Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

Quantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetracoordinated Sn compounds of the CH3SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental 119Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH3, H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-311++G** basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms.

Numerical evaluation of the modulus of longitudinal elasticity in structural round timber elements of the Eucalyptus genus

Currently, the standards that deal with the determination of the properties of rigidity and strength for structural round timber elements do not take in consideration in their calculations and mathematical models the influence of the existing irregularities in the geometry of these elements. This study has as objective to determine the effective value of the modulus of longitudinal elasticity for structural round timber pieces of the Eucalyptus citriodora genus by a technique of optimization allied to the Inverse Analysis Method, to the Finite Element Method and the Least Square Method.

Evaluation of the heating of broilers in shed by means of gas hoods and underfloor heating

This study was conducted to evaluate and compare the behavior of the heating inside poultry shed through gas hood and underfloor heating. The experiment was conducted in poultry shed belonging to the Federal Institute of Education, Science and Technology of Triângulo Mineiro Region, Uberlândia city – state of Minas Gerais (MG), Brazil. The dimensions of the shed are 24 meters long and 9.6 meters wide and with a ceiling height of 3.2 meters. The temperature was measured with an optical thermometer of Minipa brand, MT 350 model. It was used, to the analysis of temperature behavior, the public domain software FEMM 4.2, which uses finite elements techniques, with data collected from two lots. Underfloor heating is made using hot water flowing through a serpentine type system, which is installed below the bed; this hot water is from solar heaters. An energetic and economic assessment of the warming shed for raising chickens was realized. From the results obtained with the simulations, it may observe that the heating through the floor provides a more homogeneous distribution of temperature when compared with the hood heating. The flow of heat is upwards supplying, thus, the greatest need of heating of the bird, which is the pectoral part.

Relationship between weight, age and hatching success and the concentration of heavy metals in nestling blue macaw (Anodorhynchus hyacinthinus Latham, 1790) in the Pantanal,Mato Grosso do Sul

Abstract: The concentration of heavy metals (Cr, Fe, Al, As, Cd, Cu, Pb, Mo, Ni, Se and Zn) was evaluated in the blood of nestling blue macaws (Anodorhynchus hyacinthinus) captured in the Pantanal, Mato Grosso do Sul (n=26) in 2012; this was based on the hypothesis that these birds exhibit levels of these heavy metals in their organism and that these interfere in hatching success, weight and age of the chicks. Blood samples were digested with nitric acid and hydrochloric acid and the quantification of metals was performed by ICP-OES (Optical Emission Spectroscopy and Inductively Coupled Plasma). Blood samples of nestlings showed concentrations of Cr (0.10μg/g) Fe (3.06μg/g) Al (3.46μg/g), Cd (0.25μg/g) Cu (0.74μg/g), Mo (0.33μg/g), Ni (0.61μg/g), Se (0.98μg/g), and Zn (2.08μg/g). The levels of heavy metals found were not associated with weight, age and hatching success of the chicks.

Geometric nonlinear dynamic analysis of plates and shells using eight-node hexahedral finite elements with reduced integration

This work presents a geometric nonlinear dynamic analysis of plates and shells using eight-node hexahedral isoparametric elements. The main features of the present formulation are: (a) the element matrices are obtained using reduced integrations with hourglass control; (b) an explicit Taylor-Galerkin scheme is used to carry out the dynamic analysis, solving the corresponding equations of motion in terms of velocity components; (c) the Truesdell stress rate tensor is used; (d) the vector processor facilities existing in modern supercomputers were used. The results obtained are comparable with previous solutions in terms of accuracy and computational performance.

Leaf optical properties of two liana species Canavalia parviflora Benth. and Gouania virgata Reissk in different light conditions

