The C 1s and N 1s photoelectron spectra of gas-phase 5-aminotetrazole (5ATZ) were recorded using synchrotron radiation, with the aim of evaluating 1H/2H tautomer population ratios. The core-electron binding energies (CEBEs) were estimated from computational results, using the delta self-consistent-field (ΔSCF) approach. Simulated spectra were generated using these CEBEs and the results from Gaussian-n (Gn, n=1, 2 and 3) and Complete Basis Set (CBS-4M and CBS-Q) methods. Results reveal the almost exclusive predominance of the 2H-tautomer, with a 1H/2H ratio of ca. 0.12/0.88, taken from a gross analysis of the XPS C 1s spectrum, recorded at 365 K.

The properties of the light flexible device, ion jelly, which combines gelatin with an ionic liquid (IL) were recently reported being promising to develop safe and highly conductive electrolytes. This article aims for the understanding of the ion jelly conductive mechanism using dielectric relaxation spectroscopy (DRS) in the frequency range 10−1−106 Hz; the study was complemented with differential scanning calorimetry (DSC) and pulse field gradient nuclear magnetic resonance (PFG NMR) spectroscopy. The room temperature ionic liquid 1-butyl-3-methylimmidazolium dicyanamide (BMIMDCA) used as received (1.9% w/w water content) and with 6.6% (w/w) of water content and two ion jellies with two different ratios BMIMDCA/gelatin/water % (w/w), IJ1 (41.1/46.7/12.2) and IJ3 (67.8/25.6/6.6), have been characterized. A glass transition was detected by DSC for all materials allowing for classifying them as glass formers. For the ionic liquid, it was observed that the glass transition temperature decreases with the increase of water content. While in subsequent calorimetric runs crystallization was observed for BMIMDCA with negligible water content, no crystallization was detected for any of the ion jelly materials upon themal cycling. To the dielectric spectra of all tested materials, both dipolar relaxation and conductivity contribute; at the lowest frequencies, electrode and interfacial polarization highly dominate. Conductivity, which manifests much more intensity relative to dipolar reorientations, strongly evidences subdiffusive ion dynamics at high frequencies. From dielectric measures, transport properties as mobility and diffusion coefficients were extracted. Data treatment was carried out in order to deconvolute the average diffusion coefficients estimated from dielectric data in its individual contributions of cations (D+) and anions (D−). The D+ values thus obtained for IJ3, the ion jelly with the highest IL/gelatin ratio, cover a large temperature range up to room temperature and revealed excellent agreement with direct measurements from PFG NMR, obeying to the same VFT equation. For BMIMDCA6.6%water, which has the same water amount as IJ3, the diffusion coefficients were only estimated from DRS measurements over a limited temperature range; however, a single VFT equation describes both DRS and PFG NMR data. Moreover, it was found that the diffusion coefficients and mobility are similar for the ionic liquid and IJ3, which points to a role of both water and gelatin weakening the contact ion pair, facilitating the translational motion of ions and promoting its dissociation; nevertheless, it is conceivable that a critical composition of gelatin that leads to those properties. The VFT temperature dependence observed for the conductivity was found to be determined by a similar dependence of the mobility. Both conductivity and segmental motion revealed to be correlated as inferred by the relatively low values of the decoupling indexes. The obtained results show that ion jelly could be in fact a very promising material to design novel electrolytes for different electrochemical devices, having a performance close to the IL but presenting an additional stability regarding electrical measurements and resistance against crystallization relative to the bulk ionic liquid.

The main aim of this work was to assess the possibility of using biomass ashes as substitutes for cement and natural aggregates in concretes without compromising their mechanical and chemical properties. Thirteen concrete formulations were prepared with different percentages of bottom and fly ashes produced at a forest biomass power plant. These formulations were submitted to mechanical compressive strength assays, after 28, 60 and 90 days of maturation. The reference formulation F1 that was produced without biomass ashes and one formulation incorporating fly and bottom ashes, F4, were selected for further characterization. After 90 days of maturation, the selected formulations were submitted to the leaching test described in the European Standard EN12457-2 (L/S ratio of 10 L/kg, in a batch extraction cycle of 24h) by using two different leaching agents: a synthetic marine medium (ASPM medium) and a synthetic freshwater medium (ISO 6341 medium). The eluates produced were submitted to chemical characterization which comprised a set of metals (As, Sb, Se, Cu, Zn, Ba, Hg, Cd, Mo, Pb, Ni, Cr, Cr VI, Al, Fe, Mg, Na, K and Ca), pH, SO42-, F-, dissolved organic carbon, chlorides, phenolic compounds and total dissolved solids. The substitution of 10% cement by fly ashes has not promoted the reduction of the compressive strength of concrete. The new formulation F4 has presented emission levels of chemical species similar or even lower to those observed for the reference formulation F1.

