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Ferrochelatase (EC 4.99.1.1) is the terminal enzyme of the haem biosynthetic pathway and catalyses iron chelation into the protoporphyrin IX ring. Glutamate-287 (E287) of murine mature ferrochelatase is a conserved residue in all known sequences of ferrochelatase, is present at the active site of the enzyme, as inferred from the Bacillus subtilis ferrochelatase three-dimensional structure, and is critical for enzyme activity. Substitution of E287 with either glutamine (Q) or alanine (A) yielded variants with lower enzymic activity than that of the wild-type ferrochelatase and with different absorption spectra from the wild-type enzyme. In contrast to the wild-type enzyme, the absorption spectra of the variants indicate that these enzymes, as purified, contain protoporphyrin IX. Identification and quantification of the porphyrin bound to the E287-directed variants indicate that approx. 80% of the total porphyrin corresponds to protoporphyrin IX. Significantly, rapid stopped-flow experiments of the E287A and E287Q Variants demonstrate that reaction with Zn2+ results in the formation of bound Zn-protoporphyrin IX, indicating that the endogenously bound protoporphyrin IX can be used as a substrate. Taken together, these findings suggest that the structural strain imposed by ferrochelatase on the porphyrin substrate as a critical step in the enzyme catalytic mechanism is also accomplished by the E287A and E287Q variants, but without the release of the product. Thus E287 in murine ferrochelatase appears to be critical For the catalytic process by controlling the release of the product.

In this paper we extend necessary conditions for Fredholmness of singular integral operators with piecewise continuous coefficients in rearrangement-invariant spaces [K98] to the weighted case \(X(\Gamma,w)\). These conditions are formulated in terms of indices \(\alpha(Q_tw)\) and \(\beta(Q_tw)\) of a submultiplicative function \(Q_tw\), which is associated with local properties of the space, of the curve, and of the weight at the point \(t\Gamma\). Using these results we obtain a lower estimate for the essential norm \(S\) of the Cauchy singular integral operator \(S\) in reflexive weighted rearrangement-invariant spaces \(X(\Gamma, w)\) over arbitrary Carleson curves \(\Gamma\):
\[
|S|\ge\cot(\pi\lambda_{\Gamma,w}/2)
\]
where \(\lambda_{\Gamma,w} :=inf_{t\in\Gamma} min\{\alpha(Q_tw), 1 - \beta(Q_tw)\}\). In some cases we give formulas for computation of \(\alpha(Q_tw)\) and \(\beta(Q_tw)\).

The displacement model of the hybrid-{T}refftz finite element formulation is applied to the solution of geometrically and physically linear static and dynamic problems. As the approximation bases solve locally the governing system of differential equations, the errors in the approximation affect only the implementation of the boundary conditions. Potential and elastostatic problems are used to illustrate the enforcement of the boundary conditions and the convergence of the solutions in energy, stresses and displacements, under both p- and h-refinement sequences and their insensitivity to mesh distortion, incompressibility and positioning of the coordinate system of the approximation basis. Also illustrated is the use of elements with arbitrary geometry and the efficiency that can be reached by including in the bases the solutions associated with dominant local effects, in particular those associated with singular stress fields. An adaptive p-refinement algorithm that exploits the naturally hierarchical nature of the approximation bases is presented and assessed. The formulation is generalised for elastodynamic analysis in the frequency domain of both bounded and unbounded domains, which are modelled either with absorbing boundary conditions or with semi-infinite elements that satisfy the Sommerfeld condition. The performance of the formulation is illustrated with tests on the convergence of the solutions in energy, stresses and displacements and on their insensitivity to mesh distortion, wave length and position of the absorbing boundary, for a wide spectrum of forcing frequencies and under both p- and h-refinement sequences.

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The increasing degree of inter-dependency and integration of economy at a global scale motivated the globalization of scientific and technological knowledge from manufacturing, to the marketing and the strategic management of companies that act as protagonists of these processes. Globalization of markets is inter-connected with intensive incorporation of knowledge in economy. In this sense the continuous evolution of the manufacturing industry structure for an increased high intensity technology elements, namely information and communication technologies, implies that these industrial sub-sectors are conditioning the global performance of economy, the productivity gains and as a consequence the levels of economical and employment growth. This study on “R&D, Innovation and Employment Creation” for the Portuguese Observatory of Employment and Vocational Training (IEFP-MQE) is updating information on the articulation between Job creation, innovation, technology, and R&D. A diagnosis of the state of national S&T research and of processes of technological and organizational innovation was made, as well of the interfacing structures between the knowledge sector and the economical activities. Were made 12 case studies at companies with some innovation activities, interviews to unionists and to Professional associations, and public offices. Was made also a survey to a selected sample of technological infrastructures.