Lianas are plants that depend on support to reach some appreciable height, and they represent an important structural component of tropical forests. Although they predominate in clearings and gaps, some species survive in the understory. Changes in irradiance between these environments can affect leaf morphology and absorption of photosynthetic active radiation (PAR). We had examined the effects of different light regimes on leaf optical properties, chlorophyll content, specific leaf area, and leaf surface morphology in young seedlings of Canavalia parviflora Benth. (Fabaceae) and Gouania virgata Reissk (Rhamnaceae). The seedlings were distributed on workbenches covered by different layers of neutral shade netting, thus creating three levels of light intensity corresponding to about 40%, 10% and 1.5% of solar irradiance. Plants growing in full sun were used as a control. Both species exhibited an increase in reflectance in full sun and alterations in leaf morphology. Reduction in irradiance induced an increase in absorptance (decrease in reflectance and transmittance) in C. parviflora leaves in the green due to higher chlorophyll content. In G. virgata the spectral leaf changes were less observable. However, the efficiency of absorption was more pronounced in G. virgata than in C. parviflora leaves under 40%, 10% and 1.5% photon flux density (PFD). The greater efficiency of absorption in G. virgata was due to a larger specific leaf area (SLA) under these conditions. The adjustments in leaf optical properties can aid these species in overall carbon gain under limited light conditions.

In vitro radioautographic studies of the biodistribution of radiopharmaceuticals on blood elements

In the present study we evaluated the binding of the radiopharmaceuticals sodium pertechnetate (Na 99mTcO4), methylenediphosphonic acid (99mTc-MDP) and glucoheptonate acid (99mTc-GHA) to blood elements using centrifugation and radioautographic techniques. Heparinized blood was incubated with the labelled compounds for 0, 1, 2, 3, 4, 6 and 24 h. Plasma (P) and blood cells (BC) were isolated and precipitated with 5% trichloroacetic acid (TCA), and soluble (SF) and insoluble fractions (IF) were separated. Blood samples were prepared (0 and 24 h) and coated with LM-1 radioautographic emulsions and percent radioactivity (%rad) in P and BC was determined. The binding of Na 99mTcO4 (%rad) to P was 61.2% (0 h) and 46.0% (24 h), and radioautography showed 63.7% (0 h) and 43.3% (24 h). The binding to BC was 38.8% (0 h) and 54.0% (24 h), and radioautography showed 36.3% (0 h) and 56.7% (24 h). 99mTc-MDP study presented 91.1% (0 h) to P and 87.2% (24 h), and radioautography showed 67.9% (0 h) and 67.4% (24 h). The binding to BC was 8.9% (0 h) and 12.8% (24 h), and radioautography showed 32.1% (0 h) and 32.6% (24 h). 99mTc-GHA study was 90.1% (0 h) to P and 79.9% (24 h), and radioautography showed 67.2% (0 h) and 60.1% (24 h). The binding to BC was 9.9% (0 h) and 20.1% (24 h), and radioautography showed 32.8% (0 h) and 39.9% (24 h). The comparison of the obtained results suggests that the binding to plasma and blood cells in the two techniques used (radioautography and centrifugation) is qualitatively in accordance

Measuring higher order optical aberrations of the human eye: techniques and applications

In the present paper we discuss the development of "wave-front", an instrument for determining the lower and higher optical aberrations of the human eye. We also discuss the advantages that such instrumentation and techniques might bring to the ophthalmology professional of the 21st century. By shining a small light spot on the retina of subjects and observing the light that is reflected back from within the eye, we are able to quantitatively determine the amount of lower order aberrations (astigmatism, myopia, hyperopia) and higher order aberrations (coma, spherical aberration, etc.). We have measured artificial eyes with calibrated ametropia ranging from +5 to -5 D, with and without 2 D astigmatism with axis at 45º and 90º. We used a device known as the Hartmann-Shack (HS) sensor, originally developed for measuring the optical aberrations of optical instruments and general refracting surfaces in astronomical telescopes. The HS sensor sends information to a computer software for decomposition of wave-front aberrations into a set of Zernike polynomials. These polynomials have special mathematical properties and are more suitable in this case than the traditional Seidel polynomials. We have demonstrated that this technique is more precise than conventional autorefraction, with a root mean square error (RMSE) of less than 0.1 µm for a 4-mm diameter pupil. In terms of dioptric power this represents an RMSE error of less than 0.04 D and 5º for the axis. This precision is sufficient for customized corneal ablations, among other applications.

