Synthesis, mechanism of formation, and molecular orbital calculations of arylamidoximes

A simple and easy synthesis of ten arylamidoximes from arylnitriles and hydroxylamine is described. The formation of the arylamides has been observed to a much lesser extent in the present work. A new mechanism for the formation of arylamidoximes, as well as arylamides, from arylnitriles and hydroxylamine is suggested. Quantum mechanical calculations have been carried out to support this mechanism. The enthalpy of formation in conjunction with atomic charges of the reactants and intermediates helped to understand more about the generation of the products.

Ab initio calculation of the BCC Fe-Al-Mo (Iron-Aluminum-Molybdenum) phase diagram: Implications for the nature of the tau(2) phase

The metastable phase diagram of the BCC-based ordering equilibria in the Fe-Al-Mo system has been calculated via a truncated cluster expansion, through the combination of Full-Potential-Linear augmented Plane Wave (FP-LAPW) electronic structure calculations and of Cluster Variation Method (CVM) thermodynamic calculations in the irregular tetrahedron approximation. Four isothermal sections at 1750 K, 2000 K, 2250 K and 2500 K are calculated and correlated with recently published experimental data on the system. The results confirm that the critical temperature for the order-disorder equilibrium between Fe(3)Al-D0(3) and FeAl-B2 is increased by Mo additions, while the critical temperature for the FeAl-B2/A2 equilibrium is kept approximately invariant with increasing Mo contents. The stabilization of the Al-rich A2 phase in equilibrium with overstoichiometric B2-(Fe,Mo)Al is also consistent with the attribution of the A2 structure to the tau(2) phase, stable at high temperatures in overstoichiometric B2-FeAl. (C) 2009 Elsevier Ltd. All rights reserved.

Thermoelectric transport properties through a T-shaped single quantum dot

We study the thermopower, thermal conductance, electric conductance and the thermoelectric figure of merit for a gate-defined T-shaped single quantum dot (QD). The QD is solved in the limit of strong Coulombian repulsion U -> infinity, inside the dot, and the quantum wire is modeled on a tight-binding linear chain. We employ the X-boson approach for the Anderson impurity model to describe the localized level within the quantum dot. Our results are in qualitative agreement with recent experimental reports and other theoretical researches for the case of a quantum dot embedded into a conduction channel, employing analogies between the two systems. The results for the thermopower sign as a function of the gate voltage (associated with the quantum dot energy) are in agreement with a recent experimental result obtained for a suspended quantum dot. The thermoelectric figure of merit times temperature results indicates that, at low temperatures and in the crossover between the intermediate valence and Kondo regimes, the system might have practical applicability in the development of thermoelectric devices. (c) 2010 Elsevier B.V. All rights reserved.

A new nitrosyl ruthenium complex: Synthesis, chemical characterization, in vitro and in vivo antitumor activities and probable mechanism of action

This study describes the synthesis of a new ruthenium nitrosyl complex with the formula [RuCl(2)NO(BPA)] [BPA = (2-hydroxybenzyl)(2-methylpyridyl)amine ion], which was synthesized and characterized by spectroscopy, cyclic voltammetry, X-ray crystallography, and theoretical calculation data. The biological studies of this complex included in vitro cytotoxic assays, which revealed its activity against two different tumor cell lines (HeLa and Tm5), with efficacy comparable to that of cisplatin, a metal-based drug that is administered in clinical treatment. The in vivo studies showed that [RuCl2NO(BPA)] is effective in reducing tumor mass. Also, our results suggest that the mechanism of action of [RuCl(2)NO(BPA)] includes binding to DNA, causing fragmentation of this biological molecule, which leads to apoptosis. (C) 2011 Elsevier Masson SAS. All rights reserved.

