156 resultados para Photonic active filters


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The membrane-bound form of mammalian aminopeptidase P (AP-P; EC 3.4. 11.9) is a mono-zinc-containing enzyme that lacks any of the typical metal binding motifs found in other zinc metalloproteases. To identify residues involved in metal binding and catalysis, sequence and structural information was used to align the sequence of porcine membrane-bound AP-P with other members of the peptidase clan MG, including Escherichia coli AP-P and methionyl aminopeptidases. Residues predicted to be critical for activity were mutated and the resultant proteins were expressed in COS-1 cells. Immunoelectrophoretic blot analysis was used to compare the levels of expression of the mutant proteins, and their ability to hydrolyze bradykinin and Gly-Pro-hydroxyPro was assessed. Asp449, Asp460, His523, Glu554, and Glu568 are predicted to serve as metal ion ligands in the active site, and mutagenesis of these residues resulted in fully glycosylated proteins that were catalytically inactive. Mutation of His429 and His532 also resulted in catalytically inactive proteins, and these residues, by analogy with E. coli AP-P, are likely to play a role in shuttling protons during catalysis. These studies indicate that mammalian membrane-bound AP-P has an active-site configuration similar to that of other members of the peptidase clan MG, which is compatible with either a dual metal ion model or a single metal ion in the active site. The latter model is consistent, however, with the known metal stoichiometry of both the membrane-bound and cytosolic forms of AP-P and with a recently proposed model for methionyl aminopeptidase.

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Although there has been much interest in the chemistry of bimetallic transition metal complexes, compounds with naphthalene or anthracene as bridging ligands are still rare. In this article, we describe the synthesis of the homodinuclear iron complexes [Cp*Fe(μ-η4:η4-L)FeCp*] (1: L = C10H8, 2: L = C14H10; Cp* = η5-C5Me5). The complexes were characterized by 1H and 13C{1H} NMR, UV/Vis, and 57Fe Mössbauer spectroscopy, and their molecular structures were determined by X-ray crystallography. Both complexes are diamagnetic as a result of the strong magnetic coupling of the 17e FeI centers mediated by the polyarene bridge. An analysisof the redox behavior of 1 and 2 by cyclic voltammetry andUV/Vis spectroelectrochemistry shows that the complexes can be oxidized reversibly in two well-separated one-electron steps to the monocation [Cp*Fe(μ-L)FeCp*]+ and the dication [Cp*Fe(μ-L)FeCp*]2+. The reduction to the monoanion [Cp*Fe(μ-L)FeCp*]– was also observed.

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The Sea and Land Surface Temperature Radiometer (SLSTR) is a nine channel visible and infrared high precision radiometer designed to provide climate data of global sea and land surface temperatures. The SLSTR payload is destined to fly on the Ocean and Medium-Resolution Land Mission for the ESA/EU Global Monitoring for Environment and Security (GMES) Programme Sentinel-3 mission to measure the sea and land temperature and topography for near real-time environmental and atmospheric climate monitoring of the Earth. In this paper we describe the optical layout of infrared optics in the instrument, spectral thin-film multilayer design, and system channel throughput analysis for the combined interference filter and dichroic beamsplitter coatings to discriminate wavelengths at 3.74, 10.85 & 12.0 μm. The rationale for selection of thin-film materials, deposition technique, and environmental testing, inclusive of humidity, thermal cycling and ionizing radiation testing are also described.

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Electrospinning was used to generate polymer nanofibres from blends of poly-vinyl cinnamate (PVCN) and a cholesteric silicone polymer. Only blends that contained at least 40 % of PVCN produced fibres. Both differential scanning calorimetry and electron dispersion spectroscopy data indicate that the samples are miscible over a wide temperature interval. The variation of fibre diameter with concentration is nonlinear with a well-defined minimum corresponding to an 80 % PVCN blend. The fibres are birefringent with Kerr constants similar to that of cholesteric liquid crystals. Although not significant, the Kerr constant increases with increasing silicone polymer concentration.

