O estado da arte da cromatografia associada à espectrometria de massas acoplada à espectrometria de massas na análise de compostos tóxicos em alimentos

Chromatography combined with several different detection systems is one of the more used and better performing analytical tools. Chromatography with tandem mass spectrometric detection gives highly selective and sensitive analyses and permits obtaining structural information about the analites and about their molar masses. Due to these characteristics, this analytical technique is very efficient when used to detect substances at trace levels in complex matrices. In this paper we review instrumental and technical aspects of chromatography-tandem mass spectrometry and the state of the art of the technique as it is applied to analysis of toxic substances in food.

Atribuição absoluta e geral de isômeros constitucionais por espectrometria de massas: o caso das metilpiperidinas

An absolute method is described via mass spectrometry (MS) for the structural assignment of isomers within the class of methylpiperidines. The method explores both the unimolecular and bimolecular gas phase behavior of structurally diagnostic fragment ions (SDFI). For the methylpiperidnes, the isomeric 2-methyl, 3-methyl and 4-methyl 2-azabutadienyl cations are found to function as SDFI. These fragment ions are expected to be formed from all members within the class, to be stable and to retain the structural information of the precursor molecule, and to not interconvert into one another. To characterize these SDFI, both the collision induced dissociation (CID) in argon and bimolecular ion/molecule chemistry with ethyl vinyl ether were compared.

Modelagem matemática e simulação numérica do resfriamento rápido de morango com ar forçado

This work approaches the forced air cooling of strawberry by numerical simulation. The mathematical model that was used describes the process of heat transfer, based on the Fourier's law, in spherical coordinates and simplified to describe the one-dimensional process. For the resolution of the equation expressed for the mathematical model, an algorithm was developed based on the explicit scheme of the numerical method of the finite differences and implemented in the scientific computation program MATLAB 6.1. The validation of the mathematical model was made by the comparison between theoretical and experimental data, where strawberries had been cooled with forced air. The results showed to be possible the determination of the convective heat transfer coefficient by fitting the numerical and experimental data. The methodology of the numerical simulations was showed like a promising tool in the support of the decision to use or to develop equipment in the area of cooling process with forced air of spherical fruits.

Efeitos da temperatura do ar, linhagem e período do dia nas freqüências de ocorrências e tempos de expressão comportamental de matrizes pesadas

Behavioral adjustments may occur fast and with less cost than the physiological adaptations. Considering the social behavior is suggestive that the frequency and the intensity of aggressive interactions, the total social cohesion and the extent of vicious attitudes may be used to evaluate welfare. This research presents an analysis of the interactions between the experimental factors such as temperature, genetic and time of the day in the behavior of female broiler breeders under controlled environment in a climatic chamber in order to enhance the different reaction of the birds facing distinct environmental conditions. The results showed significant differences between the behaviors expressed by the studied genetics presenting the need of monitoring them in real-time in order to predict their welfare in commercial housing, due to the complexity of the environmental variables that interfere in the well being process. The research also concluded that the welfare evaluation of female broiler breeders needs to consider the time of the day during the observation of the behaviors.

Influência da temperatura do ar de secagem no calor latente de vaporização de água em feijão macassar (Vigna unguiculata (L.) Walp.), variedade sempre-verde

In order to determine the energy needed to artificially dry an agricultural product the latent heat of vaporization of moisture in the product, H, must be known. Generally, the expressions for H reported in the literature are of the form H = h(T)f(M), where h(T) is the latent heat of vaporization of free water, and f(M) is a function of the equilibrium moisture content, M, which is a simplification. In this article, a more general expression for the latent heat of vaporization, namely H = g(M,T), is used to determine H for cowpea, always-green variety. For this purpose, a computer program was developed which automatically fits about 500 functions, with one or two independent variables, imbedded in its library to experimental data. The program uses nonlinear regression, and classifies the best functions according to the least reduced chi-squared. A set of executed statistical tests shows that the generalized expression for H used in this work produces better results of H for cowpea than other equations found in literature.