MATERIALS EDUCATION AND INNOVATION: GLOBALIZATION OPENS NEW FRONTIERS, OPPORTUNITIES AND CHALLENGES

In this paper we consider evolutionary pressures that will influence materials education and its role in the present scenario of Globalization: Challenges, Opportunities and needs. The main evolutionary pressures are related to some major control variables: increase of global population, new emerging technologies such as nanotechnology, alternative energies related to climate change, multimedia convergence in global communications, health, hunger, economic asymmetries and violence. Of course, many other factors could be identified, but this paper considers these as an adequate minimum basis for strategic considerations related to current materials education planning for the 21st century. In conclusion, we propose an International Network Program for Materials Education Strategy, thinking globally but acting regionally.

A review of the tectonic evolution of the Sunsas belt, SW Amazonian Craton

The Sunsas-Aguapei province (1.20-0.95 Ga), SW Amazonian Craton, is a key area to study the heterogeneous effects of collisional events with Laurentia, which shows evidence of the Grenvillian and Sunsas orogens. The Sunsas orogen, characterized by an allochthonous collisional-type belt (1.11-1.00 Ga), is the youngest and southwestern most of the events recorded along the cratonic fringe. Its evolution occurred after a period of long quiescence and erosion of the already cratonized provinces (>1.30 Ga), that led to sedimentation of the Sunsas and Vibosi groups in a passive margin setting. The passive margin stage was roughly contemporary with intraplate tectonics that produced the Nova Brasilandia proto-oceanic basin (<1.21 Ga), the reactivation of the Ji-Parana shear zone network (1.18-1.12 Ga) and a system of aborted rifts that evolved to the Huanchaca-Aguapei basin (1.17-1.15 Ga). The Sunsas belt is comprised by the metamorphosed Sunsas and Vibosi sequences, the Rincon del Tigre mafic-ultramafic sill and granitic intrusive suites. The latter rocks yield epsilon(Nd(t)) signatures (-0.5 to -4.5) and geochemistry (S,1, A-types) suggesting their origin associated with a continental arc setting. The Sunsas belt evolution is marked by ""tectonic fronts"" with sinistral offsets that was active from c. 1.08 to 1.05 Ga, along the southern edge of the Paragua microcontinent where K/Ar ages (1.27-1.34 Ga) and the Huanchaca-Aguapei flat-lying cover attest to the earliest tectonic stability at the time of the orogen. The Sunsas dynamics is coeval with inboard crustal shortening, transpression and magmatism in the Nova Brasilandia belt (1.13-1.00 Ga). Conversely, the Aguapei aulacogen (0.96-0.91 Ga) and nearby shear zones (0.93-0.91 Ga) are the late tectonic offshoots over the cratonic margin. The post-tectonic to anorogenic stages took place after ca. 1.00 Ga, evidenced by the occurrences of intra-plate A-type granites, pegmatites, mafic dikes and sills, as well as of graben basins. Integrated interpretation of the available data related to the Sunsas orogen supports the idea that the main nucleus of Rodinia incorporated the terrains forming the SW corner of Amazonia and most of the Grenvillian margin, as a result of two independent collisional events, as indicated in the Amazon region by the Ji-Parana shear zone event and the Sunsas belt, respectively. (C) 2009 Elsevier Ltd. All rights reserved.

THE RIO APA CRATON IN MATO GROSSO DO SUL (BRAZIL) AND NORTHERN PARAGUAY: GEOCHRONOLOGICAL EVOLUTION, CORRELATIONS AND TECTONIC IMPLICATIONS FOR RODINIA AND GONDWANA

