Quiralidade em moléculas e cristais

The present contribution describes some concepts of stereochemistry and chirality in molecules and crystals. This paper also reports on the development of a simple and fast experiment to prepare and recognize conglomerate and true racemate of tartaric acid produced by mechanic mixture of commercial enantiomers and recristalization. Optical activity and melting point of mixtures are also used in the analysis.

Determinação do ponto de névoa em surfactantes não iônicos por espectroscopia de impedância elétrica

In this paper, we analyze the use of electrical impedance spectroscopy applied to determination of cloud point. The slope of admittance measured at 100 kHz is reduced to temperature above the critical value which characterizes the phase transition, in a strong indication that this process is activated during the clouding. Additionally to this study we explored the influence of parameters such as additives and temperature on the performance of phase separation of residues (silver nanoparticles) by cloud point extraction. The interaction with salt maximizes the separation of chemical residues in a progressively reduced temperature.

Application of cloud point preconcentration and flame atomic absorption spectrometry for the determination of cadmium and zinc ions in urine, blood serum and water samples

A simple, sensitive and selective cloud point extraction procedure is described for the preconcentration and atomic absorption spectrometric determination of Zn2+ and Cd2+ ions in water and biological samples, after complexation with 3,3',3",3'"-tetraindolyl (terephthaloyl) dimethane (TTDM) in basic medium, using Triton X-114 as nonionic surfactant. Detection limits of 3.0 and 2.0 µg L-1 and quantification limits 10.0 and 7.0 µg L-1were obtained for Zn2+ and Cd2+ ions, respectively. Relative standard deviation was 2.9 and 3.3, and enrichment factors 23.9 and 25.6, for Zn2+ and Cd2+ ions, respectively. The method enabled determination of low levels of Zn2+ and Cd2+ ions in urine, blood serum and water samples.

A reliable method of quantification of trace copper in beverages with and without alcohol by spectrophotometry after cloud point extraction

A new cloud point extraction (CPE) method was developed for the separation and preconcentration of copper (II) prior to spectrophotometric analysis. For this purpose, 1-(2,4-dimethylphenyl) azonapthalen-2-ol (Sudan II) was used as a chelating agent and the solution pH was adjusted to 10.0 with borate buffer. Polyethylene glycol tert-octylphenyl ether (Triton X-114) was used as an extracting agent in the presence of sodium dodecylsulphate (SDS). After phase separation, based on the cloud point of the mixture, the surfactant-rich phase was diluted with acetone, and the enriched analyte was spectrophotometrically determined at 537 nm. The variables affecting CPE efficiency were optimized. The calibration curve was linear within the range 0.285-20 µg L-1 with a detection limit of 0.085 µg L-1. The method was successfully applied to the quantification of copper in different beverage samples.

Determination of triamterene in human plasma and urine after its cloud point extraction

A new analytical approach was developed involving cloud point extraction (CPE) and spectrofluorimetric determination of triamterene (TM) in biological fluids. A urine or plasma sample was prepared and adjusted to pH 7, then TM was quickly extracted using CPE, using 0.05% (w/v) of Triton X-114 as the extractant. The main factors that affected the extraction efficiency (the pH of the sample, the Triton X-114 concentration, the addition of salt, the extraction time and temperature, and the centrifugation time and speed) were studied and optimized. The method gave calibration curves for TM with good linearities and correlation coefficients (r) higher than 0.99. The method showed good precision and accuracy, with intra- and inter-assay precisions of less than 8.50% at all concentrations. Standard addition recovery tests were carried out, and the recoveries ranged from 94.7% to 114%. The limits of detection and quantification were 3.90 and 11.7 µg L-1, respectively, for urine and 5.80 and 18.0 µg L-1, respectively, for plasma. The newly developed, environmentally friendly method was successfully used to extract and determine TM in human urine samples.

Ligandless cloud point extraction of trace amounts of palladium and rhodium in road dust samples using Span 80 prior to their determination by flame atomic absorption spectrometry

In this study, a procedure is developed for cloud point extraction of Pd(II) and Rh(III) ions in aqueous solution using Span 80 (non-ionic surfactant) prior to their determination by flame atomic absorption spectroscopy. This method is based on the extraction of Pd(II) and Rh(III) ions at a pH of 10 using Span 80 with no chelating agent. We investigated the effect of various parameters on the recovery of the analyte ions, including pH, equilibration temperature and time, concentration of Span 80, and ionic strength. Under the best experimental conditions, the limits of detection based on 3Sb for Pd(II) and Rh(III) ions were 1.3 and 1.2 ng mL-1, respectively. Seven replicate determinations of a mixture of 0.5 µg mL-1 palladium and rhodium ions gave a mean absorbance of 0.058 and 0.053 with relative standard deviations of 1.8 and 1.6%, respectively. The developed method was successfully applied to the extraction and determination of the palladium and rhodium ions in road dust and standard samples and satisfactory results were obtained.

