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.

Purpose – The purpose of this paper is to explore the deployment of RFID technology in fashion supply chain management (FSCM). It highlights the contribution of RFID to FSCM, supporting faster logistics activities, with greater products quality, cheaper and with more responsiveness, improving customer satisfaction. Design/methodology/approach – An inductive theory building approach is used to develop a conceptual model for RFID deployment in the {FSCM} context. Secondary data analysis from a sample of six companies supports the identification and discussion of the real advantages, disadvantages and barriers felt by companies in a fashion supply chain when {RFID} technology is introduced. Findings – The logistics activities in the fashion supply chain where {RFID} technology is most widely deployed are: shipping operations, tracking of raw materials, semi-finished components and finished garments, collecting finished goods, handling processes, tracking containers, tracking products from factory to store, receiving operations, monitoring, and sorting of merchandise. In most cases, the tagging operation is performed at some stage in the production process and tag reading occurs at distribution centres or at stores. The main barrier identified to the deployment of {RFID} is the problem of interoperability. The costs associated with the technology are the main disadvantage pointed out by the companies. Practical implications – A conceptual framework is proposed exploring the {RFID} advantages and disadvantages across the fashion supply chain, the main barriers to its introduction and the fashion supply chain logistics activities in which {RFID} could be found. This represents an important contribution to companies in this industry to become more aware of {RFID.} Also, new companies which are thinking of introducing this technology could overcome its barriers easily, improving its advantages and minimizing its disadvantages. Originality/value – This paper explores the deployment of {RFID} in the fashion supply chain from the perspective of technology users.

The concentration of lead in liver and kidneys of Wistar rats, fed with lead since fetal period in relation to their age and to a control group, was determined. A group of rats was exposed to lead acetate (n=30) in drinking water and the other group was exposed to normal water (n=20). Samples were collected from rats aging between 1 and 11 months and were analyzed by Energy Dispersive X-ray Fluorescence (EDXRF) without any chemical preparation. The EDXRF results were assessed by the PIXE (Proton Induced X-ray Emission) technique. The formaldehyde used to preserve the samples was also analyzed by ETAAS (Electro-Thermal Atomic Absorption Spectrometry) in order to verify if there was any loss of lead from the samples to the formaldehyde. We found that the loss was not significant (<2%). Concerning the mean values of the lead concentration measured in the contaminated soft tissues, in liver they range from 6 to 22μgg(-1), and in kidneys from 44 to 79μgg(-1). The control rats show, in general, values below the EDXRF detection limit (2μgg(-1)). The ratio kidney/liver ranges from 2 to 10 and is strongly positively correlated with the age of the animals. A Spearman correlation matrix to investigate the correlation between elemental concentrations and the dependence of these concentrations with age showed that there is a strong positive correlation with age for lead in the liver but not in the kidney. The correlation matrix showed also that the concentration of lead in these two soft tissues is not correlated. The lead accumulation in liver is made by different plateaus that strongly decrease with age. It was verified the existence of two levels of accumulation in kidney, not very highlighted, which might be indicative of a maximum accumulation level for lead in kidney.

The concentration of lead in liver and kidneys of Wistar rats, fed with lead since fetal period in relation to their age and to a control group, was determined. A group of rats was exposed to lead acetate (n=30) in drinking water and the other group was exposed to normal water (n=20). Samples were collected from rats aging between 1 and 11 months and were analyzed by Energy Dispersive X-ray Fluorescence (EDXRF) without any chemical preparation. The EDXRF results were assessed by the PIXE (Proton Induced X-ray Emission) technique. The formaldehyde used to preserve the samples was also analyzed by ETAAS (Electro-Thermal Atomic Absorption Spectrometry) in order to verify if there was any loss of lead from the samples to the formaldehyde. We found that the loss was not significant (<2%). Concerning the mean values of the lead concentration measured in the contaminated soft tissues, in liver they range from 6 to 22μgg(-1), and in kidneys from 44 to 79μgg(-1). The control rats show, in general, values below the EDXRF detection limit (2μgg(-1)). The ratio kidney/liver ranges from 2 to 10 and is strongly positively correlated with the age of the animals. A Spearman correlation matrix to investigate the correlation between elemental concentrations and the dependence of these concentrations with age showed that there is a strong positive correlation with age for lead in the liver but not in the kidney. The correlation matrix showed also that the concentration of lead in these two soft tissues is not correlated. The lead accumulation in liver is made by different plateaus that strongly decrease with age. It was verified the existence of two levels of accumulation in kidney, not very highlighted, which might be indicative of a maximum accumulation level for lead in kidney.

The spontaneous two-photon emission in hydrogenlike ions is investigated within the framework of second- order perturbation theory and Dirac’s equation. Special attention is paid to the angular correlation of the emitted photons as well as to the degree of linear polarization of one of the two photons, if the second is just observed under arbitrary angles. Expressions for the angular correlation and the degree of linear polarization are expanded in powers of cosine functions of the two-photon opening angle, whose coefficients depend on the atomic number and the energy sharing of the emitted photons. The effects of including higher (electric and magnetic) multipoles upon the emitted photon pairs beyond the electric-dipole approximation are also discussed. Calculations of the coefficients are performed for the transitions 2s1/2 → 1s1/2, 3d3/2 → 1s1/2, and 3d5/2 → 1s1/2, along the entire hydrogen isoelectronic sequence (1

The spontaneous two-photon emission in hydrogenlike ions is investigated within the framework of second- order perturbation theory and Dirac’s equation. Special attention is paid to the angular correlation of the emitted photons as well as to the degree of linear polarization of one of the two photons, if the second is just observed under arbitrary angles. Expressions for the angular correlation and the degree of linear polarization are expanded in powers of cosine functions of the two-photon opening angle, whose coefficients depend on the atomic number and the energy sharing of the emitted photons. The effects of including higher (electric and magnetic) multipoles upon the emitted photon pairs beyond the electric-dipole approximation are also discussed. Calculations of the coefficients are performed for the transitions 2s1/2 → 1s1/2, 3d3/2 → 1s1/2, and 3d5/2 → 1s1/2, along the entire hydrogen isoelectronic sequence (1 Z 100).

