reactions in atherosclerosis; An EPR spectrometry study

The copper catalysed oxidation of homocysteine has been studied by electron paramagnetic resonance (EPR) spectroscopy and spin trapping techniques to determine the nature of free radical species formed under varying experimental conditions. Three radicals; thiyl, alkyl and hydroxyl were detected with hydroxyl being predominant. A reaction mechanism is proposed involving Fenton chemistry. Inclusion of catalase to test for intermediate generation of hydrogen peroxide showed a marked reduction in amount of hydroxyl radical generated. In contrast, the addition of superoxide dismutase showed no significant effect on the level of hydroxyl radical formed. Enhanced radical formation was observed at higher levels of oxygen, an effect which has consequences for differential oxygen levels in arterial and venous systems. Implications are drawn for a higher incidence of atherosclerotic plaque formation in arteries versus veins. © 2006 - IOS Press and the authors. All rights reserved.

Integrating in silico and in vitro analysis of peptide binding affinity to HLA-Cw*0102:a bioinformatic approach to the prediction of new epitopes

Predictive models of peptide-Major Histocompatibility Complex (MHC) binding affinity are important components of modern computational immunovaccinology. Here, we describe the development and deployment of a reliable peptide-binding prediction method for a previously poorly-characterized human MHC class I allele, HLA-Cw*0102.

Functionalisation of ethylene-propylene rubber with glycidyl methacrylate in the presence of comonomer and in situ compatibilisation of PET/f-EPR blends

The main aim of this work was two fold, firstly to investigate the effect of a highly reactive comonomer, divinylbenzene (DVB), on the extent of melt grafting of glycidyl methacrylate (GMA) on ethylene-propylene rubber (EPR) using 2,5-dimethyl-2,5-bis-(tert-butyl peroxy) hexane (Trigon ox 101, Tl 01) as a free radical initiator, and to compare the results with a conventional grafting of the same monomer on EPR. To achieve this, the effect of processing conditions and chemical composition including the concentration of peroxide, GMA and DVB on the extent of grafting was investigated. The presence of the comonomer (DVB) in the grafting process resulted in a significant increase in the extent of the grafting using only a small concentration of peroxide. It was also found that the extent of grafting increased drastically with increasing the DVB concentration. Interestingly, in the comonomer system, the extent of the undesired side reaction, normally the homopolymerisation of GMA (polyGMA) was shown to have reduced tremendously and in most cases the level of polyGMA was immeasurable in the samples. Compared to a conventional EPR-g-GMACONV (in the absence of a comonomer), the presence of the comonomer DVB in the grafting system was shown to result in more branching and crosslinking (shown from an increase in melt flow index (MFI) and torque values) and this was paralleled by an increase in DVB concentration. In contrast, the extent of grafting in conventional system increased with increasing the peroxide concentration but the level of grafting was much lower than in the case of DVB. Homopolymerisation of GMA and excessive crosslinking of EPR became dominant at high peroxide concentration and this. reflects that the side reactions were favorable in the conventional grafting system. The second aim was to examine the effect of the in-situ functionalised EPR when used as a compatibiliser for binary blends. It was found that blending PET with functionalised EPR (ƒ-EPR) gave a significant improvement in terms of blend morphology as well as mechanical properties. The results showed clearly that, blending PET with ƒ-EPRDVB (prepared with DVB) was much more effective compared to the corresponding PET/ƒ-EPRCONV (without DVB) blends in which ƒ-EPRDVB having optimum grafting level of 2.1 wt% gave the most pronounced effect on the morphology and mechanical properties. On the other hand, blends of PET/ƒ-EPRDVB containing high GMA/DVB ratio was found to be unfavorable hence exhibited lower tensile properties and showed unfavorable morphology. The presence of high polyGMA concentration in ƒ-EPRCONV was found to create damaging effect on its morphology, hence resulting in reduced tensile properties (e.g. low elongation at break). However, the use of commercial terpolymers based on ethylene-methacrylate-glycidyl methacrylate (EM-GMA)or a copolymer of ethylene-glycidyl methacrylate (E-GMA) containing various GMA levels as compatibilisers in PET/EPR blends was found to be more efficient compared to PET/EPR/ƒ-EPR blends with the former blends showing finer morphology and high elongation at break. The high efficiency of the terpolymers or copolymers in compatibilising the PET/EPR blends is suggested to be partly, higher GMA content compared to the amount in ƒ-EPR and due to its low viscosity.

