The two new pincer azomethine-thiophene ligands (N,NE',N,NE')-N,N'-(thiophene-2,5-diylbis(methan-1-yl-1-ylidene))bis(naphathalen-2-ylmethanamine) (L1) and (E)-(4,6-dihydropyren-1-yl)-N-((5-((E)-(pyren-1-ylmethylimino)ethyl)thiophen-2-yl)methylene)methanamine (L2), their absorption, fluorescence and MALDI-TOF-MS spectroscopic studies are described. The two systems synthesised combine the emissive probes pyrene and naphthyl with the good chelating properties of a tridentate SN2 donor-set from a thiophene Schiff-base ligand. Both ligands gave analytically pure solid complexes with Ni(II) and Pd(II) salts. The bichromophoric pyrene derivative L2 presents two emission bands in solution, one corresponding to the monomer species and a red-shifted band attributable to the intramolecular excimer. Ni(II) and Pd(II) complexation affects the conformation in solution, increasing the monomer emission at the expense of the excimer band; this effect could be explored in metal ion sensing. System L1 behaves as a non emissive probe. In situ complexation reactions followed by MALDI-TOF-MS spectrometry without matrix support have also been performed; these experiments show that L1 could be a potential chemosensor for Ni(II) and Pd(11). (c) 2007 Elsevier B.V. All rights reserved.

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In 1999, the DEECA/INETI and the UBiA/FCT/UNL started a researching project on the partition of heavy metals during the combustion of stabilised sewage sludge (Biogran®), in a fluidised-bed reactor, and on the quality of the bottom ashes and fly ashes produced. This project was entitled Bimetal and was funded by the Portuguese Foundation for Science and Technology. In this paper only the results on the combustion of Biogran® are reported. The combustion process was performed in two different trials, in which different amounts of sewage sludge and time of combustion were applied. Several ash samples were collected from the bed (bottom ashes) and from two cyclones (first cyclone and second cyclone ashes). Sewage sludge, bed material (sand) and ash samples were submitted to the leaching process defined in the European leaching standard EN 12457-2. The eluates were characterized for a set of inorganic chemical species. The ecotoxicological levels of the eluates were determined for two biological indicators (Vibrio fischeri and Daphnia magna). The results were compared with the limit values of the CEMWE French Regulation. The samples were also ranked according to an index based on the chemical characterization of the eluates. It was observed an increase of the concentration of metals along the combustion system. The ashes trapped in the second cyclone, for both combustion trials, showed the highest concentration of metals in the eluates. Chemically, the ashes of the second cyclone were the most different ones. In the ecotoxicological point of view, the ecotoxicity levels of the eluates of the ashes, for both combustion cycles, did not follow the same pattern as observed for the chemical characterization. The ashes of the first cyclone showed the highest ecotoxicity levels for V. fischeri and D. magna. This difference on chemical and ecotoxicological results proves the need for performing both chemical and ecotoxicological characterizations of the sub-products of such type of thermal processes.

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All European countries are building structures to support collection and recovery of electric and electronic waste (WEEE). In this work, the study of a Portuguese recovery network is presented. A MILP model is developed in order to determine the best WEEE network structure as well as the associated optimal plan. Several different analyses are performed.

The emergence of multi-core processors is promoting the use of concurrency and multithreading. To raise the abstraction level of synchronization constructs is fundamental to ease the development of concurrent software, and Software Transactional Memory (STM) is a good approach towards such goal. However, execution environment issues such as the processor instruction set, caching policy, and memory model, may have strong influence upon the reliability of STM engines. This paper addresses the testing of STM engines aiming at improving their reliability and independence from execution environment. From our experience with porting and extending a specific STM engine, we report on some of the bugs found and synthesize some testing patterns that proved to be useful at testing STM engines.

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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Cork is a natural cellular and electrically insulating material which may have the capacity to store electric charges on or in its cell walls. Since natural cork has many voids, it is difficult to obtain uniform samples with the required dimensions. Therefore, a more uniform material, namely commercial cork agglomerate, usually used for floor and wall coverings, is employed in the present study. Since we know from our previous work that the electrical properties of cork are drastically affected by absorbed and adsorbed water, samples were protected by means of different polymer coatings (applied by spin-coating or soaking). Corona charging and isothermal charging and discharging currents were used to study the electrical trapping and detrapping capabilities of the samples. A comparison of the results leads to the conclusion that the most promising method for storing electric charges in this cellular material consists of drying and coating or soaking with a hydrophobic, electrically insulating polymer such as polytetraflouroethylene (Teflon (R)).

Cork is a natural cellular and electrically insulating material which may have the capacity to store electric charges on or in its cell walls. Since natural cork has many voids, it is difficult to obtain uniform samples with the required dimensions. Therefore, a more uniform material, namely commercial cork agglomerate, usually used for floor and wall coverings, is employed in the present study. Since we know from our previous work that the electrical properties of cork are drastically affected by absorbed and adsorbed water, samples were protected by means of different polymer coatings (applied by spin-coating or soaking). Corona charging and isothermal charging and discharging currents were used to study the electrical trapping and detrapping capabilities of the samples. A comparison of the results leads to the conclusion that the most promising method for storing electric charges in this cellular material consists of drying and coating or soaking with a hydrophobic, electrically insulating polymer such as polytetraflouroethylene (Teflon (R)). (c) 2007 Elsevier B.V. All rights reserved.

Cross-linked polyethylene (XLPE) is currently widely used as an insulating material for power cables due to its good physical properties, however when in use it undergoes an electrical ageing process. Its ability to trap electric charge can give rise to space charge accumulation in the bulk of the polymer and produce localised electric stresses that can lead to cable failure, since the electric field will be increased above the design stress in some regions favouring the initiation of degradation there. In this work the PEA (pulsed electro-acoustic) method was used to compare the charge dynamics in three samples (XLPE cable peelings) aged in different ways (electrothermally in the laboratory, field aged in service and thermally aged in the laboratory). Very different transient behavior was found depending upon the ageing history. This is related to differences in the migration of chemical species in the insulation layer, which are known to act as charge traps. All materials showed heterocharge peaks when the space charge reached stability, the magnitude of which seems to be related to the severity of the ageing. (c) 2007 Elsevier B.V. All rights reserved.

Cross-linked polyethylene (XLPE) is currently widely used as an insulating material for power cables due to its good physical properties, however when in use it undergoes an electrical ageing process. Its ability to trap electric charge can give rise to space charge accumulation in the bulk of the polymer and produce localised electric stresses that can lead to cable failure, since the electric field will be increased above the design stress in some regions favouring the initiation of degradation there. In this work the PEA (pulsed electro-acoustic) method was used to compare the charge dynamics in three samples (XLPE cable peelings) aged in different ways (electrothermally in the laboratory, field aged in service and thermally aged in the laboratory). Very different transient behavior was found depending upon the ageing history. This is related to differences in the migration of chemical species in the insulation layer, which are known to act as charge traps. All materials showed heterocharge peaks when the space charge reached stability, the magnitude of which seems to be related to the severity of the ageing.

The emergence of multi-core processors is promoting the use of concurrency and multithreading. To raise the abstraction level of synchronization constructs is fundamental to ease the development of concurrent software, and Software Transactional Memory (STM) is a good approach towards such goal. However, execution environment issues such as the processor instruction set, caching policy, and memory model, may have strong influence upon the reliability of STM engines. This paper addresses the testing of STM engines aiming at improving their reliability and independence from execution environment. From our experience with porting and extending a specific STM engine, we report on some of the bugs found and synthesize some testing patterns that proved to be useful at testing STM engines.

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