Resumo A cromatografia líquida acoplada à espectrometria de massas de alta resolução do tipo Orbitrap demonstrou ser uma técnica adequada para o controle de adulteração de substâncias proibidas não declaradas nos rótulos de suplementos proteicos derivados de soro de leite. Foi estabelecido um método de extração combinado a uma análise instrumental que permitiu a determinação de 105 substâncias em suplemento proteico derivado de soro de leite. O pré-tratamento das amostras consistiu na precipitação de proteínas e na extração em fase sólida, utilizando-se cartuchos com sorventes poliméricos baseados em troca catiônica. As amostras foram diretamente analisadas por CL-EMAR-Orbitrap. Foram estimados, como parâmetros de validação, seletividade, limite de detecção, repetitividade, recuperação, arraste e efeito de matriz. A repetitividade obtida foi de 96,19% e a recuperação foi de 83,80%. Arraste e efeito de matriz não foram observados. O presente método foi aplicado com sucesso na análise de amostras comerciais, nas quais foram verificadas adulterações, em sete das 11 marcas avaliadas, em diuréticos (conivaptan e politiazida) e estimulante (benfluorex).

Abstract Liquid chromatography coupled to Orbitrap high resolution mass spectrometry was shown to be an adequate technique to control the adulteration of whey protein food supplements with prohibited substances, not declared on the labels. An extraction method combined with an instrumental analysis that allowed for the determination of 105 substances in whey protein food supplements, was established. The pre-treatment of the samples consisted of protein precipitation and solid-phase extraction using weak cation exchange functionalized polymeric sorbent cartridges. The samples were directly analyzed by LC-Orbitrap-HRMS. The selectivity, limit of detection, repeatability, recovery, carryover and matrix effect were estimated as the validation parameters. The repeatability obtained was 96.19% and the recovery 83.80%, but carryover and the matrix effect were not observed. The present method was successfully applied to the analysis of commercial samples, verifying adulteration by diuretics (conivaptan and politiazide) and a stimulant (benfluorex) in seven of the eleven brands evaluated.

In this work, we report a new method for obtaining racemic β-hydroxyesters by reduction of β-ketoesters. The use of glycerol as a reactional medium in selective reduction of β-ketoesters into the corresponding alcohols was shown to be a viable and more efficient alternative compared with the conventional methodology, taking into account green chemistry prerogatives.

A complete analysis of oils and their fractions allows correlations to be defined between their composition and derivatives or related geological materials. This work focused on optimization and implementation of a method for separation and quantification of n-alkanes in Brazilian oil samples by urea adduction and GC-FID techniques. Ten samples with different ºAPI were analyzed in triplicate to quantify individual n-alkanes and cyclic/branched alkane fraction. For individual quantification of n-alkanes, internal standardization with deuterated n-tetracosane was used. The use of urea adduction for the separation and quantification of n-alkanes was highly effective, with recovery values of above 80%.

Uma nova ferramenta vem sendo cada vez mais utilizada em geoquímica orgânica. Trata-se da aplicação de inclusões fluidas hospedadas em minerais, principalmente quartzo, de amostras de rocha recuperadas de poços exploratórios. Neste trabalho foi desenvolvido um método novo e prático na análise pontual de amostras de calha oriundas de diversas profundidades para identificar a presença de petróleo em inclusões fluidas de minerais siliciclásticos e carbonáticos. O método é chamado de detecção de inclusões de petróleo e permite analisar a presença de compostos voláteis em inclusões fluidas através do esmagamento online dos grãos. Este método utiliza um sistema de injeção manual para amostras sólidas micro-scaled sealed vessel (MSSV). Além disso, é simples, relativamente rápido e apresenta uma boa reprodutibilidade. Para obter êxito nas análises torna-se essencial o controle cuidadoso dos procedimentos analíticos envolvidos, incluindo a limpeza das amostras e corridas de brancos no espectrômetro de massas. Os resultados foram comparados com procedimentos previamente propostos

