A NOVEL METHOD FOR THE DETERMINATION OF TRACE THORIUM BY DISPERSIVE LIQUID-LIQUID MICROEXTRACTION BASED ON SOLIDIFICATION OF FLOATING ORGANIC DROP

In this study, dispersive liquid-liquid microextraction based on the solidification of floating organic droplets was used for the preconcentration and determination of thorium in the water samples. In this method, acetone and 1-undecanol were used as disperser and extraction solvents, respectively, and the ligand 1-(2-thenoyl)-3,3,3-trifluoracetone reagent (TTA) and Aliquat 336 was used as a chelating agent and an ion-paring reagent, for the extraction of thorium, respectively. Inductively coupled plasma-optical emission spectrometry was applied for the quantitation of the analyte after preconcentration. The effect of various factors, such as the extraction and disperser solvent, sample pH, concentration of TTA and concentration of aliquat336 were investigated. Under the optimum conditions, the calibration graph was linear within the thorium content range of 1.0-250 µg L-1 with a detection limit of 0.2 µg L-1. The method was also successfully applied for the determination of thorium in the different water samples.

Validation study of an overall radiation balance estimation method under Ponta Grossa (PR) Brazil weather conditions

Radiation balance is the fraction of incident solar radiation upon earth surface which is available to be used in several natural processes, such as biological metabolism, water loss by vegetated surfaces, variation of temperature in farming systems and organic decomposition. The present study aimed to assess and validate the performance of two estimation models for Rn in Ponta Grossa city, Paraná State, Brazil. To this end, during the period of 04/01/2008 to 04/30/2011, from radiometric data collected by an automatic weather station set at the Experimental Station, of the State University of Ponta Grossa. We performed a linear regression study by confrontation between measurements made through radiometric balance and Rn estimates obtained from Brunt classical method, and the proposed method. Both models showed excellent performance and were confirmed by the statistical parameters applied. However, the alternative method has the advantage of requiring only global solar radiation values, temperature, and relative humidity.

QT interval in healthy dogs: which method of correcting the QT interval in dogs is appropriate for use in small animal clinics?

The electrocardiography (ECG) QT interval is influenced by fluctuations in heart rate (HR) what may lead to misinterpretation of its length. Considering that alterations in QT interval length reflect abnormalities of the ventricular repolarisation which predispose to occurrence of arrhythmias, this variable must be properly evaluated. The aim of this work is to determine which method of correcting the QT interval is the most appropriate for dogs regarding different ranges of normal HR (different breeds). Healthy adult dogs (n=130; German Shepherd, Boxer, Pit Bull Terrier, and Poodle) were submitted to ECG examination and QT intervals were determined in triplicates from the bipolar limb II lead and corrected for the effects of HR through the application of three published formulae involving quadratic, cubic or linear regression. The mean corrected QT values (QTc) obtained using the diverse formulae were significantly different (ρ<0.05), while those derived according to the equation QTcV = QT + 0.087(1- RR) were the most consistent (linear regression). QTcV values were strongly correlated (r=0.83) with the QT interval and showed a coefficient of variation of 8.37% and a 95% confidence interval of 0.22-0.23 s. Owing to its simplicity and reliability, the QTcV was considered the most appropriate to be used for the correction of QT interval in dogs.

Non-linear analysis of laminated metal matrix composites by an integrated micro/macro-mechanical model

The present paper describes an integrated micro/macro mechanical study of the elastic-viscoplastic behavior of unidirectional metal matrix composites (MMC). The micromechanical analysis of the elastic moduli is based on the Composites Cylinder Assemblage model (CCA) with comparisons also draw with a Representative Unit Cell (RUC) technique. These "homogenization" techniques are later incorporated into the Vanishing Fiber Diameter (VFD) model and a new formulation is proposed. The concept of a smeared element procedure is employed in conjunction with two different versions of the Bodner and Partom elastic-viscoplastic constitutive model for the associated macroscopic analysis. The formulations developed are also compared against experimental and analytical results available in the literature.