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Two recent works have adapted the Kalman–Bucy filter into an ensemble setting. In the first formulation, the ensemble of perturbations is updated by the solution of an ordinary differential equation (ODE) in pseudo-time, while the mean is updated as in the standard Kalman filter. In the second formulation, the full ensemble is updated in the analysis step as the solution of single set of ODEs in pseudo-time. Neither requires matrix inversions except for the frequently diagonal observation error covariance. We analyse the behaviour of the ODEs involved in these formulations. We demonstrate that they stiffen for large magnitudes of the ratio of background error to observational error variance, and that using the integration scheme proposed in both formulations can lead to failure. A numerical integration scheme that is both stable and is not computationally expensive is proposed. We develop transform-based alternatives for these Bucy-type approaches so that the integrations are computed in ensemble space where the variables are weights (of dimension equal to the ensemble size) rather than model variables. Finally, the performance of our ensemble transform Kalman–Bucy implementations is evaluated using three models: the 3-variable Lorenz 1963 model, the 40-variable Lorenz 1996 model, and a medium complexity atmospheric general circulation model known as SPEEDY. The results from all three models are encouraging and warrant further exploration of these assimilation techniques.

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Methods for recombinant production of eukaryotic membrane proteins, yielding sufficient quantity and quality of protein for structural biology, remain a challenge. We describe here, expression and purification optimisation of the human SERCA2a cardiac isoform of Ca2+ translocating ATPase, using Saccharomyces cerevisiae as the heterologous expression system of choice. Two different expression vectors were utilised, allowing expression of C-terminal fusion proteins with a biotinylation domain or a GFP- His8 tag. Solubilised membrane fractions containing the protein of interest were purified onto Streptavidin-Sepharose, Ni-NTA or Talon resin, depending on the fusion tag present. Biotinylated protein was detected using specific antibody directed against SERCA2 and, advantageously, GFP-His8 fusion protein was easily traced during the purification steps using in-gel fluorescence. Importantly, talon resin affinity purification proved more specific than Ni-NTA resin for the GFP-His8 tagged protein, providing better separation of oligomers present, during size exclusion chromatography. The optimised method for expression and purification of human cardiac SERCA2a reported herein, yields purified protein (> 90%) that displays a calcium-dependent thapsigargin-sensitive activity and is suitable for further biophysical, structural and physiological studies. This work provides support for the use of Saccharomyces cerevisiae as a suitable expression system for recombinant production of multi-domain eukaryotic membrane proteins.

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There are competing theoretical expectations and conflicting empirical results concerning the impact of partisanship on spending on active labour market policies (ALMPs). This paper argues that one should distinguish between different ALMPs. Employment incentives and rehabilitation programmes incentivize the unemployed to accept jobs. Direct job creation reduces the supply of labour by creating non-commercial jobs. Training schemes raise the human capital of the unemployed. Using regression analysis this paper shows that the positions of political parties towards these three types of ALMPs are different. Party preferences also depend on the welfare regime in which parties are located. In Scandinavia, left-wing parties support neither employment incentives nor direct job creation schemes. In continental and Liberal welfare regimes, left-wing parties oppose employment incentives and rehabilitation programmes to a lesser extent and they support direct job creation. There is no impact of partisanship on training. These results reconcile the previously contradictory findings concerning the impact of the Left on ALMPs.

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In-work benefits have been introduced in a number of Bismarckian welfare regimes in a context of austerity despite being targeted at politically weak constituents and representing a deviation from prevailing welfare institutions. This article addresses this puzzle by looking at the introduction in 2008 of an in-work benefit scheme in France, the Active Income of Solidarity. The analysis reveals that this reform was the result of a cross-cutting alliance between the conservative party and employers, as well as parts of the socialist party and the union movement. The alliance was possible thanks to actors’ multiple interpretations of the reform. The reform was difficult to oppose given its support by experts and public opinion and because it entailed an increase in revenues for low-income workers.

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An optically transparent thin-layer electrochemical (OTTLE) cell with a locally extended optical path has been developed in order to perform vibrational circular dichroism (VCD) spectroscopy on chiral molecules prepared in specific oxidation states by means of electrochemical reduction or oxidation. The new design of the electrochemical cell successfully addresses the technical challenges involved in achieving sufficient infrared absorption. The VCD-OTTLE cell proves to be a valuable tool for the investigation of chiral redox-active molecules.