PREDICTING THE BOILING POINT OF PCDD/Fs BY THE QSPR METHOD BASED ON THE MOLECULAR DISTANCE-EDGE VECTOR INDEX

The quantitative structure property relationship (QSPR) for the boiling point (Tb) of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) was investigated. The molecular distance-edge vector (MDEV) index was used as the structural descriptor. The quantitative relationship between the MDEV index and Tb was modeled by using multivariate linear regression (MLR) and artificial neural network (ANN), respectively. Leave-one-out cross validation and external validation were carried out to assess the prediction performance of the models developed. For the MLR method, the prediction root mean square relative error (RMSRE) of leave-one-out cross validation and external validation was 1.77 and 1.23, respectively. For the ANN method, the prediction RMSRE of leave-one-out cross validation and external validation was 1.65 and 1.16, respectively. A quantitative relationship between the MDEV index and Tb of PCDD/Fs was demonstrated. Both MLR and ANN are practicable for modeling this relationship. The MLR model and ANN model developed can be used to predict the Tb of PCDD/Fs. Thus, the Tb of each PCDD/F was predicted by the developed models.

Critical-point yield model to estimate yield damage caused by Cercospora zea-maydis in corn

A model to estimate damage caused by gray leaf spot of corn (Cercospora zea-maydis) was developed from experimental field data gathered during the summer seasons of 2000/01 and during the second crop season [January-seedtime] of 2001, in the southwest of Goiás state. Three corn hybrids were grown over two seasons and on two sites, resulting in 12 experimental plots. A disease intensity gradient (lesions per leaf) was generated through application, three times over the season, of five different doses of the fungicide propiconazol. From tasseling onward, disease intensity on the ear leaf (El), and El - 1, El - 2, El + 1, and El + 2, was evaluated weekly. A manual harvest at the physiological ripening stage was followed by grain drying and cleaning. Finally, grain yield in kg.ha-1 was estimated. Regression analysis, performed between grain yield and all combinations of the number of lesions on each leaf type, generated thirty linear equations representing the damage function. To estimate losses caused by different disease intensities at different corn growth stages, these models should first be validated. Damage coefficients may be used in determining the economic damage threshold.

Critical-point model to estimate yield loss caused by Asian soybean rust

ABSTRACTA model to estimate yield loss caused by Asian soybean rust (ASR) (Phakopsora pachyrhizi) was developed by collecting data from field experiments during the growing seasons 2009/10 and 2010/11, in Passo Fundo, RS. The disease intensity gradient, evaluated in the phenological stages R5.3, R5.4 and R5.5 based on leaflet incidence (LI) and number of uredinium and lesions/cm2, was generated by applying azoxystrobin 60 g a.i/ha + cyproconazole 24 g a.i/ha + 0.5% of the adjuvant Nimbus. The first application occurred when LI = 25% and the remaining ones at 10, 15, 20 and 25-day intervals. Harvest occurred at physiological maturity and was followed by grain drying and cleaning. Regression analysis between the grain yield and the disease intensity assessment criteria generated 56 linear equations of the yield loss function. The greatest loss was observed in the earliest growth stage, and yield loss coefficients ranged from 3.41 to 9.02 kg/ha for each 1% LI for leaflet incidence, from 13.34 to 127.4 kg/ha/1 lesion/cm2 for lesion density and from 5.53 to 110.0 kg/ha/1 uredinium/cm2 for uredinium density.

Accuracy and efficiency evaluation of point-centered quarter method variations for vegetation sampling in an araucaria forest

In order to verify Point-Centered Quarter Method (PCQM) accuracy and efficiency, using different numbers of individuals by per sampled area, in 28 quarter points in an Araucaria forest, southern Paraná, Brazil. Three variations of the PCQM were used for comparison associated to the number of sampled individual trees: standard PCQM (SD-PCQM), with four sampled individuals by point (one in each quarter), second measured (VAR1-PCQM), with eight sampled individuals by point (two in each quarter), and third measuring (VAR2-PCQM), with 16 sampled individuals by points (four in each quarter). Thirty-one species of trees were recorded by the SD-PCQM method, 48 by VAR1-PCQM and 60 by VAR2-PCQM. The level of exhaustiveness of the vegetation census and diversity index showed an increasing number of individuals considered by quadrant, indicating that VAR2-PCQM was the most accurate and efficient method when compared with VAR1-PCQM and SD-PCQM.

