Abstract.  The concept of intermediate band solar cell (IBSC) is, apparently, simple to grasp. However, since the idea was proposed, our understanding has improved and some concepts can now be explained more clearly than when the concept was initially introduced. Clarifying these concepts is important, even if they are well known for the advanced researcher, so that research efforts can be driven in the right direction from the start. The six pieces of this work are: Does a miniband need to be formed when the IBSC is implemented with quantum dots? What are the problems for each of the main practical approaches that exist today? What are the simplest experimental techniques to demonstrate whether an IBSC is working as such or not? What is the issue with the absorption coefficient overlap and the Mott's transition? What would the best system be, if any?

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One of the major scientific challenges that tissue engineering and regenerative medicine (TERM) faces to move from benchtop to bedside regards biomaterials development, despite the latest advances in polymer processing technologies. A variety of scaffolds processing techniques have been developed and include solvent casting and particles leaching, compression molding and particle leaching, thermally induced phase separation, rapid prototyping, among others. Supercritical fluids appear as an interesting alternative to the conventional methods for processing biopolymers as they do not require the use of large amounts of organic solvents and the processes can be conducted at mild temperatures. However, this processing technique has only recently started to receive more attention from researchers. Different processing methods based on the use of supercritical carbon dioxide have been proposed for the creation of novel architectures based on natural and synthetic polymers and these will be unleashed in this paper. © 2013 Elsevier B.V. All rights reserved.

One of the major scientific challenges that tissue engineering and regenerative medicine (TERM) faces to move from benchtop to bedside regards biomaterials development, despite the latest advances in polymer processing technologies. A variety of scaffolds processing techniques have been developed and include solvent casting and particles leaching, compression molding and particle leaching, thermally induced phase separation, rapid prototyping, among others. Supercritical fluids appear as an interesting alternative to the conventional methods for processing biopolymers as they do not require the use of large amounts of organic solvents and the processes can be conducted at mild temperatures. However, this processing technique has only recently started to receive more attention from researchers. Different processing methods based on the use of supercritical carbon dioxide have been proposed for the creation of novel architectures based on natural and synthetic polymers and these will be unleashed in this paper. © 2013 Elsevier B.V. All rights reserved.

{Two synthetic strategies of tetrathiomolybdate-metal clusters with the potential to be used as NMR structural probes for the location of the metal cofactor in the orange protein (ORP) are described. The first strategy is based on the substitution reaction in which small organic ligands bind directly to the metal centre in a molybdenumcopper hetero-dinuclear cluster. Interaction between {[}PPh4]2{[}MoS4CuCl] and either aliphatic {[}beta-mercaptoethanol (b-me)] or aromatic {[}o-aminobenzenethiol (abt)] thiols in the presence of a strong base resulted in the formation of {[}Ph4P]2{[}S2MoS2Cu(b-me)] (1a) and {[}Et4N]2{[}S2MoS2Cu(abt)]center dot H2O center dot 0.25DMF (1b), which can be used to obtain intermolecular NOEs. The compound 1a readily hydrolyzed to {[}Ph4P]2{[}OSMoS2Cu(b-me)] (1ahydro) in contact with a protic solvent. The second strategy consisted of the incorporation of cadmium into tetrathiomolybdate ({[}MoS4]2), which gives rise to the trinuclear cluster compound {[}PPh4]2{[}(MoS4)2Cd] (2). All clusters were characterized spectroscopically and their structure determined by X-ray diffraction. The NMR spectroscopic data are consistent with the formation of a complex with a 1:1 ratio of \{MoS4Cu\} and thiol. The 113Cd NMR chemical shift of compound 2 is consistent with the cadmium having a tetrahedral geometry and coordinated by four sulfur ligands. The tetraphenylphosphonium cation in compound 1a was replaced by a tetramethylammonium countercation originating in the water-soluble compound {[}Me4N-1a]. Solubility in aqueous buffers is a requirement for incorporating this cluster into apo-ORP. These compounds will be used to identify the exact location of the ORP heterometallic cluster using NMR methodologies.}

{Reaction of {[}Co(eta(5)-C5H5)(CO)(2)], 1, with 1,1'-bis(diphenylphosphino)ferrocene (dppf) yields the new trinuclear complex {[}Co(eta(5)-C5H5)(CO)](2)(mu-dppf), 2, which was structurally characterised by single crystal X-ray diffraction and showed two Co(eta(5)-C5H5)(CO) moieties covalently linked by a dppf bridge. Electrochemical studies in dichloromethane revealed that both Co(I) and Fe(II) in the precursors were oxidized to Co(II)/Co(III) and Fe(III), respectively. On the other hand, in 2 the two first oxidation waves were assigned to Co, the Fe(II) centre requiring a higher potential than in free dppf. DFT calculations showed that the HOMOs of 2 were localised in the Co fragments, owing to the destabilisation of the Co(eta(5)-C5H5)(CO) orbitals after binding dppf. (C) 2012 Elsevier B.V. All rights reserved.}

