Study of the oxygen vacancy influence on magnetic properties of Fe- and Co-doped SnO2 diluted alloys

Transition-metal (TM)-doped diluted magnetic oxides (DMOs) have attracted attention from both experimental and theoretical points of view due to their potential use in spintronics towards new nanostructured devices and new technologies. In the present work, we study the magnetic properties of Sn0.96TM0.04O2 and Sn0.96TM0.04O1.98(V (O))(0.02), where TM = Fe and Co, focusing in particular in the role played by the presence of O vacancies nearby the TM. The calculated total energy as a function of the total magnetic moment per cell shows a magnetic metastability, corresponding to a ground state, respectively, with 2 and 1 mu(B)/cell, for Fe and Co. Two metastable states, with 0 and 4 mu(B)/cell were found for Fe, and a single value, 3 mu(B)/cell, for Co. The spin-crossover energies (E (S)) were calculated. The values are E (S) (0/2) = 107 meV and E (S) (4/2) = 25 meV for Fe. For Co, E (S) (3/1) = 36 meV. By creating O vacancies close to the TM site, we show that the metastablity and E (S) change. For iron, a new state appears, and the state with zero magnetic moment disappears. The ground state is 4 mu(B)/cell instead of 2 mu(B)/cell, and the energy E (S) (2/4) is 30 meV. For cobalt, the ground state is then found with 3 mu(B)/cell and the metastable state with 1 mu(B)/cell. The spin-crossover energy E (S) (1/3) is 21 meV. Our results suggest that these materials may be used in devices for spintronic applications that require different magnetization states.

Effect of pH and temperature on the global compactness, structure, and activity of cellobiohydrolase Cel7A from Trichoderma harzianum

Due to its elevated cellulolytic activity, the filamentous fungus Trichoderma harzianum (T. harzianum) has considerable potential in biomass hydrolysis application. Cellulases from Trichoderma reesei have been widely used in studies of cellulose breakdown. However, cellulases from T. harzianum are less-studied enzymes that have not been characterized biophysically and biochemically as yet. Here, we examined the effects of pH and temperature on the secondary and tertiary structures, compactness, and enzymatic activity of cellobiohydrolase Cel7A from T. harzianum (Th Cel7A) using a number of biophysical and biochemical techniques. Our results show that pH and temperature perturbations affect Th Cel7A stability by two different mechanisms. Variations in pH modify protonation of the enzyme residues, directly affecting its activity, while leading to structural destabilization only at extreme pH limits. Temperature, on the other hand, has direct influence on mobility, fold, and compactness of the enzyme, causing unfolding of Th Cel7A just above the optimum temperature limit. Finally, we demonstrated that incubation with cellobiose, the product of the reaction and a competitive inhibitor, significantly increased the thermal stability of Th Cel7A. Our studies might provide insights into understanding, at a molecular level, the interplay between structure and activity of Th Cel7A at different pH and temperature conditions.

Late Adverse Effects of the Coadministration of Valproate and Lamotrigine

Individuals treated with combined valproate-lamotrigine rarely present late adverse effects (unrelated to introduction and titration). We describe four patients in whom such effects occurred after continuous, long-term use of valproate-lamotrigine (at 9 months to 2 years after final antiepileptic drug adjustment). The patients presented heterogeneous disturbances, including ataxia, vertigo, and headache, and rare movement disorders, such as tics and abnormal eye movements. Although these effects are heterogeneous in their occurrence and timing, they can alert physicians to the possibility of late neurologic disturbances, and must be considered in order to avoid unnecessary ancillary tests. Treatment discontinuation is unnecessary, given that a small decrease in dose led to remission of these adverse effects. (c) 2012 Elsevier Inc. All rights reserved.