Produção de alface hidropônica em três ambientes de cultivo

It was proposed to evaluate the hydroponic lettuce production, variety Vera, on inclined benches with channels of 100 mm, and Nutrient Film Technique, as answer to carbon dioxide application and evaporative cooling. There were five cycles of cultivation from March, 20th to April, 17th (C1); from May, 25th to June, 29th (C2); from July, 13th to August, 20th (C3); from August, 27th to October, 10th (C4); from December, 12th to January, 10th (C5). In three greenhouses were tested the following systems: (A1) without evaporative cooling air CO2 aerial injection, (A2) with CO2 aerial injection and without evaporative cooling and (A3) with CO2 aerial injection and pad-fan evaporative cooling system. The fresh and dry mass of leaves in grams, number of leaves and leaf area in square millimeter were evaluated. The completely randomized statistical analysis was used. The cycle C1 were used 48 replications, for cycles C2, C3 and C5 were used 64 replications and C5 were used 24 replications. The results showed that greenhouse with evaporative cooling system and CO2 allow better development and greater lettuce yield. It was possible to conclude that the aerial injection of CO2, in the absence of evaporative cooling system, did not lead increasing the lettuce productivity to most cycles. Bigger lettuce leaf areas were found in periods with higher temperatures.

Educação do corpo e vida ao ar livre : natureza e educação fisica em São Paulo (1930-1945)

Universidade Estadual de Campinas . Faculdade de Educação Física

Hidrólise do óleo de Azadirachta indica em água subcrítica e determinação da composição dos triacilglicerídeos e ácidos graxos por cromatografia gasosa de alta resolução a alta temperatura e cromatografia gasosa de alta resolução acoplada à espectrometria de massas

The development of modern analytical tools plays an important role in quality control. The main purpose of this study was to explore the use of subcritical water as a versatile analytical tool, employed simultaneously as a reagent and solvent, as well as the application of high temperature-high resolution gas chromatography (HT-HRGC) to develop a procedure for the analysis of triacylglycerides and fatty acids in Azadirachta indica A. Juss. (Neem) oil without the need for solvents, chemical reagents, or catalytic agents. The developed method presented satisfactory results and is in agreement with the concepts of Green Analytical Chemistry (GAC).

Seqüenciamento de peptídeos usando espectrometria de massas: um guia prático

This paper introduces the basics of peptide mass spectra interpretation applied to proteomics and is directed to chemists, biochemists and biologists. The manuscript presents a well detailed protocol aiming to serve as a first choice guide for understanding peptide sequencing. The tutorial was elaborated based on both a thorough bibliographic revision and the author's experience. In order to prove the applicability of the proposed guide, spectra obtained on different instruments have been successfully interpreted by applying the presented rational.

Eletroforese capilar acoplada à espectrometria de massas (CE-MS): vinte anos de desenvolvimento

CE-MS has been increasingly used for analysis of a vast array of compounds. This article reviews the different electrophoretic modes, interfaces and mass analyzers that are commonly used in the CE-MS coupling, as well as the technique advantages and performance characteristics. A large compilation of CE-MS applications is also presented. Therefore, this review is both a guide for beginners and a collection of key references for people who are familiar to the technique. Furthermore, this is the first CE-MS review published in a Brazilian journal and marks the installation of the first two commercial CE-MS units in Sao Paulo State.

Queimadas de cana-de-açúcar: Avaliação de efeitos na qualidade do ar e na saúde respiratória de crianças

Pesquisa em Espírito Santo do Turvo (SP) analisou poluição atmosférica causada por queima de cana-de-açúcar e saúde respiratória de crianças. Realizaram-se medições de PM10, PTS e NO2, durante safra, em 2004 e 2005, em pátio de escola, e aplicou-se questionário para avaliar morbidade respiratória referida dos alunos. No município, há cultivo de cana, queimada no pré-corte e usina próxima à área urbana. Resultados dos questionários foram comparados àqueles obtidos em Juquitiba (SP) previamente. As medições de poluentes, realizadas em dias em que havia queima de cana, estiveram abaixo dos padrões de qualidade do ar. Entretanto, foram indicadas altas prevalências de sintomas e doenças respiratórias.