The innovation in the employment behaviour is particularly clear in what concerns the sector composition of the employment changes: the persistent decrease of the industrial employment (even if within a framework of some recovery of the industrial product), a slight expansion in the employment on the tertiary sector, and an important growth of the employment in the construction and public works activities. We can identify then a considerable sector mutation concerning the industrial and the services sectors but also a growth of the atypical forms of employment. Portugal continues not being able to respond to the labour market needs (improvement in the education sector is critical to the catch-up process). The Portuguese cases studied point out to organisational changes supported by ICT, but not determined/induced by it. For most of the changes that were recently developed, ICT had an important role. We didn’t found explicit technological determinism in the relation between ICT and social exclusion.

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{Nitrite reductase from the sulfate-reducing bacterium Desulfovibrio desulfuricans ATCC 27774 is a multihaem (type c) membrane-bound enzyme that catalyzes the dissimilatory conversion of nitrite to ammonia. Crystals of the oxidized form of this enzyme were obtained using PEG and CaCl2 as precipitants in the presence of 3-(decylmethylammonium)propane-1-sulfonate and belong to the space group P2(1)2(1)2(1), With unit-cell parameters a = 78.94

The socio-economic subsystem encompassing fisheries may be defined as including not only the harvesting sector but also several related activities occurring both upstream (shipbuilding, gear manufacture) and downstream (processing, distribution and trade). But these closely interrelated economic activities can also be set within a much broader system which would include the ecological, institutional and political influences which frame economic behaviour. The value of this broader conceptualisation is that it treats fisheries not as an isolated and independent economic activity but as part of a more holistic and complex system. This broader perspective is of particular significance when attempting to examine the concept of regional dependence. The socio-economic subsystem for fisheries is dominated by small and medium sized enterprises (SMEs). And Peniche emerges as one of Portugal’s most important fishing ports whether measured in terms of the volume of landings or the total numbers of fishermen. It also has one of the highest levels of fisheries dependence of all coastal municipalities in Portugal with over 20% of its workforce currently engaged in fisheries related employment, faces a daunting and uncertain future. The social fabric of fisheries dependent communities also suffers serious damage; once again, the technocratic approach to management has no solutions to offer. It is essential, therefore, to turn away from the existing approach and to develop instead new forms of intervention; in short, to provide a new vision. This implies change not only to the policy process but also in the attitudes of the social actors and in the preoccupations of fisheries related research. An integrated approach is required based on participative action and the development of an integrated information network.

In this paper for a public debate promoted by the Portuguese President of Republic in 2000, we start from the basic definitions of information society and discuss the main measures proposed as targets in the firld of work and employment. Structural changes are analysed related with the economical and social dimensions of the information society, especially those related to the work organisation, education and training, and the labour markets. Finally recommendations are made on the topics of innovation, employment and development of information society.

The self-assembly of Ag[BF(4)] with trans-azobenzene in dichloromethane yields a new coordination polymer ([Ag(mu -trans-azobenzene)H(2)O] [BF(4)])(n) which was characterized by X-ray single crystal diffraction. The crystal consists of 1-D zigzag cationic chains made up from [Ag(H(2)O)](+) units linked by trans-azobenzene bridges and BF(4)(-) anions. Hydrogen bonding interactions between the chains and BF(4)(-) anions occur via intermolecular C-H . . .F and O-H . . .F contacts, and the crystal displays a 2-D supramolecular structure.

The reaction between [Cu(NCMe)(4)][PF6] and 1,1'-bis-(diphenylphosphino)-ferrocene (dppf) in several ratios, solvents, and conditions led to the synthesis and structural characterization of the Cu(I) complexes [Cu(dppf)(Odppf)] [PF6] (1), [(dppf)Cu(mu -dppf)Cu(dppf)][PF6](2) (2), and [(dppf)Cu(mu -Cl)(2)Cu(dppf)] (3). Although 1 and the cation in 2 were known, the first was structurally characterized for the first time, exhibiting a significant asymmetry in the coordination sphere of Cu(I)) owing to the presence of oxygen. In 2, the PF6- anion led to an interesting crystal packing with large open channels containing water. Finally, DFT calculations on a model of 3 showed that its HOMO exhibits, besides Fe, a significant Cu and Cl character, which is reflected in its electrochemical properties.

This paper summarises the methodological approach and main results of the MARHE project (Employment and Human Resources in the Fisheries Socio-Economic System). This project had as its main aim the search for alternative futures for the fisheries sector in Portugal, with particular attention being paid to the human resources situation and the working and living conditions of the fisheries-dependent populations in the coastal areas. This is a particularly interesting case, since fisheries were once an important activity and they are now in deep recession, even though it is generally recognised that the future utilisation of maritime resources offer an immense potential. As part of the research, a Delphi exercise was implemented involving in two successive stages some of the leading actors and experts dealing with the sector in Portugal. Other initiatives were held in the context of the MARHE project providing direct and indirect inputs to the scenarios and recommendations that were put forward in the sequence of the Delphi exercise. Overall the activities described in the paper contributed to the mobilisation of major actors and to discussions that may have practical implication for the future of the sector, if certain conditions are now met in the follow up to the project.

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