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The growing energy consumption in the residential sector represents about 30% of global demand. This calls for Demand Side Management solutions propelling change in behaviors of end consumers, with the aim to reduce overall consumption as well as shift it to periods in which demand is lower and where the cost of generating energy is lower. Demand Side Management solutions require detailed knowledge about the patterns of energy consumption. The profile of electricity demand in the residential sector is highly correlated with the time of active occupancy of the dwellings; therefore in this study the occupancy patterns in Spanish properties was determined using the 2009–2010 Time Use Survey (TUS), conducted by the National Statistical Institute of Spain. The survey identifies three peaks in active occupancy, which coincide with morning, noon and evening. This information has been used to input into a stochastic model which generates active occupancy profiles of dwellings, with the aim to simulate domestic electricity consumption. TUS data were also used to identify which appliance-related activities could be considered for Demand Side Management solutions during the three peaks of occupancy.

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The question of what explains variation in expenditures on Active Labour Market Programs (ALMPs) has attracted significant scholarship in recent years. Significant insights have been gained with respect to the role of employers, unions and dual labour markets, openness, and partisanship. However, there remain significant disagreements with respects to key explanatory variables such the role of unions or the impact of partisanship. Qualitative studies have shown that there are both good conceptual reasons as well as historical evidence that different ALMPs are driven by different dynamics. There is little reason to believe that vastly different programs such as training and employment subsidies are driven by similar structural, interest group or indeed partisan dynamics. The question is therefore whether different ALMPs have the same correlation with different key explanatory variables identified in the literature? Using regression analysis, this paper shows that the explanatory variables identified by the literature have different relation to distinct ALMPs. This refinement adds significant analytical value and shows that disagreements are at least partly due to a dependent variable problem of ‘over-aggregation’.

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European labour markets are increasingly divided between insiders in full-time permanent employment and outsiders in precarious work or unemployment. Using quantitative as well as qualitative methods, this thesis investigates the determinants and consequences of labour market policies that target these outsiders in three separate papers. The first paper looks at Active Labour Market Policies (ALMPs) that target the unemployed. It shows that left and right-wing parties choose different types of ALMPs depending on the policy and the welfare regime in which the party is located. These findings reconcile the conflicting theoretical expectations from the Power Resource approach and the insider-outsider theory. The second paper considers the regulation and protection of the temporary work sector. It solves the puzzle of temporary re-regulation in France, which contrasts with most other European countries that have deregulated temporary work. Permanent workers are adversely affected by the expansion of temporary work in France because of general skills and low wage coordination. The interests of temporary and permanent workers for re-regulation therefore overlap in France and left governments have an incentive to re-regulate the sector. The third paper then investigates what determines inequality between median and bottom income workers. It shows that non-inclusive economic coordination increases inequality in the absence of compensating institutions such as minimum wage regulation. The deregulation of temporary work as well as spending on employment incentives and rehabilitation also has adverse effects on inequality. Thus, policies that target outsiders have important economic effects on the rest of the workforce. Three broader contributions can be identified. First, welfare state policies may not always be in the interests of labour, so left parties may not always promote them. Second, the interests of insiders and outsiders are not necessarily at odds. Third, economic coordination may not be conducive to egalitarianism where it is not inclusive.

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This paper considers the effect of using a GARCH filter on the properties of the BDS test statistic as well as a number of other issues relating to the application of the test. It is found that, for certain values of the user-adjustable parameters, the finite sample distribution of the test is far-removed from asymptotic normality. In particular, when data generated from some completely different model class are filtered through a GARCH model, the frequency of rejection of iid falls, often substantially. The implication of this result is that it might be inappropriate to use non-rejection of iid of the standardised residuals of a GARCH model as evidence that the GARCH model ‘fits’ the data.

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The phosphine-stabilised gold cluster [Au6(Ph2P-o-tolyl)6](NO3)2 is converted into an active nanocatalyst for the oxidation of benzyl alcohol through low-temperature peroxide-assisted removal of the phosphines, avoiding the high-temperature calcination process. The process was monitored using in-situ X-ray absorption spectroscopy, which revealed that after a certain period of the reaction with tertiary butyl hydrogen peroxide, the phosphine ligands are removed to form nanoparticles of gold which matches with the induction period seen in the catalytic reaction. Density functional theory calculations show that the energies required to remove the ligands from the [Au6Ln]2+ increase significantly with successive removal steps, suggesting that the process does not occur at once but sequentially. The calculations also reveal that ligand removal is accompanied by dramatic re-arrangements in the topology of the cluster core.