Substitution-Newton-Raphson method applied to the modeling of a vapour compression refrigeration system using different representations of the thermodynamic properties of R-134a

This paper gives a detailed presentation of the Substitution-Newton-Raphson method, suitable for large sparse non-linear systems. It combines the Successive Substitution method and the Newton-Raphson method in such way as to take the best advantages of both, keeping the convergence features of the Newton-Raphson with the low requirements of memory and time of the Successive Substitution schemes. The large system is solved employing few effective variables, using the greatest possible part of the model equations in substitution fashion to fix the remaining variables, but maintaining the convergence characteristics of the Newton-Raphson. The methodology is exemplified through a simple algebraic system, and applied to a simple thermodynamic, mechanical and heat transfer modeling of a single-stage vapor compression refrigeration system. Three distinct approaches for reproducing the thermodynamic properties of the refrigerant R-134a are compared: the linear interpolation from tabulated data, the use of polynomial fitted curves and the use of functions derived from the Helmholtz free energy.

Using the best linear predictor (BLP) in the selection between and among half-sib progenies of the CMS-39 maize population

Data of corn ear production (kg/ha) of 196 half-sib progenies (HSP) of the maize population CMS-39 obtained from experiments carried out in four environments were used to adapt and assess the BLP method (best linear predictor) in comparison with to the selection among and within half-sib progenies (SAWHSP). The 196 HSP of the CMS-39 population developed by the National Center for Maize and Sorghum Research (CNPMS-EMBRAPA) were related through their pedigree with the recombined progenies of the previous selection cycle. The two methodologies used for the selection of the twenty best half-sib progenies, BLP and SAWHSP, led to similar expected genetic gains. There was a tendency in the BLP methodology to select a greater number of related progenies because of the previous generation (pedigree) than the other method. This implies that greater care with the effective size of the population must be taken with this method. The SAWHSP methodology was efficient in isolating the additive genetic variance component from the phenotypic component. The pedigree system, although unnecessary for the routine use of the SAWHSP methodology, allowed the prediction of an increase in the inbreeding of the population in the long term SAWHSP selection when recombination is simultaneous to creation of new progenies.

An improved HPLC method for the quantitation of 6-mercaptopurine and its metabolites in red blood cells

A procedure is described for the rapid determination of the intra-erythrocyte concentration of 6-mercaptopurine (6-MP) and its metabolites, 6-thioguanine nucleotides (6-TGN) and 6-methylmercaptopurine (6-MMP). Erythrocytes (8 x 10(8) cells) in 350 µl Hanks solution containing 7.5 mg dithiothreitol were treated with 50 µl 70% perchloric acid. The precipitate was removed by centrifugation (13,000 g) and the supernatant hydrolyzed at 100°C for 45 min. After cooling, 100 µl was analyzed directly by HPLC using a Radialpack Resolve C18 column eluted with methanol-water (7.5:92.5, v/v) containing 100 mM triethylamine. 6-TG, 6-MP and the hydrolysis product of 6-MMP, 4-amino-5-(methylthio)carbonyl imidazole, were monitored at 342, 322 and 303 nm using a Shimadzu SPD-M10A diode array UV detector. The analytes eluted at 5.3, 6.0 and 10.2 min, respectively. The calibration curves were linear (r² > 0.998), and the analytical recoveries were 73.2% for 6-TG, 119.1% for 6-MP and 97.4% for 6-MMP. The intra- and inter-assay variations were highest for 6-MP (9.6 and 14.3%, respectively). The lowest detectable concentrations were 3, 3 and 25 pmol/8 x 10(8) erythrocytes for 6-TG, 6-MP and 6-MMP, respectively. The quantification limits (coefficients of variation <15%) were 8, 10 and 70 pmol/8 x 10(8) erythrocytes for 6-TG, 6-MP and 6-MMP, respectively. The method was applied to the analysis of 183 samples from 36 children under chemotherapy for acute lymphoblastic leukemia. The concentrations of the metabolites in the red cells of the patients ranged from 0 to 1934 pmol/8 x 10(8) erythrocytes for 6-TGN, and from 0 to 105.8 and 0 to 45.9 nmol/8 x 10(8) erythrocytes for 6-MP and 6-MMP, respectively. The procedure gave results that were in agreement with those obtained with other methods designed to detect cases of non-compliance with treatment, including patient interviews and medical evaluation, among others, demonstrating its applicability to monitoring the treatment of leukemic children.