Reactive processing of polymers: structural characterization of products by 1H and 13C NMR spectroscopy for glycidyl methacrylate grafting onto EPR in the absence and presence of a reactive comonomer

Grafted GMA on EPR samples were prepared in a Thermo-Haake internal mixer by free radical melt grafting reactions in the absence (conventional system; EPR-g-GMA(CONV)) and presence of the reactive comonomer divinyl benzene, DVB (EPR-g-GMA(DVB)). The GMA-homopolymer (poly-GMA), a major side reaction product in the conventional system, was almost completely absent in the DVB-containing system, the latter also resulted in a much higher level of GMA grafting. A comprehensive microstructure analysis of the formed poly-GMA was performed based on one-dimensional H-1 and C-13 NMR spectroscopy and the complete spectral assignments were supported by two-dimensional NMR techniques based on long range two and three bond order carbon-proton couplings from HMBC (Heteronuclear Multiple Bond Coherence) and that of one bond carbon-proton couplings from HSQC (Heteronuclear Single Quantum Coherence), as well as the use of Distortionless Enhancement by Polarization Transfer (DEPT) NMR spectroscopy. The unambiguous analysis of the stereochemical configuration of poly-GMA was further used to help understand the microstructures of the GMA-grafts obtained in the two different free radical melt grafting reactions, the conventional and comonomer-containing systems. In the grafted GMA, in the conventional system (EPR-g-GMA(CONV)), the methylene protons of the GMA were found to be sensitive to tetrad configurational sequences and the results showed that 56% of the GMA sequence in the graft is in atactic configuration and 42% is in syndiotactic configuration whereas the poly-GMA was predominantly syndiotactic. The differences in the microstructures of the graft in the conventional EPR-g-GMA(CONV) and the DVB-containing (EPR-g-GMA(DVB)) systems is also reported (C) 2009 Elsevier Ltd. All rights reserved.

Broadly tunable CW green-to-red laser source based on frequency doubling of a quantum-dot external cavity diode laser in a PPKTP waveguide

Here we present a compact tunable all-room-temperature frequency-doubling scheme, using a periodically poled potassium titanyl phosphate (PPKTP) waveguide and a QD-ECDL. A broad wavelength tunability of the second harmonic generated light (SHG) in the spectral region between 567.7 and 629.1 nm was achieved, with maximum conversion efficiencies in range of 0.34%-7.9%. The maximum output power for the SHG light was 4.11 mW at 591.5 nm, achieved for 52 mW of launched pump power at 1183 nm, resulting in a conversion efficiency of 7.9%.

Generation of CW tunable visible light by SHG of QD laser in a PPKTP waveguide

We demonstrate a CW tunable compact all-room-temperature laser system in the visible spectral region from 567.7 nm to 629.1 nm, by frequency doubling in a periodically-poled KTP waveguide crystal using a tunable quantum-dot external-cavity diode laser.

Orange light generation from a PPKTP waveguide end pumped by a cw quantum-dot tunable laser diode

A compact all-room-temperature frequency-doubling scheme generating cw orange light with a periodically poled potassium titanyl phosphate waveguide and a quantum-dot external cavity diode laser is demonstrated. A frequency-doubled power of up to 4.3 mW at the wavelength of 612.9 nm with a conversion efficiency exceeding 10% is reported. Second harmonic wavelength tuning between 612.9 nm and 616.3 nm by changing the temperature of the crystal is also demonstrated. © Springer-Verlag 2010.

Power-controlled phase-matching and instability of CW propagation in multicore optical fibers with a central core

We present modulation instability analysis including azimuthal perturbations of steady-state continuous wave (CW) propagation in multicore-fiber configurations with a central core. In systems with a central core, a steady CW evolution regime requires power-controlled phase matching, which offers interesting spatial-division applications. Our results have general applicability and are relevant to a range of physical and engineering systems, including high-power fiber lasers, optical transmission in multicore fiber, and systems of coupled nonlinear waveguides. © 2013 Optical Society of America.

Revealing statistical properties of quasi-CW fibre lasers in bandwidth-limited measurements

We introduce a general technique how to reveal in experiments of limited electrical bandwidth which is lower than the optical bandwidth of the optical signal under study, whether the statistical properties of the light source obey Gaussian distribution or mode correlations do exist. To do that one needs to perform measurements by decreasing the measurement bandwidth. We develop a simple model of bandwidth-limited measurements and predict universal laws how intensity probability density function and intensity auto-correlation function of ideal completely stochastic source of Gaussian statistics depend on limited measurement bandwidth and measurement noise level. Results of experimental investigation are in good agreement with model predictions. In particular, we reveal partial mode correlations in the radiation of quasi-CW Raman fibre laser.