Antioxidant Effects of Quercetin and Catechin Encapsulated into PLGA Nanoparticles

Polymeric nanoparticles (PLGA) have been developed for the encapsulation and controlled release of quercetin and catechin. Nanoparticles were fabricated using a solvent displacementmethod. Physicochemical properties were measured by light scattering, scanning electron microscopy and zeta-potential, X-ray diffraction, infrared spectroscopy and differential scanning calorimetry. Encapsulation efficiency and in vitro release profiles were obtained from differential pulse voltammetry experiments. Antioxidant properties of free and encapsulated flavonoids were determined by TBARS, fluorescence spectroscopy and standard chelating activity methods. Relatively small (d approximate to 400 nm) polymeric nanoparticles were obtained containing quercetin or catechin in a non-crystalline form (EE approximate to 79%) and the main interactions between the polymer and each flavonoid were found to consist of hydrogen bonds. In vitro release profiles were pH-dependant, the more acidic pH, the faster release of each flavonoid from the polymeric nanoparticles. The inhibition of the action of free radicals and chelating properties, were also enhanced when quercetin and catechin were encapsulated within PLGA nanoparticles. The information obtained from this study will facilitate the design and fabrication of polymeric nanoparticles as possible oral delivery systems for encapsulation, protection and controlled release of flavonoids aimed to prevent oxidative stress in human body or food products.

An Overview of Relevant Aspects on VIM of Spar and Monocolumn Platforms

Vortex-induced motions (VIM) of floating structures are very relevant for the design of mooring and riser systems. In the design phase, spar and monocolumn VIM behavior, as well as semisubmersible and tension leg platform flow-induced motions, is studied and evaluated. This paper provides a checklist of topics and evidence from a number of sources to justify the selection that should be considered when designing spars or monocolumn platforms regarding the VIM phenomenon. An overview of the influential aspects of the VIM is presented such as heading, external appendages of the hull, concomitant presence of waves and currents, motion suppressor, draft condition (immersed portion of the hull), and external damping due to the presence of risers. Previous works concerning the VIM studies on spar and monocolumn platforms are also addressed. Whenever possible, the results of experiments from diverse authors on this matter are presented and compared. [DOI: 10.1115/1.4003698]

Ab initio studies of pristine and oxidized Cu3Au(100) and (111) surfaces

We review the previous literature and our recent work on first-principles studies of Cu3Au(100) and (111) surfaces, with focus on the segregation of atomic species to the surface at pristine conditions and in the presence of oxygen. In particular, the combined use of experimental and theoretical tools to achieve chemical identification at an atomic level of the surface species is emphasized and discussed.

Comparison of ultrasonography and histopathology for the diagnosis of endometritis in Holstein-Friesian cows

Reproductive diseases are a great barrier to dairy production, as they diminish fertility and cause economic loss. In this context, endometritis plays an important role. Different diagnostic techniques exist for endometritis that vary in sensitivity and specificity. This work aimed to evaluate and compare ultrasonographic and histopathological examinations, and combinations thereof, for the diagnosis of endometritis by determining their sensitivity, specificity, and kappa agreement coefficients using endometrial cytology as the gold standard. We developed an adaptive reading score to perform histological examination of the uterus. In this study, 76 Holstein-Friesian cows, 21 to 47 d postpartum, without vaginal catarrh were submitted to gynecological examinations, including ultrasonographic examination, an endometrial cytology examination, and a uterine biopsy. Our results indicate that ultrasonography is a practical and effective diagnostic method, and a combination of the determination of intrauterine fluid and cervical diameter was the most efficient ultrasonographic method, with 50% sensitivity and 88% specificity. Histopathological examination was a useful diagnostic method that provided rich detail on endometrial inflammation, and allowed evaluation of different components of the tissue such as the epithelium, lamina propria, endometrial glands, and blood vessels; this method had 44% sensitivity and 92% specificity for diagnosis of endometritis.

Metal binding selectivity of oxa-aza macrocyclic ligand: a DFT study of first- and second-row transition metal for four coordination systems

A detailed theoretical study of the 1,7,1l,17-tetraoxa-2,6,12,16-tetraaza-cycloeicosane ligand ([20]AneN(4)O(4)) coordinated to Fe2+, Co2+, Ni2+, Ru2+, Rh2+, and Pd2+ transition metal ions was carried out with the B3LYP method. Two different cases were performed: when nitrogen is the donor atom (1a (q) ) and also with the oxygen as the donor atom (1b (q) ). For all the cases performed in this study 1a (q) structures were always more stable than the 1b (q) ones. Considering each row is possible to see that the energy increases with the increase of the atomic number. The M2+ cation binding energies for the 1a (q) complexes increase with the following order: Fe2+ < Ru2+ < Co2+ < Ni2+ < Rh2+ < Pd2+.