{Zinc alkyl cations supported by N,N-BIAN-type bidentate ligands were found to be highly active in the immortal ROP of epsilon-caprolactone to yield narrowly disperse and chain length-controlled poly(epsilon-caprolactone), whether in solution or bulk polymerization conditions.}

{{A series of Ar-BIAN-based copper(I) complexes (where Ar-BIAN = bis(aryl) acenaphthenequinonediimine) were synthesised and characterised by H-1 and C-13 NMR spectroscopies, FT-IR spectroscopy, MALDI-TOF-MS spectrometry, cyclic voltammetry and single crystal X-ray diffraction. The bis-chelated complexes of general formula {[}Cu(Ar-BIAN)(2)]BF4 (where Ar = C6H5 (1), 4-iPrC(6)H(4) (3), 2-iPrC(6)H(4) (4)) were prepared by reaction of {[}Cu(NCMe)(4)]BF4 with two equivalents of the corresponding Ar-BIAN ligands, in dichloromethane, while the mono-chelated complexes of the type {[}Cu(Ar-BIAN)L2]BF4 (where Ar = 2,6-iPr(2)C(6)H(3)

Green and lean paradigms have been adopted by companies in order to manage their relationships with suppliers in a supply chain management context, but nearly always separately and with little understanding of their influence on company performance. This paper proposes a theoretical framework for the analysis of the influence of green and lean upstream supply chain management practices on the sustainable development of businesses. To attend this objective, a set of performance measures covering economic (operational cost, environmental cost, and inventory cost), environmental (business wastage, green image, and CO 2 emission), and social (corruption risk, supplier screening and local supplier) perspectives is proposed. An explanatory case study was conducted at a Portuguese automaker to test qualitatively the validity of the proposed theoretical framework. From the case study, a model is suggested, which encompasses the relationships between green and lean upstream supply chain practices and sustainable business development.

Barium zinc borosilicate glasses with a molar composition xBaO-(60-x)ZnO-30B 2O 3-10SiO 2, where x ranged from 0 to 60 mol%, were prepared using melt-quenching method. The effect of BaO substitution for ZnO on the sintering, crystallization, and dielectric characteristics has been investigated. The behavior of the studied barium zinc borosilicate glasses was mainly determined by the relative amount of the structural modifier oxides (BaO and ZnO) and the ionic size, and field strength of the modifying cations (Ba 2+, Zn 2+). Increased amounts of BaO decreased both glass transition temperature and crystallization temperature, while increasing the relative dielectric constant. Sintering occurred before crystallization for glasses where substitution of BaO for ZnO was up to 30 mol%, but for higher substitution levels, crystallization occurred during the sintering process hindering densification. © 2012 The American Ceramic Society.

Ferritins are ubiquitous and can be found in practically all organisms that utilize Fe. They are composed of 24 subunits forming a hollow sphere with an inner cavity of similar to 80 angstrom in diameter. The main function of ferritin is to oxidize the cytotoxic Fe2+ ions and store the oxidized Fe in the inner cavity. It has been established that the initial step of rapid oxidation of Fe2+ (ferroxidation) by H-type ferritins, found in vertebrates, occurs at a diiron binding center, termed the ferroxidase center. In bacterial ferritins, however, X-ray crystallographic evidence and amino acid sequence analysis revealed a trinuclear Fe binding center comprising a binuclear Fe binding center (sites A and B), homologous to the ferroxidase center of H-type ferritin, and an adjacent mononuclear Fe binding site (site C). In an effort to obtain further evidence supporting the presence of a trinuclear Fe binding center in bacterial ferritins and to gain information on the states of the iron bound to the trinuclear center, bacterial ferritin from Desulfovibrio vulgaris (DvFtn) and its E130A variant was loaded with substoichiometric amounts of Fe2+, and the products were characterized by Mossbauer and EPR spectroscopy. Four distinct Fe species were identified: a paramagnetic diferrous species, a diamagnetic diferrous species, a mixed valence Fe2+Fe3+ species, and a mononuclear Fe2+ species. The latter three species were detected in the wild-type DvFtn, while the paramagnetic diferrous species was detected in the E130A variant. These observations can be rationally explained by the presence of a trinuclear Fe binding center, and the four Fe species can be properly assigned to the three Fe binding sites. Further, our spectroscopic data suggest that (1) the fully occupied trinuclear center supports an all ferrous state, (2) sites B and C are bridged by a mu-OH group forming a diiron subcenter within the trinuclear center, and (3) this subcenter can afford both a mixed valence Fe2+Fe3+ state and a diferrous state. Mechanistic insights provided by these new findings are discussed and a minimal mechanistic scheme involving O-O bond cleavage is proposed.

The C 1s and N 1s photoelectron spectra of gas-phase 5-aminotetrazole (5ATZ) were recorded using synchrotron radiation, with the aim of evaluating 1H/2H tautomer population ratios. The core-electron binding energies (CEBEs) were estimated from computational results, using the delta self-consistent-field (ΔSCF) approach. Simulated spectra were generated using these CEBEs and the results from Gaussian-n (Gn, n=1, 2 and 3) and Complete Basis Set (CBS-4M and CBS-Q) methods. Results reveal the almost exclusive predominance of the 2H-tautomer, with a 1H/2H ratio of ca. 0.12/0.88, taken from a gross analysis of the XPS C 1s spectrum, recorded at 365 K.

Building energy management may simultaneously integrate multiple energy areas and sources of information. The coordination of synergies allow better-informed decisions, such as performing forecasts and adjustments of energy production and storage, while adapting electrical loads to off-peak times, when energy rates are lower. This work targets the improvement and optimization of energy management operations in buildings and large complexes, by introducing a conceptual model for supporting real-time advanced reasoning and inference towards efficient energy management.