The Rio Apa cratonic fragment crops out in Mato Grosso do Sul State of Brazil and in northeastern Paraguay. It comprises Paleo-Mesoproterozoic medium grade metamorphic rocks, intruded by granitic rocks, and is covered by the Neoproterozoic deposits of the Corumbi and Itapocurni Groups. Eastward it is bound by the southern portion of the Paraguay belt. In this work, more than 100 isotopic determinations, including U-Pb SHRIMP zircon ages, Rb-Sr and Sm-Nd whole-rock determinations, as well as K-Ar and Ar-Ar mineral ages, were reassessed in order to obtain a complete picture of its regional geological history. The tectonic evolution of the Rio Apa Craton starts with the formation of a series of magmatic arc complexes. The oldest U-Pb SHRIMP zircon age comes from a banded gneiss collected in the northern part of the region, with an age of 1950 +/- 23 Ma. The large granitic intrusion of the Alumiador Batholith yielded a U-Pb zircon age of 1839 +/- 33 Ma, and from the southeastern part of the area two orthogneisses gave zircon U-Pb ages of 1774 +/- 26 Ma and 1721 +/- 25 Ma. These may be coeval with the Alto Terere metamorphic rocks of the northeastern corner, intruded in their turn by the Baia das Garcas granitic rocks, one of them yielding a zircon U-Pb age of 1754 +/- 49 Ma. The original magmatic protoliths of these rocks involved some crustal component, as indicated by the Sm-Nd TDm model ages, between 1.9 and 2.5 Ga. Regional Sr isotopic homogenization, associated with tectonic deformation and medium-grade metamorphism occurred at approximately 1670 Ma, as suggested by Rb-Sr whole rock reference isochrons. Finally, at 1300 Ma ago, the Ar work indicates that the Rio Apa Craton was affected by widespread regional heating, when the temperature probably exceeded 350 degrees C. Geographic distribution, age and isotopic signature of the fithotectonic units suggest the existence of a major suture separating two different tectonic domains, juxtaposed at about 1670 Ma. From that time on, the unified Rio Apa continental block behaved as one coherent and stable tectonic unit. It correlates well with the SW corner of the Amazonian Craton, where the medium-grade rocks of the Juruena-Rio Negro tectonic province, with ages between 1600 and 1780 Ma, were reworked at about 1300 Ma. Looking at the largest scale, the Rio Apa Craton is probably attached to the larger Amazonian Craton, and the actual configuration of southwestern South America is possibly due to a complex arrangement of allochthonous blocks such as the Arequipa, Antofalla and Pampia, with different sizes, that may have originated as disrupted parts of either Laurentia or Amazonia, and were trapped during later collisions of these continental masses.

The position of the Amazonian Craton in supercontinents

This paper examines the extensive regions of Proterozoic accretionary belts that either formed most of the Amazonian Craton, or are marginal to its southeastern border. Their overall geodynamic significance is considered taking into account the paleogeographic reconstruction of Columbia, Rodinia and Gondwana. Amazonia would be part of Columbia together With Laurentia, North China and Baltica, forming a continuous, continental landmass linked by the Paleo- to Mesoproterozoic mobile belts that constitute large portions of it. The Rodinia supercontinent was formed in the Mesoproterozoic by the agglutination of the existing cratonic fragments, such as Laurentia and Amazonia, during contemporary continental collisions worldwide. The available paleomagnetic data suggest that Laurentia and Amazonia remained attached until at least 600 Ma. Since all other cratonic units Surrounding Laurentia have already rifted away by that time, the separation between Amazonia and Laurentia marks the final break-up of Rodinia with the opening of the lapetus ocean. (C) 2009 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

Towards high-resolution shell midden archaeology: Experimental and ethnoarchaeology in Tierra del Fuego (Argentina)

This paper discusses the ongoing ethnoarchaeological research carried out in Yamana shell middens of Tierra del Fuego. Ethnoarchaeology is used in this research as a tool to improve the archaeological methodology by testing it against anthropological, ethnographical and ethnological sources for achieving more accurate reconstructions of past societies. The ethnographical/ethnological information also is coupled with an experimental approach devised to understand physical and social processes, such as site formation processes and resource use and management. Specifically, this experimental approach was applied to the archaeological sites Tunel VII and Lanashuaia I (Tierra del Fuego, Argentina). (C) 2011 Elsevier Ltd and INQUA. All rights reserved.