Characterization of selectivity and pharmacophores of type 1 sea anemone toxins by screening seven Na-v sodium channel isoforms

During their evolution, animals have developed a set of cysteine-rich peptides capable of binding various extracellular sites of voltage-gated sodium channels (VGSC). Sea anemone toxins that target VGSCs delay their inactivation process, but little is known about their selectivities. Here we report the investigation of three native type 1 toxins (CGTX-II, delta-AITX-Bcg1a and delta-AITX-Bcg1b) purified from the venom of Bunodosoma cangicum. Both delta-AITX-Bcg1a and delta-AITX-Bcg1b toxins were fully sequenced. The three peptides were evaluated by patch-clamp technique among Nav1.1-1.7 isoforms expressed in mammalian cell lines, and their preferential targets are Na(v)1.5 > 1.6 > 1.1. We also evaluated the role of some supposedly critical residues in the toxins which would interact with the channels, and observed that some substitutions are not critical as expected. In addition, CGTX-II and delta-AITX-Bcg1a evoke different shifts in activation/inactivation Boltzmann curves in Nav1.1 and 1.6. Moreover, our results suggest that the interaction region between toxins and VGSCs is not restricted to the supposed site 3 (S3-54 linker of domain IV), and this may be a consequence of distinct surface of contact of each peptide vs. targeted channel. Our data suggest that the contact surfaces of each peptide may be related to their surface charges, as CGTX-II is more positive than delta-AITX-Bcg1a and delta-AITX-Bcg1b. (C) 2011 Elsevier Inc. All rights reserved.

A Note on Large Deviations for the Stable Marriage of Poisson and Lebesgue with Random Appetites

Let IaS,a"e (d) be a set of centers chosen according to a Poisson point process in a"e (d) . Let psi be an allocation of a"e (d) to I in the sense of the Gale-Shapley marriage problem, with the additional feature that every center xi aI has an appetite given by a nonnegative random variable alpha. Generalizing some previous results, we study large deviations for the distance of a typical point xaa"e (d) to its center psi(x)aI, subject to some restrictions on the moments of alpha.

Development of Ternary and Quaternary Catalysts for the Electrooxidation of Glycerol

This work consisted in the preparation of platinum-based catalysts supported on carbon (Vulcan XC-72) and investigation of their physicochemical and electrochemical properties. Catalysts of the C/Pt-Ni-Sn-Me (Me = Ru or Ir) type were prepared by the Pechini method at temperature of 350 degrees C. Four different compositions were homemade: C/Pt60Sn10Ni30, C/Pt60Sn10Ni20Ru10, C/Pt60Sn10Ni10Ru20, and C/Pt60Sn10Ni10Ir20. These catalysts were electrochemically and physically characterized by cyclic voltammetry (CV), chronoamperometry (CA) in the presence of glycerol 1.0 mol dm(-3), X-ray diffraction (XRD), and high-resolution transmission electron microscopy (HRTEM). XRD results showed the main peaks of face-centered cubic Pt. The particle sizes obtained from XRD and HRTEM experiments were close to values ranging from 3 to 8.5 nm. The CV results indicate behavior typical of Pt-based catalysts in acid medium. The CV and CA data reveal that quaternary catalysts present the highest current density for the electrooxidation of glycerol.

Population size of threatened and endemic birds of the Cerrado in Estacao Ecologica de Itirapina, a fragmented area in the State of Sao Paulo, Brazil

The pressures for land use change have led to an increasing isolation of habitat remnants throughout the world. The goal of this study was to estimate the population size and density of some endemic and threatened species in a nature reserve in the Cerrado biome. One hundred and thirty four point transects were undertaken at the Estacao Ecologica de Itirapina (EEI), one of the last natural grassland savannah remnants in Sao Paulo state, in the south-east of Brazil between September and December 2006 and densities estimated for seven species (four endemic to the Cerrado, one near-endemic and two grassland specialists). Neither species reached the minimum viable population size of 500-5000 individuals. Four species, White-banded Tanager, White-rumped Tanager, Black-throated Saltator and Sharp-tailed Tyrant have populations ranging from 112 to 248 individuals, while the other species have a low population (< 60 individuals). The mean densities of Sharp-tailed Tyrant and Cock-tailed Tyrant in the EEI grassland showed similar values to those observed in larger areas of the Cerrado, which may indicate that the EEL grassland area is well conserved. In spite of the restricted size of the EEI, small areas can maintain some endemic and threatened bird populations, thus contributing to local biodiversity and the ecological processes in the region. The capacity of fragments of Cerrado (similar to 2,000 ha) to maintain populations of endemic and threatened bird species is unlikely to be effective in the long term.