Two synthetic strategies of tetrathiomolybdate-metal clusters with the potential to be used as NMR structural probes for the location of the metal cofactor in the orange protein (ORP) are described. The first strategy is based on the substitution reaction in which small organic ligands bind directly to the metal centre in a molybdenumcopper hetero-dinuclear cluster. Interaction between [PPh4]2[MoS4CuCl] and either aliphatic [beta-mercaptoethanol (b-me)] or aromatic [o-aminobenzenethiol (abt)] thiols in the presence of a strong base resulted in the formation of [Ph4P]2[S2MoS2Cu(b-me)] (1a) and [Et4N]2[S2MoS2Cu(abt)]center dot H2O center dot 0.25DMF (1b), which can be used to obtain intermolecular NOEs. The compound 1a readily hydrolyzed to [Ph4P]2[OSMoS2Cu(b-me)] (1ahydro) in contact with a protic solvent. The second strategy consisted of the incorporation of cadmium into tetrathiomolybdate ([MoS4]2), which gives rise to the trinuclear cluster compound [PPh4]2[(MoS4)2Cd] (2). All clusters were characterized spectroscopically and their structure determined by X-ray diffraction. The NMR spectroscopic data are consistent with the formation of a complex with a 1:1 ratio of {MoS4Cu} and thiol. The 113Cd NMR chemical shift of compound 2 is consistent with the cadmium having a tetrahedral geometry and coordinated by four sulfur ligands. The tetraphenylphosphonium cation in compound 1a was replaced by a tetramethylammonium countercation originating in the water-soluble compound [Me4N-1a]. Solubility in aqueous buffers is a requirement for incorporating this cluster into apo-ORP. These compounds will be used to identify the exact location of the ORP heterometallic cluster using NMR methodologies.

The short Cu2+-S(Met) bond in pseudoazurin (PAz) results in the presence of two relatively intense S-p(pi) and S-p(sigma) charge transfer (CT) transitions. This has enabled resonance Raman (rR) data to be obtained for each excited state. The rR data show very different intensity distribution patterns for the vibrations in the 300-500 cm(-1) region. Time-dependent density functional theory (TDDFT) calculations have been used to determine that the change in intensity distribution between the S-p(pi) and S-p(sigma) excited states reflects the differential enhancement of S(Cys) backbone modes with Cu-S(Cys)-C-beta out-of-plane (oop) and in-plane (ip) bend character in their respective potential energy distributions (PEDs). The rR excited state distortions have been related to ground state reorganization energies (lambda s) and predict that, in addition to M-L stretches, the Cu-S(Cys)-C-beta oop bend needs to be considered. DFT calculations predict a large distortion in the Cu-S(Cys)-C-beta oop bending coordinate upon reduction of a blue copper (BC) site; however, this distortion is not present in the X-ray crystal structures of reduced BC sites. The lack of Cu-S(Cys)-C-beta oop distortion upon reduction corresponds to a previously unconsidered constraint on the thiolate ligand orientation in the reduced state of BC proteins and can be considered as a contribution to the entatic/rack nature of BC sites. (C) 2012 Elsevier Inc. All rights reserved.

Theoretical transition energies and probabilities for He-, Li and Be-like Praseodymium ions are calcu- lated in the framework of the multi-configuration Dirac-Fock method (MCDF), including QED corrections. These calculated values are compared to recent experimental data obtained in the Livermore SuperEBIT electron beam ion trap facility [1].

Theoretical transition energies and probabilities for He-, Li and Be-like Praseodymium ions are calcu- lated in the framework of the multi-configuration Dirac-Fock method (MCDF), including QED corrections. These calculated values are compared to recent experimental data obtained in the Livermore SuperEBIT electron beam ion trap facility [1].

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Nitrous oxide reductase (N(2)OR) catalyses the final step of the denitrification pathway-the reduction of nitrous oxide to nitrogen. The catalytic centre (CuZ) is a unique tetranuclear copper centre bridged by inorganic sulphur in a tetrahedron arrangement that can have different oxidation states. Previously, Marinobacter hydrocarbonoclasticus N(2)OR was isolated with the CuZ centre as CuZ*, in the [1Cu(2+) : 3Cu(+)] redox state, which is redox inert and requires prolonged incubation under reductive conditions to be activated. In this work, we report, for the first time, the isolation of N(2)OR from M. hydrocarbonoclasticus in the 'purple' form, in which the CuZ centre is in the oxidized [2Cu(2+) : 2Cu(+)] redox state and is redox active. This form of the enzyme was isolated in the presence of oxygen from a microaerobic culture in the presence of nitrate and also from a strictly anaerobic culture. The purple form of the enzyme was biochemically characterized and was shown to be a redox active species, although it is still catalytically non-competent, as its specific activity is lower than that of the activated fully reduced enzyme and comparable with that of the enzyme with the CuZ centre in either the [1Cu(2+) : 3Cu(+)] redox state or in the redox inactive CuZ* state.

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The objective of the paper is to help to understand recent changes in the structure of R&D activities, by analyzing data on the expenditure of the business sector in research and development (R&D). The results are framed in an international context, through comparison with indicators from the most developed countries, divided by technological intensity and economic activity. The study reveals that the indicators of Portuguese R&D expenditure in the business sector are closely linked both to fiscal policy and to high foreign direct investment in knowledge-intensive industries. It also links these indicators to phenomena such as the abundance of skilled labor in pharmaceutical industries and the government intervention in some sectors of the economy (namely health and rail transportation).

Electrical Protective Devices are key elements in the electrical network. Their purpose is to perform fault detection in electric power systems, by analysing power system voltages and currents. In order to achieve a more centralized control, protective devices can be connected using Web Services through a Service-Oriented Architecture (SOA) approach. This work targets planning and specification of a mapping between Abstract Communication Service Interface (ACSI) Reporting and Device Profile for Web Services (DPWS) Eventing to achieve a better protective electrical devices control, obtaining an event based alert software system, replacing conventional polling-based systems.