Various S = 3/2 EPR signals elicited from wild-type and variant Azotobacter vinelandii nitrogenase MoFe proteins appear to reflect different conformations assumed by the FeMo-cofactor with different protonation states. To determine whether these presumed changes in protonation and conformation reflect catalytic capacity, the responses (particularly to changes in electron flux) of the alpha H195Q, alpha H195N, and alpha Q191 K variant MoFe proteins (where His at position 195 in the alpha subunit is replaced by Gln/Asn or Gln at position alpha-191 by Lys), which have strikingly different substrate-reduction properties, were studied by stopped-flow or rapid-freeze techniques. Rapid-freeze EPR at low electron flux (at 3-fold molar excess of wild-type Fe protein) elicited two transient FeMo-cofactor-based EPR signals within 1 s of initiating turnover under N-2 with the alpha H195Q and alpha H195N variants, but not with the alpha Q191K variant. No EPR signals attributable to P cluster oxidation were observed for any of the variants under these conditions. Furthermore, during turnover at low electron flux with the wild-type, alpha H195Q or alpha H195N MoFe protein, the longer-time 430-nm absorbance increase, which likely reflects P cluster oxidation, was also not observed (by stopped-flow spectrophotometry); it did, however, occur for all three MoFe proteins under higher electron flux. No 430-nm absorbance increase occurred with the alpha Q191K variant, not even at higher electron flux. This putative lack of involvement of the P cluster in electron transfer at low electron flux was confirmed by rapid-freeze Fe-57 Mossbauer spectroscopy, which clearly showed FeMo-factor reduction without P cluster oxidation. Because the wild-type, alpha H195Q and alpha H195N MoFe proteins can bind N-2, but alpha Q195K cannot, these results suggest that P cluster oxidation occurs only under high electron flux as required for N-2 reduction. (C) 2007 Elsevier Inc. All rights reserved.

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In this work (Al,Ti) and (Al,Ti,N) films with composition gradient in depth starting either with pure Al or pure Ti were deposited on Si, glass and Au at room temperature in a DC magnetron discharge without bias. The plasma parameters, for both custom made cathodes, were determined and the process was real-time controlled to obtain in the plasma the necessary deposition changes in relative metal abundances to get the desired depth profile composition on the films. In this work the process was designed to get a constant gradient for the composition depth profile. The morphology of the films was analysed by SEM while the composition gradients were measured by SIMS, XPS and RBS, confirming preset nominal depth composition profile of the films. To obtain (Al,Ti,N) thin films with gradient depth composition, N2 must be supplied to the discharges. The plasma behaviour is modified in the presence of N2 and the influence on the film characteristics is studied using the same techniques referred above. The (Al,Ti) and (Al,Ti,N) film properties are compared. We succeed in validating the coating technique opening new application possibilities.

A requirement of many surface science studies is the capability to alter a sample temperature in a controlled mode. Sample preparation procedures such as heating or cooling ramps, high temperature spikes, fast annealing, or simply maintaining a sample at a very high, or very low, temperature are common. To address these issues, we describe the design and the construction of a multipurpose sample holder. Key points of this design are operation in an extended temperature range from liquid nitrogen (LN(2)) temperature to approximately 1300 K, temperature control during heating and cooling, low thermal inertia with rates up to 50 K s(-1) (heating) and -20 K s(-1) (cooling), and small heated volume to minimize background problems in thermal desorption spectroscopy (TDS) spectra. With this design the sample can be flash heated from LN(2) temperature to 1300 K and cooled down again in less than 100 s. This sample holder was mounted and tested in a multitechnique apparatus and adds a large number of sample preparation procedures as well as TDS to the list of already available surface analysis techniques.

To achieve highly accurate controlled depositions a specially designed vapour source, for metals with low to medium melting temperature, was developed. A quartz crystal microbalance is fitted inside the evaporation chamber to provide real-time rate and thickness monitoring. A carefully planned geometry allows maintaining a small deposition area centred on the sample without compromising flow rate measurements. Dosing rates as low as 0.02 ML/min are easily achieved, therefore providing true sub-monolayer control. This source was tested and calibrated for Ag and is being successfully used to study the growth of Ag clusters on TiO2.

We describe a detailed study of scanning electron microscopy (SEM) combined with energy dispersive spectroscopy (EDS) analysis to study composition and structure of 500nm thick polycrystalline GaN samples. The films have been deposited by cyclic-pulsed laser deposition (cyclic-PLD) with a Nd:YAG nanosecond pulsed laser at 1064nm. SEM pictures of the GaN layers revealed a structure composed of grains with typical dimensions of 200nm. Coalescence of the grains was more evident for a 1 mu m thick sample. EDS mapping of the GaN layer was performed for Ga, N, O, and Al and could be related with the corresponding SEM scan. Both EDS and XPS composition analyses pointed to a Ga rich (or N deficient) GaN layer. (c) 2007 Elsevier Ltd. All rights reserved.