Is the unfolding of the group discussion off-pattern? Improving coordination support in educational forums using mobile devices

A forum is a valuable tool to foster reflection in an in-depth discussion; however, it forces the course mediator to continually pay close attention in order to coordinate learners` activities. Moreover, monitoring a forum is time consuming given that it is impossible to know in advance when new messages are going to be posted. Additionally, a forum may be inactive for a long period and suddenly receive a burst of messages forcing forum mediators to frequently log on in order to know how the discussion is unfolding to intervene whenever it is necessary. Mediators also need to deal with a large amount of messages to identify off-pattern situations. This work presents a piece of action research that investigates how to improve coordination support in a forum using mobile devices for mitigating mediator`s difficulties in following the status of a forum. Based on summarized information extracted from message meta-data, mediators consult visual information summaries on PDAs and receive textual notifications in their mobile phone. This investigation revealed that mediators used the mobile-based coordination support to keep informed on what is taking place within the forum without the need to log on their desktop computer. (C) 2009 Elsevier Ltd. All rights reserved.

A multi-GPU algorithm for large-scale neuronal networks

Large-scale simulations of parts of the brain using detailed neuronal models to improve our understanding of brain functions are becoming a reality with the usage of supercomputers and large clusters. However, the high acquisition and maintenance cost of these computers, including the physical space, air conditioning, and electrical power, limits the number of simulations of this kind that scientists can perform. Modern commodity graphical cards, based on the CUDA platform, contain graphical processing units (GPUs) composed of hundreds of processors that can simultaneously execute thousands of threads and thus constitute a low-cost solution for many high-performance computing applications. In this work, we present a CUDA algorithm that enables the execution, on multiple GPUs, of simulations of large-scale networks composed of biologically realistic Hodgkin-Huxley neurons. The algorithm represents each neuron as a CUDA thread, which solves the set of coupled differential equations that model each neuron. Communication among neurons located in different GPUs is coordinated by the CPU. We obtained speedups of 40 for the simulation of 200k neurons that received random external input and speedups of 9 for a network with 200k neurons and 20M neuronal connections, in a single computer with two graphic boards with two GPUs each, when compared with a modern quad-core CPU. Copyright (C) 2010 John Wiley & Sons, Ltd.

Can mass dissociation patterns of transition-metal complexes be predicted from electrochemical data?

The Cooks kinetic method has been very convenient to correlate the relative dissociation rates obtained by collision-induced fragmentation experiments with the energies of two related bonds in molecules and complexes in the gas phase. Reliable bond energy data are, however, not always available, particularly for polynuclear transition-metal complexes, such as the triruthenium acetate clusters of the general formula [Ru(3) (mu(3)-O)(mu-CH(3)COO)(6)(py)(2)(L)](+), where L = ring substituted N-heterocyclic ligands. Accordingly, their gas-phase collision-induced tandem mass spectrometry (CID MS/MS) dissociation patterns have been analyzed pursuing a relationship with the more easily accessible redox potentials (E(1/2)) and Lever`s E(L) parameters. In fact, excellent linear correlations of In(1/2A(L)/A(py)), where A(py) and A(L) are the abundance of the fragments retaining the pyridine (py) and L ligand, respectively, with E(1/2) and E(L) were found. This result shows that those electrochemical parameters are correlated with bond energies and can be used in the analysis of the dissociation data. Such modified Cooks method can be used, for example, to determine the electronic effects of substituents on the metal-ligand bonds for a series of transition-metal complexes. Copyright (C) 2008 John Wiley & Sons, Ltd.

