The objective of the paper is to contribute to the understanding of the knowledge economy in Portugal, presenting data and revealing specific characteristics of the Portuguese business R&D, using a framework of available tools such as international comparisons, technology intensity and sectors of the economy. This study concludes that Portuguese business R&D expenditures reveals strong elements of economic terciarization, and an important presence of foreign direct investment in knowledge intensive industries. Furthermore, the study revealed less significant determinants such as the existence of skill labour in pharmaceutical industries and the role of the state in some sectors (wealth and rail transportation).

The biaxial nematic phase was recently observed in different thermotropic liquid crystals, namely bent-core compounds, side-chain polymers, bent-core dimers, and organosiloxane tetrapodes. In this work, a series of experiments with a nematic organosiloxane tetrapode where nuclear magnetic resonance (NMR) spectra are collected while the sample is continuously rotating around an axis perpendicular to the magnetic field, are discussed in conjunction with the analysis of a deuterium NMR experiment on the same system reported earlier. The sample used is a mixture of a deuterated probe with the tetrapode. The mixture exhibits a nematic range between -40 degrees C and 37 degrees C. The results of the two independent, but complementary deuterium NMR experiments confirm the existence of a biaxial nematic phase for temperatures below 0 degrees C with high values of the asymmetry parameter at low temperatures. The presence of slow movements of the tetrapode mesogenic units in the low-temperature regime could also be detected through the analysis of the NMR spectra. Simulations indicate that these movements are mainly slow molecular reorientations of the mesogenic units associated with the presence of collective modes in the nematic phases of this compound. In the case of tetrapodes, recent investigations attribute the origin of biaxiality to the hindering of reorientations of the laterally attached mesogenic units which constitute the tetrapode. This study relates the molecular movements with the nematic biaxial ordering of the system.

We carry out a detailed deuterium nuclear magnetic resonance (NMR) study of local nematic ordering in polydomain nematic elastomers. This system has a close analogy to the random-anisotropy spin glass. We find that, in spite of the quadrupolar nematic symmetry in three dimensions requiring a first-order transition, the order parameter in the quenched "nematic glass" emerges via a continuous phase transition. In addition to this remarkable effect, by a careful analysis of the NMR line shape, we deduce that the local director fluctuations grow in a critical manner around the transition point. This could become an essential experimental evidence for the quenched disorder changing the order of discontinuous transition.

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In order to contribute to the understanding of the origin of biaxial nematic ordering in tetrapodes, a deuterium NMR study was performed on mixtures of monomers from organosiloxane tetrapodes with a deuterated nematic probe. Contrary to the tetrapode system previously studied, which exhibits a biaxial nematic phase, the results for monomers are compatible, within the experimental error, with uniaxial nematic ordering in the whole nematic range. The data are in agreement with the conjecture that the nematic biaxial behaviour is related to hindering of the mesogenic units' rotational movements, arising from interdigitation and connection to the central silicon core.

The multicopper enzyme nitrous oxide reductase (N2OR) catalyzes the final step of denitrification, the two-electron reduction of N2O to N-2. This enzyme is a functional homodimer containing two different multicopper sites: CuA and CuZ. CuA is a binuclear copper site that transfers electrons to the tetranuclear copper sulfide CuZ, the catalytic site. In this study, Pseudomonas nautica cytochrome C-552 was identified as the physiological electron donor. The kinetic data show differences when physiological and artificial electron donors are compared [cytochrome vs methylviologen (MV)]. In the presence of cytochrome c(552), the reaction rate is dependent on the ET reaction and independent of the N2O concentration. With MV, electron donation is faster than substrate reduction. From the study of cytochrome c(552) concentration dependence, we estimate the following kinetic parameters: K-mc512 = 50.2 +/- 9.0 mu M and V-maxc551 1.8 +/- 10.6 units/mg. The N2O concentration dependence indicates a K-mN2O of 14.0 +/- 2.9 mu M using MV as the electron donor. The pH effect on the kinetic parameters is different when MV or cytochrome c(552) is used as the electron donor (pK(a) = 6.6 or 8.3, respectively). The kinetic study also revealed the hydrophobic nature of the interaction, and direct electron transfer studies showed that CuA is the center that receives electrons from the physiological electron donor. The formation of the electron transfer complex was observed by H-1 NMR protein-protein titrations and was modeled with a molecular docking program (BiGGER). The proposed docked complexes corroborated the ET studies giving a large number of solutions in which cytochrome c(552) is placed near a hydrophobic patch located around the CuA center.

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Fractional central differences and derivatives are studied in this article. These are generalisations to real orders of the ordinary positive (even and odd) integer order differences and derivatives, and also coincide with the well known Riesz potentials. The coherence of these definitions is studied by applying the definitions to functions with Fourier transformable functions. Some properties of these derivatives are presented and particular cases studied.

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