A new tool has been increasingly used in organic geochemistry; it is the application of fluid inclusions hosted in minerals, mainly quartz, from rock samples recovered in basin wells. In this paper we develop a new practical screening method to identify the presence of petroleum in fluid inclusions from siliciclastic and carbonatic minerals. The method is called detection of petroleum inclusions and allows analyzing the presence of volatiles in oil fluid inclusions extracted by online crushing from cuttings samples. This method offers the advantage of working with solid samples, as a micro-scaled sealed vessel (MSSV) system. Moreover it is simple, relatively fast and presents a satisfactory reproducibility. For the successful analysis it is essential to carefully control the analytical procedures, including the cleaning of samples and blank runs. Results were compared with previously reported methods

A técnica de cromatografia líquida acoplada a um espectrômetro de massas com ionização "electrospray" (LC-ESI-MS/MS) foi usada para a determinação simultânea de resíduos de dez sulfonamidas (SAs: sulfacetamida, sulfatiazol, sulfamerazina, sulfametazina, sulfametoxipiridazina, sulfametazol, sulfacloropiridazina, sulfametoxazol, sulfadimetoxina e sulfaquinoxalina) em ovos. As amostras foram preparadas por precipitação das proteínas com acetonitrila seguida por extração em fase sólida. Após remoção do solvente e reconstituição, os extratos finais foram injetados no LC-ESI-MS/MS no modo positivo para todas as sulfonamidas. O método validado resultou em recuperação entre 87 e 116% com desvios padrão relativo entre 8,5 e 27,2%, CCα entre 101,0 e 122,1 ng g-1 e CCβ entre 114,5 e 138,8 ng g-1. O método analítico, no qual foram utilizadas amostras fortificadas, foi validado baseado na Decisão da Comissão 2002/657/CE

Liquid chromatography- electrospray ionization - tandem mass spectrometry (LC-ESI-MS/MS) was used to simultaneous determination of ten sulfonamide (SAs) residues (sulfacetamide, sulfathiazole, sulfamerazine, sulfamethazine, sulfamethoxypyridazine, sulfamethizole, sulfachloropyridazine, sulfamethoxazole, sulfadimethoxine and sulfaquinoxaline) in eggs. Samples were extracted with acetonitrile and the supernatants were cleaned up by solid phase extraction. After solvent evaporation and reconstitution, aliquots of the final extracts were injected into a LC-ESI-MS/MS in positive mode for all sulfonamides. The validated method resulted in recoveries ranging between 87 and 116% with relative standard deviations between 8.5 and 27.2%, CCα between 101.0 and 122.1 ng g-1, and CCβ between 114.5 and 138.8 ng g-1. The analytical method, using fortified samples, was validated based on the Commission Decision 2002/657/EC

Hidrocarbonetos policíclicos aromáticos (HPAs) foram identificados e quantificados em amostras de água e sedimento em 12 pontos da Baía de Guanabara. As amostras foram analisadas por CG-EM para verificar o grau de contaminação através do monitoramento do ecossistema afetado após o derramamento de óleo que ocorreu em 18 de janeiro de 2000. As concentrações totais de HPAs encontradas nas amostras de sedimento apresentaram valores na faixa de 77 a 7751 µg kg-1 em peso seco e de não detectado a 1592 ng L-1 em amostras de água. A maioria das amostras de sedimento foi classificada como altamente contaminada (HPA > 500 µg kg-1) enquanto a concentração nas amostras de água não apresentou valores suficientemente alto para causar alguma toxidez aos organismos aquáticos. A concentração de HPAs na Baía de Guanabara, quando comparada com outras regiões costeiras, está relativamente alta. Foi utilizada a razão entre HPAs de baixa massa molar/alta massa molar (BMM/AMM), fenantreno/antraceno e benzo[a]antraceno/criseno como indicadores da origem dos HPAs, os quais demonstraram que a grande parte da contaminação da Baía de Guanabara é derivada da queima de combustíveis.

Polycyclic aromatic hydrocarbons (PAHs) were identified and quantified in sediment and water samples from 12 sites in the north-northeast region of the Guanabara Bay. The samples were analyzed by GC-MS to assess the degree of contamination by monitoring the affected ecosystem after an oil spill that occurred in January 18, 2000. Total PAH concentrations ranged from 77 to 7,751 µg kg-1 dry weight in surficial sediment samples and from not detected to 1592 ng L-1 in water samples. The majority of sediment samples were classified as highly contaminated (total PAH > 500 µg kg-1) while for water samples the concentration of PAHs was not sufficiently high to induce acute toxicity to aquatic organisms. In comparison with other coastal areas, PAH concentrations in Guanabara Bay are relatively high. The ratios of low molecular weight/high molecular weight (LMW/HMW) PAHs, phenanthrene/anthracene and benzo[a]anthracene/chrysene, are sensitive indicators of the origin of PAH pollution, which have shown to be mostly from fuel combustion in the Guanabara Bay.