Protection of plasmid DNA by a Ginkgo biloba extract from the effects of stannous chloride and the action on the labeling of blood elements with technetium-99m

Ginkgo biloba extract (EGb) is a phytotherapeutic agent used for the treatment of ischemic and neurological disorders. Because the action of this important extract is not fully known, assays using different biological systems need to be performed. Red blood cells (RBC) are labeled with technetium-99m (Tc-99m) and used in nuclear medicine. The labeling depends on a reducing agent, usually stannous chloride (SnCl2). We assessed the effect of different concentrations of EGb on the labeling of blood constituents with Tc-99m, as sodium pertechnetate (3.7 MBq), and on the mobility of a plasmid DNA treated with SnCl2 (1.2 µg/ml) at room temperature. Blood was incubated with EGb before the addition of SnCl2 and Tc-99m. Plasma (P) and RBC were separated and precipitated with trichloroacetic acid, and soluble (SF-P and SF-RBC) and insoluble (IF-P and IF-RBC) fractions were isolated. The plasmid was incubated with Egb, SnCl2 or EGb plus SnCl2 and agarose gel electrophoresis was performed. The gel was stained with ethidium bromide and the DNA bands were visualized by fluorescence in an ultraviolet transilluminator system. EGb decreased the labeling of RBC, IF-P and IF-RBC. The supercoiled form of the plasmid was modified by treatment with SnCl2 and protected by 40 mg/ml EGb. The effect of EGb on the tested systems may be due to its chelating action with the stannous ions and/or pertechnetate or to the capability to generate reactive oxygen species that could oxidize the stannous ion.

Quantitative evidence for neurofilament heavy subunit aggregation in motor neurons of spinal cords of patients with amyotrophic lateral sclerosis

Amyotrophic lateral sclerosis (ALS), a neurodegenerative disease of unknown etiology, affects motor neurons leading to atrophy of skeletal muscles, paralysis and death. There is evidence for the accumulation of neurofilaments (NF) in motor neurons of the spinal cord in ALS cases. NF are major structural elements of the neuronal cytoskeleton. They play an important role in cell architecture and differentiation and in the determination and maintenance of fiber caliber. They are composed of three different polypeptides: light (NF-L), medium (NF-M) and heavy (NF-H) subunits. In the present study, we performed a morphological and quantitative immunohistochemical analysis to evaluate the accumulation of NF and the presence of each subunit in control and ALS cases. Spinal cords from patients without neurological disease and from ALS patients were obtained at autopsy. In all ALS cases there was a marked loss of motor neurons, besides atrophic neurons and preserved neurons with cytoplasmic inclusions, and extensive gliosis. In control cases, the immunoreaction in the cytoplasm of neurons was weak for phosphorylated NF-H, strong for NF-M and weak for NF-L. In ALS cases, anterior horn neurons showed intense immunoreactivity in focal regions of neuronal perikarya for all subunits, although the difference in the integrated optical density was statistically significant only for NF-H. Furthermore, we also observed dilated axons (spheroids), which were immunopositive for NF-H but negative for NF-M and NF-L. In conclusion, we present qualitative and quantitative evidence of NF-H subunit accumulation in neuronal perikarya and spheroids, which suggests a possible role of this subunit in the pathogenesis of ALS.

Essential regulatory elements for NHE3 gene transcription in renal proximal tubule cells

The objectives of the present study were to identify the cis-elements of the promoter absolutely required for the efficient rat NHE3 gene transcription and to locate positive and negative regulatory elements in the 5’-flanking sequence (5’FS), which might modulate the gene expression in proximal tubules, and to compare this result to those reported for intestinal cell lines. We analyzed the promoter activity of different 5’FS segments of the rat NHE3 gene, in the OKP renal proximal tubule cell line by measuring the activity of the reporter gene luciferase. Because the segment spanning the first 157 bp of 5’FS was the most active it was studied in more detail by sequential deletions, point mutations, and gel shift assays. The essential elements for gene transcription are in the region -85 to -33, where we can identify consensual binding sites for Sp1 and EGR-1, which are relevant to NHE3 gene basal transcription. Although a low level of transcription is still possible when the first 25 bp of the 5’FS are used as promoter, efficient transcription only occurs with 44 bp of 5’FS. There are negative regulatory elements in the segments spanning -1196 to -889 and -467 to -152, and positive enhancers between -889 and -479 bp of 5’FS. Transcription factors in the OKP cell nuclear extract efficiently bound to DNA elements of rat NHE3 promoter as demonstrated by gel shift assays, suggesting a high level of similarity between transcription factors of both species, including Sp1 and EGR-1.