We report the 98% assignment of the apo-form of an orange protein, containing a novel Mo-Cu cluster isolated from Desulfovibrio gigas. This protein presents a region where backbone amide protons exchange fast with bulk solvent becoming undetectable. These residues were assigned using C-13-detection experiments.

The possibility of preparation of ophthalmic drug delivery systems using compressed anti-solvent technology was evaluated. Eudragit RS 100 and RL 100 were used as drug carriers, acetazolamide was the model drug processed. Compressed anti-solvent experiments were carried out as a semi-continuous or a batch operation from a liquid solution of polymer(s) + solute dissolved in acetone. Both techniques allowed the recovery of composite particles, but the semi-continuous operation yielded smaller and less aggregated populations than the batch operation. The release behaviour of acetazolamide from the prepared microparticles was studied and most products exhibited a slower release than the single drug. Moreover, the release could be controlled to some extent by varying the ratio of the two Eudragit used in the formulation and by selecting one or the other anti-solvent technique. Simple diffusion models satisfactorily described the release profiles. Composites specifically produced by semi-continuous technique have a drug release rate controlled by a diffusion mechanism, whereas for composites produced by the batch operation, the polymer swelling also contributes to the overall transport mechanism. © 2006 Elsevier B.V. All rights reserved.

The possibility of preparation of ophthalmic drug delivery systems using compressed anti-solvent technology was evaluated. Eudragit RS 100 and RL 100 were used as drug carriers, acetazolamide was the model drug processed. Compressed anti-solvent experiments were carried out as a semi-continuous or a batch operation from a liquid solution of polymer(s) + solute dissolved in acetone. Both techniques allowed the recovery of composite particles, but the semi-continuous operation yielded smaller and less aggregated populations than the batch operation. The release behaviour of acetazolamide from the prepared microparticles was studied and most products exhibited a slower release than the single drug. Moreover, the release could be controlled to some extent by varying the ratio of the two Eudragit used in the formulation and by selecting one or the other anti-solvent technique. Simple diffusion models satisfactorily described the release profiles. Composites specifically produced by semi-continuous technique have a drug release rate controlled by a diffusion mechanism, whereas for composites produced by the batch operation, the polymer swelling also contributes to the overall transport mechanism. © 2006 Elsevier B.V. All rights reserved.

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Carbon dioxide solubility in a natural biodegradable polymer, namely poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and the diffusion coefficients are reported. Equilibrium solubility of dense carbon dioxide in PHBV was studied by a gravimetric method in a temperature range from 308 to 313 K and a pressure range from 10.0 to 15.0 MPa. The copolymer presented Fickian behavior and Fick's diffusion model was applied to determine the amount of carbon dioxide present in the samples after a predermined exposure time as well as the diffusion coefficients. Diffusion coefficients for the sorption under supercritical (sc) conditions and desorption at ambient conditions were determined and compared. To evaluate the influence of the HV content in the amount of maximum sorption degree of the polymer, different samples of PHBV copolymers were tested and the sorption curves are here presented. © 2006 Elsevier B.V. All rights reserved.

The micronization of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) from organic solutions using supercritical antisolvent (SAS) technique has been successfully achieved. SAS experiments were carried out at different operational conditions and microspheres with mean diameters ranging from 3 to 9 $μ$m were obtained. The effect of CO2 and liquid flow, temperature and pressure on particle size and particle size distribution was evaluated. The microspheres were precipitated from a dichloromethane (DCM) solution. The best process conditions for this mixture were, according to our study, 40 °C, 100 bar, 1 mL min-1 liquid flow and 10 L min-1 carbon dioxide flow. Experiments with polymers containing different HV percentages were carried out. The powders obtained became more spherical as the HV content decreased. © 2006 Elsevier B.V. All rights reserved.

Supercritical fluid impregnation was tested to prepare a new ophthalmic drug delivery device. Poly(methylmethacrylate-co-ethylhexylacrylate-co-ethyleneglycoldimethacr ylate), P(MMA-EHA-EGDMA) has been proposed by Mariz [M. Mariz, Preparação de uma lente intra-ocular dotada de um sistema de libertação controlada de fármaco, Master Thesis, Universidade de Coimbra, 1999] as a promising matrix to be used for intraocular delivery of anti-inflammatory drugs used in eye surgery. This matrix was successfully impregnated with flurbiprofen, a non-steroidal anti-inflammatory agent. The success of the impregnation was evaluated by scanning electron microscopy (SEM) analysis and also by in vitro drug release studies. The effect of some operating parameters was evaluated, namely, pressure and contact time. The operating pressure will influence both the solubility of the drug in the supercritical fluid but also the sorption degree of the polymeric matrix in the presence of carbon dioxide. The solubility of the drug in carbon dioxide and the sorption degree are reported in previous studies. A comparison between the batch and the semi-continuous impregnation process is also presented. The supercritical fluid impregnation proved to be feasible for the preparation of a new ophthalmic drug delivery system. The drug release profiles suggest that the drug can be released up to three months, which is a major advantage for the prevention of the inflammatory response after ophthalmic surgery. © 2007 Elsevier B.V. All rights reserved.