The concept of research and the controversy among classical models for C, T & I, outdated by the development of knowledge and Post-modern society needs were revisited through the (3) Quadrants advanced by Donald Stokes in the mid-nineties. The scientific community to fit into these Quadrants was faced with many difficulties and reacted by issuing pseudo-facts, accepted by under-prepared technocrats as viable justifications for conducting research in face of these new paradigms. In a poor country full of contrast and needs such as Brazil, this attitude satisfies the bureaucracy and academic elite, but frustrates government and society, that do not get, in the expected measure, the benefits of their commitment with the Teaching, Research and Extension Sectors mainly embedded in the Public University system. An extension, in fact a contradictory approach, to Pasteur's Quadrant, is proposed to characterize this situation: The Syndrome of Ruetsap's Quadrant.

One of the most widely used physico-chemical characterizations of hydrocarbon mixtures is the determination of their boiling point distribution. Knowledge of the boiling range of crude oils and petroleum products is essential to ensure the correct specification of final products and to control refinery processes. Simulated distillation, a GC based process, has been playing this role for the past decades in the petroleum industry. The main purpose of this work is to show the fundamentals of this technique as well as its present trends.

Apresentam-se, neste estudo, os números relativos ao controle de doping em nosso país, em competição e fora de competição do ano de 2003, e consideram-se as ações preventivas desenvolvidas. Todos os controles foram feitos de acordo com as técnicas e procedimentos orientados pela Agência Mundial Antidoping (AMA), sendo então realizada uma estatística descritiva dos mesmos. Os resultados mostram 3.797 exames realizados, sendo 3.266 controles em competição e 531 fora de competição, com caráter de surpresa. A maior parte dos controles em competição (92,1%) e fora dela (92,4%) foi realizada pelo LAB DOP, da Universidade Federal do Rio de Janeiro (UFRJ). O futebol profissional foi responsável por grande parte dos controles em competição, 2.975 (91,1%), apresentando oito positivos e um percentual baixo de 0,27%, quando comparado com dados da literatura internacional. A grande maioria dos controles fora de competição foi realizada pelo Comitê Olímpico Brasileiro (COB), durante a preparação de nossos atletas para os XIV Jogos Pan-Americanos, na República Dominicana (92,4%). Foram encontrados 19 exames positivos nos controles em competição e seis positivos fora de competição, dentre os quais dois atletas de eqüestre que se negaram a ceder uma amostra biológica. O percentual encontrado em competição (0,5%) é menor do que o descrito internacionalmente, que é de 1,80, com exceção da luta de braço (30%), do tênis de mesa paraolímpico (10%), do atletismo (6,1%) e do ciclismo (4,6%). Nos exames fora de competição, foi observada uma incidência maior do que a descrita internacionalmente no fisiculturismo (33,33%), em eqüestre (22,2%), no boxe (7,6%). Na natação (2,5%) e no atletismo (1,8%), estão um pouco elevados e a média encontrada (1,1%) pode ser descrita como estando ainda na média internacional (0,9%). Os trabalhos de prevenção do COB, da Confederação Brasileira de Futebol (CBF) e do LAB DOP da UFRJ são referidos no presente artigo, juntamente com a nova legislação antidoping proposta pelo Ministério do Esporte.