Optical coherence tomography imaging of the basal ganglia: feasibility and brief review

Optical coherence tomography (OCT) is a promising medical imaging technique that uses light to capture real-time cross-sectional images from biological tissues in micrometer resolution. Commercially available optical coherence tomography systems are employed in diverse applications, including art conservation and diagnostic medicine, notably in cardiology and ophthalmology. Application of this technology in the brain may enable distinction between white matter and gray matter, and obtainment of detailed images from within the encephalon. We present, herein, the in vivo implementation of OCT imaging in the rat brain striatum. For this, two male 60-day-old rats (Rattus norvegicus, Albinus variation, Wistar) were stereotactically implanted with guide cannulas into the striatum to guide a 2.7-French diameter high-definition OCT imaging catheter (Dragonfly™, St. Jude Medical, USA). Obtained images were compared with corresponding histologically stained sections to collect imaging samples. A brief analysis of OCT technology and its current applications is also reported, as well as intra-cerebral OCT feasibility on brain mapping during neurosurgical procedures.

Effect of blanching time on selective mineral elements extraction from the spinach substitute (Tetragonia expansa) commonly used in Brazil

The true spinach (Spinacia oleracea) does not grow well in warm climates and for that reason is not commercialized in Brazil. Instead, a spinach substitute (Tetragonia expansa), originally from New Zealand, is widely used in the country. There is scant information on the mineral profile and none on the soluble mineral fraction of this vegetable. The solubility of a mineral is one of the important factors for its absorption. For this reason, the calcium, magnesium, iron, manganese, copper, zinc, potassium, and sodium soluble fractions in the raw spinach substitute were determined and the effect of blanching times on the solubility of these minerals was investigated. Blanching times of 1, 5, and 15 minutes were employed. The magnesium, manganese, potassium, and sodium soluble fractions increased sizably with shorter blanching time. Longer blanching time (15 minutes) caused large losses of minerals. The soluble mineral fractions can contribute poorly to diet in terms of potassium, magnesium, manganese, and zinc. The spinach substitute cannot be considered a dietary source of calcium, iron and copper due to the insolubility of these minerals in the vegetable, possibly caused by the large oxalate content.

Mineral characterization of native fruits from the southern region of Brazil

Although the greatest variety of Brazilian flora is in the Amazon region, the Southern region of Brazil also has an estimated number of at least 5,000 species of vascular native plants. These species have been neglected as potential food sources, remaining unknown and under-utilized and limiting the potential variety in the diet of Brazilians and other peoples. Therefore the aim of this study was to characterize the mineral composition and content present in seven native fruit species of Southern Brazil using inductively coupled plasma optical emission spectrometry (ICP-OES). The essential element concentrations in the fruit samples were higher or similar to the values reported for traditional fruits. The araticum-do-mato fruit samples had high concentrations of the elements Ca, K, and Cu, and trace elements such as Pb and Sr. Mandacaru-de-três-quinas had predominance of Ba, Bi, and Ga, and the essential elements Mg and Mn. Uvaia and guabiroba had the highest levels of Al and Cr, but uvaia had high levels of Fe and Zn. The pindo palm had high amounts of Cd and Ni, and the yellow guava had high concentrations of Na, while red guava had high levels of Co.

Physicochemical composition, minerals, and pesticide residues in organic grape juices

Demand for organic products is intensified in many countries each year. Following this trend, Brazil produces increasing volumes of organic grape juice. In this way, a survey of organic grape juices made from grapes produced according to this system was carried out where physicochemical composition, minerals, trace elements, and pesticide residues were determined. Variables related to grape juice composition were performed by physicochemical procedures; minerals and trace elements, by inductively plasma optical emission spectrometry; pesticide residues, by liquid chromatography-mass spectrometry. Main results show that the physicochemical composition of organic grape juices was in general in accordance to the Brazilian legislation. The mean concentrations of trace elements were very low, varying from 0.002 (Cd) to 0.970 (Ba) mg L–1. Pesticide residues were not detected in any sample analyzed (MRL= 10 µg L–1). These results show that the Serra Gaúcha viticultural region present conditions to produce organic grape juices, despite the adverse climate factors that occurs in some years. Nevertheless, these products should be made with grape varieties, such as the labrusca ones, less susceptibles to the main grapevine pathogens.