An HPLC-UV method for the measurement of permeability of marker drugs in the Caco-2 cell assay

The Caco-2 cell line has been used as a model to predict the in vitro permeability of the human intestinal barrier. The predictive potential of the assay relies on an appropriate in-house validation of the method. The objective of the present study was to develop a single HPLC-UV method for the identification and quantitation of marker drugs and to determine the suitability of the Caco-2 cell permeability assay. A simple chromatographic method was developed for the simultaneous determination of both passively (propranolol, carbamazepine, acyclovir, and hydrochlorothiazide) and actively transported drugs (vinblastine and verapamil). Separation was achieved on a C18 column with step-gradient elution (acetonitrile and aqueous solution of ammonium acetate, pH 3.0) at a flow rate of 1.0 mL/min and UV detection at 275 nm during the total run time of 35 min. The method was validated and found to be specific, linear, precise, and accurate. This chromatographic system can be readily used on a routine basis and its utilization can be extended to other permeability models. The results obtained in the Caco-2 bi-directional transport experiments confirmed the validity of the assay, given that high and low permeability profiles were identified, and P-glycoprotein functionality was established.

Body composition measures of obese adolescents by the deuterium oxide dilution method and by bioelectrical impedance

The objectives of the present study were to describe and compare the body composition variables determined by bioelectrical impedance (BIA) and the deuterium dilution method (DDM), to identify possible correlations and agreement between the two methods, and to construct a linear regression model including anthropometric measures. Obese adolescents were evaluated by anthropometric measures, and body composition was assessed by BIA and DDM. Forty obese adolescents were included in the study. Comparison of the mean values for the following variables: fat body mass (FM; kg), fat-free mass (FFM; kg), and total body water (TBW; %) determined by DDM and by BIA revealed significant differences. BIA overestimated FFM and TBW and underestimated FM. When compared with data provided by DDM, the BIA data presented a significant correlation with FFM (r = 0.89; P < 0.001), FM (r = 0.93; P < 0.001) and TBW (r = 0.62; P < 0.001). The Bland-Altman plot showed no agreement for FFM, FM or TBW between data provided by BIA and DDM. The linear regression models proposed in our study with respect to FFM, FM, and TBW were well adjusted. FFM obtained by DDM = 0.842 x FFM obtained by BIA. FM obtained by DDM = 0.855 x FM obtained by BIA + 0.152 x weight (kg). TBW obtained by DDM = 0.813 x TBW obtained by BIA. The body composition results of obese adolescents determined by DDM can be predicted by using the measures provided by BIA through a regression equation.

In-house method validation and occurrence of alpha-, beta-endosulfan, endosulfan sulphate, lambda-cyhalothrin, procymidone and trifluralin residues in strawberry

A method for determination of organohalogen pesticides in strawberry by gas chromatography with electron capture detection was validated and applied in a monitoring program. Linearity, matrix effects, and day effect were evaluated for the analytes alpha-endosulfan, beta-endosulfan, endosulfan sulphate, lambda-cyhalothrin, procymidone, and trifluralin. The linear range varied according to the chromatographic response of the analyte. Significant matrix effects were observed. The mean recoveries ranged from 74.6 to 115.4%, with repeatability standard deviations between 1.6 and 21.0% and intermediate precision between 5.9 and 21.0%. Detection, quantification and decision limit, and detection capacity ranged from 0.003 to 0.007 mg/kg, 0.005 to 0.013 mg/kg; 0.003 to 3.128 mg/kg; and 0.005 to 3.266 mg/kg, respectively. The method was fit for the purpose of monitoring organohalogen residues in strawberries. Residues of these pesticides were detected in 124 of the 186 samples analyzed between 2009 and 2011 in the state of Minas Gerais. Nine of them did not comply with the current legislation requirements; among them, seven (3.8%) had residues of unauthorized pesticide for the culture of strawberry, one (0.5%) had residues above the maximum residue limit, and another one (0.5%) exhibited both non-conformities.