{We prove the existence of weak solutions for the forward and backward statistical transport equations associated with the 2D Euler equations. Such solutions can be interpreted, respectively, as a statistical Lagrangian and a statistical Eulerian description of the motion of the fluid.}

We extend a result of Bottcher and Silbermann on higher order asymptotics of determinants of block Toeplitz matrices with symbols in Wiener algebras with power weights to the case of Wiener algebras with general weights satisfying natural submultiplicativity, monotonicity, and regularity conditions.

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If indicators of international competitivity of the Portuguese industry reveal very strong weaknesses in the field of education and vocational training, the achievement of a solution is not based only (and should not!) in a decisive increase of investment and support in the education and training system. It seem not logical to think in that way, once normally when one tries to solve a problem that is done in the context of that same problem. Eventually there are other strategies. Which are, then, the fields where is necessary to orient the investiment to improve an industrial competitivity? To try to answer this question, we analise one of the sectors that have contributed the most for an improvement of the Portuguese economical performance, and for a true innovative process as in terms of industrial product, or in terms of manufacturing and distribution processes. Is the automotive sector where that happens, taken in its two most important sub-sectors: the one of automobile manufacturing and assembly, and the one of components manufacturing.

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No abstract is available for this item.

The foresight and scenario building methods can be an interesting reference for social sciences, especially in terms of innovative methods for labour process analysis. A scenario – as a central concept for the prospective analysis – can be considered as a rich and detailed portrait of a plausible future world. It can be a useful tool for policy-makers to grasp problems clearly and comprehensively, and to better pinpoint challenges as well as opportunities in an overall framework. The features of the foresight methods are being used in some labour policy making experiences. Case studies developed in Portugal will be presented, and some conclusions will be drawn in order to organise a set of principles for foresight analysis applied to the European project WORKS on the work organisation re-structuring in the knowledge society, and on the work design methods for new management structures of virtual organisations.

On 19 and 20 October 2006, the Research Centre on Enterprise and Work Organisation (IET) organised the first international conference on “Foresight Studies on Work in the Knowledge Society”. It took place at the auditorium of the new Library of FCT-UNL and had the support of the research project “CodeWork@VO” (financed by FCT-MCTES and co-ordinated by INESC, Porto). The conference related to the European research project “Work Organisation and Restructuring in the Knowledge Society” (WORKS), which is financed by the European Commission. The main objective of the conference was to analyse and discuss research findings on the trends of work structures in the knowledge society, and to debate on new work organisation models and new forms of work supported by ICT.

Algunos de los fenómenos donde el concepto de “globalización” es aplicado incluyen la internacionalización de los mercados, la globalización de la cultura, el dominio político hegemónico del mundo por algunos estados poderosos, o grupos de estados, el poder creciente de organismos supranacionales, y el desarrollo de una división global de trabajo. De acuerdo con Radice, la globalización é generalmente definida como “un proceso a través de lo cual una proporción creciente de transacciones económicas, sociales e culturales ocurre directamente o indirectamente entre partners de países distintos” (Radice, 2004: 154). Un ponto de partida para entender la división global del trabajo debe ser la investigación de los modos como las empresas se reestructuran, una vez que son los actores-llave en la decisión sobre que trabajo debe ser encontrado y donde. Las “cadenas de valor” descriven cada etapa en el proceso productivo de un producto o un servicio final. La palabra “valor” en la frase “cadena de valor” dice respecto al valor añadido. Cada etapa en la cadena de valor implica recibir inputs, procesarlos, y entonces pasarlos a la unidad siguiente en la cadena, con el valor que está sendo adicionado no proceso. As unidades separadas da cadena de valor pueden estar dentro da misma empresa (in-house) o en distintas empresas (outsourced). Similarmente pueden estar en un mismo local, o en otra localización. La normalización de muchos procesos del negocio, combinada con la digitalización da información y el desarrollo de redes de telecomunicaciones de elevada capacidad ha tornado posible el trabajo tele-mediado, pudiendo este ser externalizado y/o re-localizado, conduciendo à introducción de una división de trabajo internacional no trabajo de procesamiento de información. Esta comunicación presentará algunos resultados derivados do proyecto europeo WORKS, donde son estudiados casos portugueses de empresas que justamente se integran en

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