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.

Sensitivity tests to reductive gases such as methane, hydrogen and ethane were performed on zinc oxide (ZnO) thin films. The highest value of sensitivity was obtained for the film with a high electrical resistivity and a low thickness. The variation of the operating temperature of the film leads to a significant change in the sensitivity of the sensor with an ideal operating temperature dependence of the gas used. The sensitivity of the ZnO thin films changes linear with the increase of the gas concentration. However these films seem to be more appropriated for the detection of hydrogen following by methane and than for ethane since the value of sensitivity obtained are higher and its variation with the gas concentration more pronounced.

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Highly textured transparent conducting ZnO:Al thin films have been prepared by r.f. magnetron sputtering. The films were deposited on polyester (Mylar type D, 100 μm thickness) and glass substrates at room temperature. Surface stylus profiling, X-ray diffraction, scanning electron microscopy, transmission electron microscope and Hall effect measurements as a function of temperature, using the van der Pauw technique have characterized the films. The samples are polycrystalline with a hexagonal wurtzite structure and a strong crystallographic c-axis orientation (002) perpendicular to the substrate surface (columnar structure). The ZnO:Al thin films with a resistivity as low as 3.6×10-2 Ωcm have been obtained, as deposited. © 2001 Materials Research Society.

Highly textured transparent conducting ZnO:Al thin films have been prepared by r.f. magnetron sputtering. The films were deposited on polyester (Mylar type D, 100 μm thickness) and glass substrates at room temperature. Surface stylus profiling, X-ray diffraction, scanning electron microscopy, transmission electron microscope and Hall effect measurements as a function of temperature have been used to characterize the produced films. The samples are polycrystalline with a hexagonal wurtzke structure and a strong crystallographic c-axis orientation (002) perpendicular to the substrate surface (columnar structure). The ZnO:Al thin films with a resistivity as low 3.6×10-2 Ωcm have been obtained, as deposited.

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The performances of silicon carbide position sensitive detectors in relation to position color selection applications were presented. The devices were deposited on glass substrates coated with a transparent conductive oxide layer based on indium tin oxide film (ITO). On top of the ITP layer a pin structure produced by plasma enhanced chemical vapor deposition technique was deposited. The set of data achieved indicated that the undoped silicon carbide layers presented a low density of states, which explained high dark conductivity values obtained and the type of performances recorded on the PSD devices produced.

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Aluminium doped zinc oxide thin films (ZnO:Al) have been deposited on polyester (Mylar type D, 100 μm thickness) substrates at room temperature by r.f. magnetron sputtering. The structural, morphological, optical and electrical properties of the deposited films have been studied. The samples are polycrystalline with a hexagonal wurtzite structure and a strong crystallographic c-axis orientation (002) perpendicular to the substrate surface. The ZnO:Al thin films with 85% transmittance in the visible and infra-red region and a resistivity as low as 3.6×102 Ωcm have been obtained, as deposited. The obtained results are comparable to those ones obtained on glass substrates, opening a new field of low cost, light weight, small volume, flexible and unbreakable large area optoelectronic devices. © 2001 Materials Research Society.

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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.