PSA and androgen-related gene (AR, CYP17, and CYP19) polymorphisms and the risk of adenocarcinoma at prostate biopsy

The aim of the present study was to examine the impact of polymorphisms in prostate-specific antigen (PSA) and androgen-related genes (AR, CYP17, and CYP19) on prostate cancer (PCa) risk in selected high-risk patients who underwent prostate biopsy. Blood samples and prostate tissues were obtained for DNA analysis. Single-nucleotide polymorphisms in the 50-untranslated regions (UTRs) of the PSA (substitution A > G at position -158) and CYP17 (substitution T > C at 50-UTR) genes were detected by polymerase chain reaction (PCR)-restriction fragment length polymorphism assays. The CAG and TTTA repeats in the AR and CYP19 genes, respectively, were genotyped by PCR-based GeneScan analysis. Patients with the GG genotype of the PSA gene had a higher risk of PCa than those with the AG or AA genotype (OR = 3.79, p = 0.00138). The AA genotype was associated with lower PSA levels (6.44 +/- 1.64 ng/mL) compared with genotypes having at least one G allele (10.44 +/- 10.06 ng/mL) (p = 0.0687, 95% CI - 0.3146 to 8.315, unpaired t-test). The multivariate analysis confirmed the association between PSA levels and PSA genotypes (AA vs. AG+GG; chi(2) = 0.0482) and CYP19 (short alleles homozygous vs. at least one long allele; chi(2) = 0.0110) genotypes. Genetic instability at the AR locus leading to somatic mosaicism was detected in one PCa patient by comparing the length of AR CAG repeats in matched peripheral blood and prostate biopsy cores. Taken together, these findings suggest that the PSA genotype should be a clinically relevant biomarker to predict the PCa risk.

Espacialização da temperatura do ar anual no estado de Alagoas com diferentes modelos digitais de elevação e resoluções espaciais

The aim of this study was to establish a digital elevation model and its horizontal resolution to interpolate the annual air temperature for the Alagoas State by means of multiple linear regression models. A multiple linear regression model was adjusted to series (11 to 34 years) of annual air temperatures obtained from 28 weather stations in the states of Alagoas, Bahia, Pernambuco and Sergipe, in the Northeast of Brazil, in function of latitude, longitude and altitude. The elevation models SRTM and GTOPO30 were used in the analysis, with original resolutions of 90 and 900 m, respectively. The SRTM was resampled for horizontal resolutions of 125, 250, 500, 750 and 900 m. For spatializing the annual mean air temperature for the state of Alagoas, a multiple linear regression model was used for each elevation and spatial resolution on a grid of the latitude and longitude. In Alagoas, estimates based on SRTM data resulted in a standard error of estimate (0.57 degrees C) and dispersion (r(2) = 0.62) lower than those obtained from GTOPO30 (0.93 degrees C and 0.20). In terms of SRTM resolutions, no significant differences were observed between the standard error (0.55 degrees C; 750 m - 0.58 degrees C; 250m) and dispersion (0.60; 500 m - 0.65; 750 m) estimates. The spatialization of annual air temperature in Alagoas, via multiple regression models applied to SRTM data showed higher concordance than that obtained with the GTOPO30, independent of the spatial resolution.

Energy of the first excited state of (43)Ar

Results of proton-proton-gamma coincidence measurements using the (36)S+(9)Be reaction revealed a gamma ray of 201.27 +/- 0.16 keV that most probably corresponds to the transition between the predicted 7/2(-) first excited state to the 5/2(-) ground state of (43)Ar.

Elongated shape isomers in the (36)Ar nucleus

A recent analysis of the (12)C + (24)Mg scattering [W. Sciani et al., Phys. Rev. C 80, 034319 (2009)] suggests the existence of a hyperdeformed band in the (36)Ar nucleus, completely in line with the predictions of alpha [W. D. M. Rae and A. C. Merchant, Phys. Lett. B279, 207 (1992)] and binary cluster calculations [J. Cseh et al., Phys. Rev. C 70, 034311 (2004)]. Here we review the structural understanding of the superdeformed and the hyperdeformed states of (36)Ar and present new results on the shape isomers as well. Special attention is paid to the clusterization of these states, which indicates the appropriate reaction channels for their formation.