A relativistic analysis of the polarization properties of light elastically scattered by atomic hydrogen is performed, based on the Dirac equation and second-order perturbation theory. The relativistic atomic states used for the calculations are obtained by making use of the finite basis set method and are expressed in terms of B splines and B polynomials. We introduce two experimental scenarios in which the light is circularly and linearly polarized, respectively. For each of these scenarios, the polarization-dependent angular distribution and the degrees of circular and linear polarization of the scattered light are investigated as a function of scattering angle and photon energy. Analytical expressions are derived for the polarization-dependent angular distribution which can be used for scattering by both hydrogenic as well as many-electron systems. Detailed computations are performed for Rayleigh scattering by atomic hydrogen within the incident photon energy range 0.5 to 5 keV. Particular attention is paid to the effects that arise from higher (nondipole) terms in the expansion of the electron-photon interaction.

A relativistic analysis of the polarization properties of light elastically scattered by atomic hydrogen is performed, based on the Dirac equation and second-order perturbation theory. The relativistic atomic states used for the calculations are obtained by making use of the finite basis set method and are expressed in terms of B splines and B polynomials. We introduce two experimental scenarios in which the light is circularly and linearly polarized, respectively. For each of these scenarios, the polarization-dependent angular distribution and the degrees of circular and linear polarization of the scattered light are investigated as a function of scattering angle and photon energy. Analytical expressions are derived for the polarization-dependent angular distribution which can be used for scattering by both hydrogenic as well as many-electron systems. Detailed computations are performed for Rayleigh scattering by atomic hydrogen within the incident photon energy range 0.5 to 5 keV. Particular attention is paid to the effects that arise from higher (nondipole) terms in the expansion of the electron-photon interaction.

Concurrent programs that are free of unsynchronized ac- cesses to shared data may still exhibit unpredictable concurrency errors called atomicity violations, which include both high-level dataraces and stale-value errors. Atomicity violations occur when programmers make wrong assumptions about the atomicity scope of a code block, incorrectly splitting it in two or more atomic blocks and allow them to be interleaved with other atomic blocks. In this paper we propose a novel static analysis algorithm that works on a dependency graph of program variables and detects both high-level dataraces and stale-value errors. The algorithm was implemented for a Java Bytecode analyzer and its effectiveness was evaluated with some well known faulty programs. The results obtained show that our algorithm performs better than previous approaches, achieving higher precision for small and medium sized programs, making it a good basis for a practical tool.

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].

A new expression for the total K-shell ionization cross section by electron impact based on the rela- tivistic extension of the binary encounter Bethe (RBEB) model, valid from ionization threshold up to relativistic energies, is proposed. The new MRBEB expression is used to calculate the K-shell ionization cross sections by electron impact for the selenium atom. Comparison with all, to our knowledge, available experimental data shows good agreement.

A new expression for the total K-shell ionization cross section by electron impact based on the rela- tivistic extension of the binary encounter Bethe (RBEB) model, valid from ionization threshold up to relativistic energies, is proposed. The new MRBEB expression is used to calculate the K-shell ionization cross sections by electron impact for the selenium atom. Comparison with all, to our knowledge, available experimental data shows good agreement.

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This paper aims to study the influence of eco-innovation practices on eco-efficiency of business, which embraces environmental and economic performance. Four hypotheses are drawn up based on the existing literature in green supply chain and considering the business innovation. A survey questionnaire was used to collect data on a sample of {USA} and Portuguese innovative organizations. Multivariate statistics and Partial Least Squares ({PLS)} path modelling techniques were used to test the proposed hypothesis. The statistical analysis allows to conclude that there are differences between the eco-innovation practices deployed by organizations belonging to different sectors and with different sizes. Also, it was found that the level of implementation of the different eco-innovation practices by organizations influence the eco-efficiency of businesses.

This work presents an experimental study concerning the post-punching behaviour of flat slabs strengthened with a new technique based on post-tensioning with anchorages by bonding using an epoxy adhesive. This strengthening technique proved efficient with respect to ultimate and serviceability states. Five slab specimens were tested in the post-punching range and it was found that the post-punching resistance was on average 78{%} of the punching resistance. This paper reports the development of strand forces and slab displacements from the beginning of the tests, including the bond stresses developed at several stages of the loading process. It was observed that top reinforcement bars were capable of transmitting post-punching loads to the prestressing strands. Taking this into account and based on the load bath envisaged from the column to the slab, expressions for the vertical load capacities corresponding to the parts of the load path are presented and compared with the experimental results, showing their ability to predict both ultimate loads and modes of failure. Compared with other strengthening techniques, the one proposed here not only upgrades ultimate and serviceability behaviour but also adds post-punching resistance, which is a great advantage in the event of progressive collapse, since it may avoid the collapse of an entire structure, thus reducing the risk of material and human losses.

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.