This study presents the statistics of doping control, in- and out-of-competition in Brazil during the year 2003 and also shows the preventive actions developed. We have asked four laboratories and their coordinators to inform us about the controls on Brazilian athletes performed during the year 2003. All controls were performed under the World Anti-doping Agency's (WADA) rules and regulations. Our results show that 3,797 controls were performed in this year, being 3,266 in-competition and 531 out-of-competition controls. Most of the in-competition (92.16%) and out-of-competition tests (92.47%) were performed by LAB DOP, the doping control laboratory of the Chemical Institute of the Rio de Janeiro Federal University (UFRJ), one of the South American accredited laboratories. Professional soccer was the sport where most of the in-competition controls were performed (2.975 = 91.1%), with eight positive findings and a very low percent of positives (0.27%) when compared to the international literature. Most of the out-of-competition tests were performed by the Brazilian Olympic Committee (COB), during the preparation of our athletes for participating in the XIV Pan-American Games, at the Dominican Republic (92.47%). The positive result found was 19 positive in in-competition test and six in out-of-competition test. Two equestrian athletes refused to be tested. The percentage of positive in-competition (0.58%) is lower than the international percentages described, that ranges from 1 to 2%, with the exceptions of arm-fighting (30%), Paralympics table-tennis (10%), track and field (6.15%) and cycling (4.69%). The out-of-competition tests were found to have a greater incidence of positive results in bodybuilding (33.33%), equestrian (22.22%) and boxing (7.69%). The results of swimming (2.56%), track and field (1.89%) were in agreement with international data. The preventive actions of COB, the Brazilian Soccer Confederation and LAB DOP were shown in this article, altogether with the new anti-doping law from the Brazilian Sports Ministry.

El presente estudio presenta los números relativos al control de dopaje en nuestro país, en competencia y fuera de competencia en el año 2003, considerando además las acciones preventivas desarrolladas. Todos los controles fueron realizados de acuerdo con las técnicas y los procedimientos orientados por la Agencia Mundial Antidopaje (AMA) siendo la misma una estadística descriptiva de los mismos. Los resultados mostraron 3.797 exámenes siendo 3.266 en competencia y 531 fuera de competencia con carácter sorpresivo. La mayor parte de los controles en competencia (92,1%) y fuera de la competencia (92,4%) fueron realizados por el LAB DOP, de la Universidad Federal de Rio de Janeiro (UFRJ). El fútbol profesional fue responsable por gran parte de los controles en competencia 2.975 (91,1%), presentando ocho positivos en un porcentaje bajo de 0,27%, comparado con los datos de la literatura internacional. La gran mayoría de los casos de controles fuera de competencia fueron realizados por el Comité Olímpico Brasileño (COB), durante la preparación de nuestros atletas para los XIV Juegos Pan-Americanos, en la República Dominicana (92,4%). Fueron encontrados 19 casos positivos en los controles en competencia y seis en los controles fuera de competencia. Dentro de los cuales dos de los atletas de ecuestre se negaron a brindar la muestra biológica. El porcentaje encontrado en competencia (0,5%) es menor que el que se describe internacionalmente que es de 1,8%, con excepción de la lucha (30%), del tenis de mesa paralimpico (10%), del atletismo (6,1%) y del ciclismo (4,6%). En los exámenes fuera de competencia se ha observado una incidencia mayor que la descripta internacionalmente en el fisicoculturismo (33,33%), en ecuestre (22,2%), en boxeo (7,6%). En natación (2,5%) y en atletismo (1,8%), están un poco elevados de la media encontrada (1,1%) lo que lo podría definir como estando en la media internacional (0,9%). Los trabajos de prevención del COB, de la Brasileña de Fútbol (CBF) y del LAB DOP de la UFRJ están referidos en el presente artículo juntamente con la nueva legislación antidopaje propuesta por el Ministerio del Deporte.

A qualidade do ar em ambientes industriais tem sido palco de estudos desde a segunda metade do século XX. Resultados bem documentados apontaram que a exposição prolongada a poluentes químicos, proveniente do consumo, produção, armazenamento etc., pode causar danos à saúde do trabalhador. Recentemente, estudos direcionados a ambientes não industriais mostraram correlações surpreendentes entre a qualidade do ar e os efeitos causados à saúde. O sistema de ventilação artificial tem sido a principal causa de reclamações e de um alto índice de absenteísmo. Os sintomas relacionados com a qualidade do ar em ambientes não industriais são reconhecidos pela Organização Mundial da Saúde que os identifica como "Síndrome dos Edifícios Doentes". No Brasil, há poucos estudos relacionando qualidade do ar em ambientes fechados e saúde. O presente trabalho pretende mapear as pesquisas já realizadas no País, visando, com isso, incentivar novos estudos nessa área, em virtude de sua importância para a saúde da população.