Influence of the generated power, measurement bandwidth, and noise level on intensity statistics of a quasi-CW Raman fiber laser

In the present paper we numerically study instrumental impact on statistical properties of quasi-CW Raman fiber laser using a simple model of multimode laser radiation. Effects, that have the most influence, are limited electrical bandwidth of measurement equipment and noise. To check this influence, we developed a simple model of the multimode quasi- CW generation with exponential statistics (i.e. uncorrelated modes). We found that the area near zero intensity in probability density function (PDF) is strongly affected by both factors, for example both lead to formation of a negative wing of intensity distribution. But far wing slope of PDF is not affected by noise and, for moderate mismatch between optical and electrical bandwidth, is only slightly affected by bandwidth limitation. The generation spectrum often becomes broader at higher power in experiments, so the spectral/electrical bandwidth mismatch factor increases over the power that can lead to artificial dependence of the PDF slope over the power. It was also found that both effects influence the ACF background level: noise impact decreases it, while limited bandwidth leads to its increase. © (2014) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.

Spectral narrowing of CW light in optical fibers with normal dispersion

Spectrum narrowing of CW light was observed experimentally in optical transmission fibers with normal dispersion. The effect's theoretical interpretation as an effective self-pumping parametric amplification of the spectrum's central part is confirmed by numerical modeling. OCIS codes: (060.4370) Nonlinear optics, fibers; (190.4410) Nonlinear optics, parametric processes; (190.4380); Nonlinear optics, four-wave mixing. © OSA 2015.

Spatio-temporal generation regimes in quasi-CW Raman fiber lasers

We present experimental measurements of intensity spatiotemporal dynamics in quasi-CW Raman fiber laser. Depending on the power, the laser operates in different spatio-temporal regimes varying from partial mode-locking near the generation threshold to almost stochastic radiation and a generation of short-lived pulses at high power. The transitions between the generation regimes are evident in intensity spatio-temporal dynamics. Two-dimensional auto-correlation functions provide an additional insight into temporal and spatial properties of the observed regimes.

Ginzburg-Landau turbulence in quasi-CW Raman fiber lasers

Fiber lasers operating via Raman gain or based on rare-earth-doped active fibers are widely used as sources of CW radiation. However, these lasers are only quasi-CW: their intensity fluctuates strongly on short time scales. Here the framework of the complex Ginzburg-Landau equations, which are well known as an efficient model of mode-locked fiber lasers, is applied for the description of quasi-CW fiber lasers. The vector Ginzburg-Landau model of a Raman fiber laser describes the experimentally observed turbulent-like intensity dynamics, as well as polarization rogue waves. Our results open debates about the common underlying physics of operation of very different laser types - quasi-CW lasers and passively mode-locked lasers. Fiber lasers operating via Raman gain or based on rare-earth-doped active fibers are widely used as sources of CW radiation. However, these lasers are only quasi-CW: their intensity fluctuates strongly on short time scales. Here the framework of the complex Ginzburg-Landau equations, which are well known as an efficient model of mode-locked fiber lasers, is applied for the description of quasi-CW fiber lasers. The vector Ginzburg-Landau model of a Raman fiber laser describes the experimentally observed turbulent-like intensity dynamics, as well as polarization rogue waves. Our results open debates about the common underlying physics of operation of very different laser types - quasi-CW lasers and passively mode-locked lasers.

Implementing a knowledge management system within an NHS hospital:a case study exploring the roll-out of an Electronic Patient Record (EPR)

This research aims to contribute to understanding the implementation of knowledge management systems (KMS) in the field of health through a case study, leading to theory building and theory extension. We use the concept of the business process approach to knowledge management as a theoretical lens to analyse and explore how a large teaching hospital developed, executed and practically implemented a KMS. A qualitative study was conducted over a 2.5 year period with data collected from semi-structured interviews with eight members of the strategic management team, 12 clinical users and 20 patients in addition to non-participant observation of meetings and documents. The theoretical propositions strategy was used as the overarching approach for data analysis. Our case study provides evidence that true patient centred approaches to supporting care delivery with a KMS benefit from process thinking at both the planning and implementation stages, and an emphasis on the knowledge demands resulting from: the activities along the care pathways; where cross-overs in care occur; and knowledge sharing for the integration of care. The findings also suggest that despite the theoretical awareness of KMS implementation methodologies, the actual execution of such systems requires practice and learning. Flexible, fluid approaches through rehearsal are important and communications strategies should focus heavily on transparency incorporating both structured and unstructured communication methods.