Erosion factors and magnetic susceptibility in differet compartments of a slope in Gilbués-PI, Brazil

The erosion is the degradation of soil with effects on crop productivity and pollution of the environment. To understand the spatial variability of this phenomenon, geostatistical techniques and concepts of soil-landscape can be used to identify landscape compartments with different potential of erosion. The aim of this study was to understand the factors of erosion in landscape compartments and the relations with the magnetic susceptibility (MS) of the soils in a slope in Gilbués, state of Piauí (PI), Brazil. Sampling meshes were set in compartments I and II with 121 points and in compartment III with 99 points spaced every 10 meters. There was significant difference to erodibility (K) and risk of erosion (RE); the spatial variability of MS was lower than the factors of soil erosion. The soil losses (A), the natural erosion potential (NEP), the RE and the MS had spatial relation with the topographic factor, indicating dependence of the erosion with the relief. We concluded that losses of soil, natural erosion potential and risk of erosion have spatial relation with the topographic factor, showing the dependence of the erosion factors with the relief. The soil magnetic susceptibility can be used as an auxiliary variable in the indirect quantification of the erodibility factor and the risk of soil erosion.

Bimodal pore distribution on soils under conservation management system for coffee crop

This study aims at detailing bimodal pore distribution by means of water retention curve in an oxidic-gibbsitic Latosol and in a kaolinitic cambisol Latossol under conservation management system of coffee crop. Samples were collected at depths of 20; 40; 80; 120 and 160 cm on coffee trees rows and between rows under oxidic-gibbsitic Latosol (LVd) and kaolinitic cambisol Latossol (LVAd). Water retention curve was determined at matrix potentials (Ψm) -1; -2; -4; -6; -10 kPa obtained from the suction unit; the Ψm of -33; -100; -500; -1,500 kPa were obtained by the Richards extractor, and WP4-T psychrometer was used to determine Ψm -1,500 to -300,000 kPa. The water retention data were adjusted to the double van Genuchten model by nonlinear model procedures of the R 2.12.1 software. Was estimated the model parameter and inflection point slope. The system promoted changes in soil structure and water retention for the conditions evaluated, and both showed bimodal pores distribution, which were stronger in LVd. There was a strong influence of mineralogy gibbsitic in the water retention more negative than Ψm -1500 kPa, reflected in the values of the residual water content.

Evaluation of roof slope and exposure with different roofing materials in reduced models of animal production facilities in spring and summer

The present study was conducted at the Department of Rural Engineering and the Department of Animal Morphology and Physiology of FCAV/Unesp, Jaboticabal, SP, Brazil. The objective was to verify the influence of roof slope, exposure and roofing material on the internal temperature of reduced models of animal production facilities. For the development of the research, 48 reduced and dissemble models with dimensions 1.00 × 1.00 × 0.50 m were used. The roof was shed-type, and the models faced to the North or South directions, with 24 models for each side of exposure. Ceramic, galvanized-steel and fibro tiles were used to build the roofs. Slopes varied between 20, 30, 40 and 50% for the ceramic tile and 10, 30, 40 and 50% for the other two. Inside the models, temperature readings were performed at every hour, for 12 months. The results were evaluated in a general linear model in a nested 3 × 4 × 2 factorial arrangement, in which the effects of roofing material and exposure were nested on the factor Slope. Means were compared by the Tukey test at 5% of probability. After analyzing the data, we observed that with the increase in the slope and exposure to the South, there was a drop in the internal temperature within the model at the geographic coordinates of Jaboticabal city (SP/Brazil).

Critical aspects on the behavior of material from the mechanical tool-workpiece interaction in single point diamond turning

Some material aspects such as grain size, purity and anisotropy exert an important influence on surface quality, especially in single point diamond turning. The aim of this paper is to present and discuss some critical factors that can limit the accuracy of ultraprecision machining of non-ferrous metals and to identify the effects of them on the cutting mechanism with single point diamond tools. This will be carried out through observations of machined surfaces and chips produced using optical and scanning electron microscopy. Solutions to reduce the influence of some of these limiting factors related with the mechanism of generation of mirror-like surfaces will be discussed.

Local Web Buckling in Tapered Composite Beams: A Parametric Study

Composite flooring systems supported by tapered (varying web depth) beams are very attractive from an economic point of view. However, the tapered beam sections are fabricated from plate by welding, and are susceptible to imperfection effects. These may interact with the localised compressive stress field that is generated in the web at a slope change in the lower flange to cause local web buckling. A substantial parametric study using a non-linear elasto-plastic finite element program and covering practical ranges of the important parameters including the area of the tension flange, taper slope and web thickness is reported. Moment-rotation relations, peak moments and failure mechanisms have been predicted. The validity of the work is supported by the good correlation obtained between the results of the parametric study and experimental data.