Studies on chemo- and diastereo-selectivity of the Diels-Alder reactions of sulfinyltoluquinones with cyclopentadiene

Sulfinyltoluquinones (2a-2c) were submitted to thermal or catalyzed [4+2] cycloaddition reactions with cyclopentadiene. For p-tolylsulfinyltoluquinones (2b) and (2c), almost complete C2-C3-chemo- and unlike-diastereoselectivity was achieved by catalysis with ZnBr(2), yielding adducts 6. Under thermal conditions, Diels-Alder reaction took place at the C5-C6 double bonds of quinones 2a-2c, generating mixtures of diastereoisomeric like- and unlike-adducts 4.

Cytotoxic and genotoxic effects of tambjamine D, an alkaloid isolated from the nudibranch Tambja eliora, on Chinese hamster lung fibroblasts

Marine organisms have been shown to be potential sources of bioactive compounds with pharmaceutical applications. Previous chemical investigation of the nudibranch Tambja eliora led to the isolation of the alkaloid tambjamine D. Tambjamines have been isolated from marine sources and belong to the family of 4-methoxypyrrolic-derived natural products, which display promising immunosuppressive and cytotoxic properties. Their ability to intercalate DNA and their pro-oxidant activity may be related to some of the biological effects of the 4-methoxypyrrolic alkaloids. The aim of the present investigation was to determine the cytotoxic, pro-oxidant and genotoxic properties of tambjamine D in V79 Chinese hamster lung fibroblast cells. Tambjamine D displayed a potent cytotoxic effect in V79 cells (IC50 1.2 mu g/mL) evaluated by the MTT assay. Based on the MTT result, V79 cells were treated with different concentrations of tambjamine D (0.6. 1.2. 2.4 and 4.8 mu g/mL). After 24 h, tambjamine D reduced the number of viable cells in a concentration-dependent way at all concentrations tested. assessed by the trypan blue dye exclusion test. The hemolytic assay showed that the cytotoxic activity of tambjamine D was not related to membrane disruption (EC50 > 100 mu g/mL). Tambjamine D increased the number of apoptotic cells in a concentration-dependent manner at all concentrations tested according to acridine orange/ethidium bromide staining, showing that the alkaloid cytotoxic effect was related to the induction of apoptosis. MTT reduction was stimulated by tambjamine D, which may indicate the generation of reactive oxygen species. Accordingly, treatment of cells with tambjamine D increased nitrite/nitrate at all concentrations and TBARS production starting at the concentration corresponding to the IC50. Tambjamine D, also, induced DNA strand breaks and increased the micronucleus cell frequency as evaluated by comet and micronucleus tests, respectively, at all concentrations evaluated. showing a genotoxic risk induced by tambjamine D. (C) 2008 Elsevier Ireland Ltd. All rights reserved.

Biobased films prepared from NaOH/thiourea aqueous solution of chitosan and linter cellulose

In the present study, films based on linter cellulose and chitosan were prepared using an aqueous solution of sodium hydroxide (NaOH)/thiourea as the solvent system. The dissolution process of cellulose and chitosan in NaOH/thiourea aqueous solution was followed by the partial chain depolymerization of both biopolymers, which facilitates their solubilization. Biobased films with different chitosan/cellulose ratios were then elaborated by a casting method and subsequent solvent evaporation. They were characterized by X-ray analysis, scanning electron microscopy (SEM), atomic force microscopy (AFM), thermal analysis, and tests related to tensile strength and biodegradation properties. The SEM images of the biofilms with 50/50 and 60/40 ratio of chitosan/cellulose showed surfaces more wrinkled than the others. The AFM images indicated that higher the content of chitosan in the biobased composite film, higher is the average roughness value. It was inferred through thermal analysis that the thermal stability was affected by the presence of chitosan in the films; the initial temperature of decomposition was shifted to lower levels in the presence of chitosan. Results from the tests for tensile strength indicated that the blending of cellulose and chitosan improved the mechanical properties of the films and that an increase in chitosan content led to production of films with higher tensile strength and percentage of elongation. The degradation study in a simulated soil showed that the higher the crystallinity, the lower is the biodegradation rate.