Air quality in industrial environments has been studied since the second half of the 20th century. Well-documented results show that exposure to chemical pollutants through their consumption, production, and storage can damage workers' health. New research focusing on non-industrial environments has shown unexpected correlations between air quality and health effects. Artificial ventilation systems have been related to health-related complaints and a high rate of absenteeism. Symptoms related to air quality in non-industrial environments are recognized by the World Health Organization and encompassed under the so-called sick building syndrome (SBS). In Brazil there are few studies comparing indoor air quality and health. The present study is intended to map the studies already conducted in Brazil in order to encourage further research in this area, due to its importance for public health.

A qualidade do ar em ambientes industriais tem sido palco de estudos desde a segunda metade do século XX. Resultados bem documentados apontaram que a exposição prolongada a poluentes químicos, proveniente do consumo, produção, armazenamento etc., pode causar danos à saúde do trabalhador. Recentemente, estudos direcionados a ambientes não industriais mostraram correlações surpreendentes entre a qualidade do ar e os efeitos causados à saúde. O sistema de ventilação artificial tem sido a principal causa de reclamações e de um alto índice de absenteísmo. Os sintomas relacionados com a qualidade do ar em ambientes não industriais são reconhecidos pela Organização Mundial da Saúde que os identifica como "Síndrome dos Edifícios Doentes". No Brasil, há poucos estudos relacionando qualidade do ar em ambientes fechados e saúde. O presente trabalho pretende mapear as pesquisas já realizadas no País, visando, com isso, incentivar novos estudos nessa área, em virtude de sua importância para a saúde da população.

Air quality in industrial environments has been studied since the second half of the 20th century. Well-documented results show that exposure to chemical pollutants through their consumption, production, and storage can damage workers' health. New research focusing on non-industrial environments has shown unexpected correlations between air quality and health effects. Artificial ventilation systems have been related to health-related complaints and a high rate of absenteeism. Symptoms related to air quality in non-industrial environments are recognized by the World Health Organization and encompassed under the so-called sick building syndrome (SBS). In Brazil there are few studies comparing indoor air quality and health. The present study is intended to map the studies already conducted in Brazil in order to encourage further research in this area, due to its importance for public health.

The fractIons of dichloromethane extracts of leaves from andiroba (Carapa guianensis - Meliaceae), caapi (Banisteriopsis caapi - Malpighiaceae), cocoa (Theobroma cacao - Sterculiaceae), Brazil nut (Bertholletia excelsa - Lecytidaceae), cupuaçu (Theobroma grandiflorum - Sterculiaceae), marupá (Simaruba amara - Simaroubaceae) and rubber tree (Hevea brasiliensis - Euphorbiaceae), were analyzed by HT-HRGC and HT-HRGC-MS. Esters of homologous series of fatty acids and long chain alcohols, phytol, amyrines and tocopherols were characterized. The characterization of the compounds was based mainly in mass spectra data and in addition by usual spectrometric data (¹H and 13C NMR, IR).

Erythropoietin is an endogenous hormone of glicoproteic nature secreted by the kidneys and is the main regulator of the erythropoiesis. An alteration in its production generates a disturbance in the plasmatic concentration giving rise to several types of pathologies related to the hematopoietic system. The recombinant forms of erythropoietin have indiscriminately been used by athletes, mainly in endurance sports, by increasing the erythrocytes concentration, generating a better delivery of oxygen to the muscle tissue. The administration of recombinant erythropoietin was prohibited by the International Olympic Committee and its use considered as doping. This review has the intention to describe the physical, biological and pharmacokinetic properties of the endogenous erythropoietin, as well as its recombinant form, describing also its use in sports and the process of searching methodologies for its detection in doping control.

During the last two decades there has been increasing concern within the scientific community related to the effects of indoor air quality on health. Changes in building design devised to improve energy efficiency and new synthetic building materials have contributed to increase pollutant concentrations. These factors have generated poor air quality and caused the development of a lot of symptoms known as Sick Building Syndrome (SBS). In Brazil, there are few studies in this area, collected in this review to support researches and awareness of the need to adopt preventive measures to reach a better quality for the Indoor Environment.