Spectroscopic and computational methods have been used to determine the protonation state of the edge sulfur ligand in the Cu4S2 CuZ form of the active site of nitrous oxide reductase (N2OR) in its 3CuICuII (1-hole) and 2CuI2CuII (2-hole) redox states. The EPR, absorption, and MCD spectra of 1-hole CuZ indicate that the unpaired spin in this site is evenly delocalized over CuI, CuII, and CuIV. 1-hole CuZ is shown to have a mu2-thiolate edge ligand from the observation of S-H bending modes in the resonance Raman spectrum at 450 and 492 cm-1 that have significant deuterium isotope shifts (-137 cm-1) and are not perturbed up to pH 10. 2-hole CuZ is characterized with absorption and resonance Raman spectroscopies as having two Cu-S stretching vibrations that profile differently. DFT models of the 1-hole and 2-hole CuZ sites are correlated to these spectroscopic features to determine that 2-hole CuZ has a mu2-sulfide edge ligand at neutral pH. The slow two electron (+1 proton) reduction of N2O by 1-hole CuZ is discussed and the possibility of a reaction between 2-hole CuZ and O2 is considered.

A sociedade organizou-se para fazer frente a necessidades como o tratamento e acompanhamento de crianças ou jovens com Síndrome de Down, Surdez, Autismo, entre outras patologias. Como resultado, surgiram distintas organizações com o objetivo de lidar com estes casos, compostas por médicos, terapeutas, psicólogos, sociólogos e outros profissionais, mas excluindo profissionais dedicados ao desenvolvimento de novas tecnologias. Por outro lado, alunos finalistas de cursos tecnológicos desenvolvem normalmente um projeto tecnológico do início na disciplina final dos seus cursos - Projeto/Dissertação de fim de curso. Este artigo propõe um método para aplicar o esforço e entusiasmo de tais alunos às causas sociais mencionadas através do desenvolvimento de Jogos.

Journal of Physics B: Atomic, Molecular and Optical Physics, 48(2015) 144027. doi:10.1088/0953-4075/48/14/144027

Journal of Physics B: Atomic, Molecular and Optical Physics, 48(2015) 144027. doi:10.1088/0953-4075/48/14/144027

Sand pile and Bean models have already been applied to describe single grain HTS bulks. An extension to that approach was used to model multiseed bulks, needed for several practical applications as electric motors or flywheels with superconducting bearings. The use of genetic algorithms was then proposed to determine intra- and intergrain current densities, and application to two and three seeds samples using trapped flux experimental measurements was exemplified. However, this model assumed some simplifications, as equal properties in grain boundaries between neighboring grains. In this paper an extension to this methodology is proposed and evaluated by analyzing measurements performed in plans at different distances from surfaces of samples with three seeds. Discussion of its influence on a practical application is also explored.

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In this study, we report solution-processed amorphous zinc tin oxide transistors exhibiting high operational stability under positive gate bias stress, translated by a recoverable threshold voltage shift of about 20{%} of total applied stress voltage. Under vacuum condition, the threshold voltage shift saturates showing that the gate-bias stress is limited by trap exhaustion or balance between trap filling and emptying mechanism. In ambient atmosphere, the threshold voltage shift no longer saturates, stability is degraded and the recovering process is impeded. We suggest that the trapping time during the stress and detrapping time in recovering are affected by oxygen adsorption/desorption processes. The time constants extracted from stretched exponential fitting curves are ≈106 s and 105 s in vacuum and air, respectively.

Molybdenum is found in the active site of enzymes usually coordinated by one or two pyranopterin molecules. Here, we mimic an enzyme with a mononuclear molybdenum-bis pyranopterin center by incorporating molybdenum in rubredoxin. In the molybdenum-substituted rubredoxin, the metal ion is coordinated by four sulfurs from conserved cysteine residues of the apo-rubredoxin and two other exogenous ligands, oxygen and thiol, forming a Mo((VI))-(S-Cys)4(O)(X) complex, where X represents -OH or -SR. The rubredoxin molybdenum center is stabilized in a Mo(VI) oxidation state, but can be reduced to Mo(IV) via Mo(V) by dithionite, being a suitable model for the spectroscopic properties of resting and reduced forms of molybdenum-bis pyranopterin-containing enzymes. Preliminary experiments indicate that the molybdenum site built in rubredoxin can promote oxo transfer reactions, as exemplified with the oxidation of arsenite to arsenate.

Given the proliferation and enhanced capabilities of mobile devices, their computational and storage resources can now be combined in a wireless cloud of nearby mobile devices, a mobile edge-cloud. These clouds are of particular interest in low connectivity scenarios, e.g., sporting events and disaster scenarios. In these dynamic clouds it is necessary to reliably disseminate and share data, and also to offload data processing computations to other devices in the edge-cloud. We are particularly interested in supporting storage services in these new type of edge-clouds, as a mean to enable data sharing, dissemination and querying, as well as to serve as a distributed file system for offloaded computations. In this Ph.D. thesis, we propose to address these questions by researching on the usage of ad-hoc clouds of mobile devices to develop an efficient storage service capable of providing high availability and reliability.

Electrochemically active bacteria (EAB) have the capability to transfer electrons to cell exterior, a feature that is currently explored for important applications in bioremediation and biotechnology fields. However, the number of isolated and characterized EAB species is still very limited regarding their abundance in nature. Colorimetric detection has emerged recently as an attractive mean for fast identification and characterization of analytes based on the use of electrochromic materials. In this work, WO3 nanoparticles were synthesized by microwave assisted hydrothermal synthesis and used to impregnate non-treated regular office paper substrates. This allowed the production of a paper-based colorimetric sensor able to detect EAB in a simple, rapid, reliable, inexpensive and eco-friendly method. The developed platform was then tested with Geobacter sulfurreducens, as a proof of concept. G. sulfurreducens cells were detected at latent phase with an RGB ratio of 1.10 ± 0.04, and a response time of two hours.