Biaxial nematic phase in the Maier-Saupe model for a mixture of discs and cylinders

We analyze the global phase diagram of a Maier-Saupe lattice model with the inclusion of shape-disordered degrees of freedom to mimic a mixture of oblate and prolate molecules (discs and cylinders). In the neighborhood of a Landau multicritical point, solutions of the statistical problem can be written as a Landau-de Gennes expansion for the free energy. If the shape-disordered degrees of freedom are quenched, we confirm the existence of a biaxial nematic structure. If orientational and disorder degrees of freedom are allowed to thermalize, this biaxial solution becomes thermodynamically unstable. Also, we use a two-temperature formalism to mimic the presence of two distinct relaxation times, and show that a slight departure from complete thermalization is enough to stabilize a biaxial nematic phase.

Induction of cellulase and hemicellulase activities of Thermoascus aurantiacus by xylan hydrolyzed products

Thermoascus aurantiacus is able to secrete most of the hemicellulolytic and cellulolytic enzymes. To establish the xylanase inducers of T. aurantiacus, the mycelia were first grown on glucose up until the end of the exponential growth phase, followed by washing and re-suspension in a basal medium without a carbon source. Pre-weighed amounts of xylose (final concentration of 3.5 mg/ml), xylobiose (7 mg/ml) and hydrolyzed xylan from sugarcane bagasse (HXSB) which contained xylose, xylobiose and xylotriose (6.8 mg/ml) were evaluated as inducers of xylanase. It was observed that xylose did not suppress enzyme induction of T. aurantiacus when used in low concentrations, regardless of whether it was inoculated with xylobiose. Xylobiose promoted fast enzyme production stopping after 10 h, even at a low consumption rate of the carbon source; therefore xylobiose appears to be the natural inducer of xylanase. In HXSB only a negligible xylanase activity was determined. Xylose present in HXSB was consumed within the first 10 h while xylobiose was partially hydrolyzed at a slow rate. The profile of alpha-arabinofuranosidase induction was very similar in media induced with xylobiose or HXSB, but induction with xylose showed some positive effects as well. The production profile for the xylanase was accompanied by low levels of cellulolytic activity. In comparison, growth in HXSB resulted in different profiles of both xylanase and cellulase production, excluding the possibility of xylanase acting as endoglucanases.

The role of wax and resin in the nestmate recognition system of a stingless bee, Tetragonisca angustula

Recent research has shown that entrance guards of the stingless bee Tetragonisca angustula make less errors in distinguishing nestmates from non-nestmates than all other bee species studied to date, but how they achieve this is unknown. We performed four experiments to investigate nestmate recognition by entrance guards in T. angustula. We first investigated the effect of colony odours on acceptance. Nestmates that acquired odour from non-nestmate workers were 63% more likely to be rejected while the acceptance rate of non-nestmates treated with nestmate odour increased by only 7%. We further hypothesised that guards standing on the wax entrance tube might use the tube as an odour referent. However, our findings showed that there was no difference in the acceptance of non-nestmates by guards standing on their own colony's entrance tube versus the non-nestmate's entrance tube. Moreover, treatment of bees with nestmate and non-nestmate resin or wax had a negative effect on acceptance rates of up to 65%, regardless of the origin of the wax or resin. The role of resin as a source of recognition cues was further investigated by unidirectionally transferring resin stores between colonies. Acceptance rates of nestmates declined by 37% for hives that donated resin, contrasting with resin donor hives where acceptance of non-nestmates increased by 21%. Overall, our results confirm the accuracy of nestmate recognition in T. angustula and reject the hypothesis that this high level of accuracy is due to the use of the wax entrance tubes as a referent for colony odour. Our findings also suggest that odours directly acquired from resin serve no primary function as nestmate recognition cues. The lack of consistency among colonies plus the complex results of the third and fourth experiments highlight the need for further research on the role of nest materials and cuticular profiles in understanding nestmate recognition in T. angustula.