Resumo As características intrínsecas de muitas frutas tropicais causam grandes perdas pós-colheita e impedem sua comercialização como frutas frescas. As informações sobre sua composição são cruciais para definir as condições de processamento e identificar oportunidades de desenvolvimento de produtos. No entanto, os métodos analíticos geralmente usados para quantificar açúcares e ácidos orgânicos são caros e demorados. A análise simultânea por Cromatografia Líquida-Ionização por Electrospray-Espectrometria de Massa (LC-ESI-MS/MS) é uma técnica muito sensível e reproduzível, permitindo a quantificação simultânea precisa em sistemas complexos. Assim, desenvolvemos um método LC-ESI-MS/MS de monitoramento de reações múltiplas (MRM) usando coluna de fase reversa para detectar e quantificar açúcares e alguns ácidos orgânicos em apenas quatro minutos, em frutas selecionadas: araza (Psidium cattleianum), ceriguela (Spondias purpurea), manga (Mangifera indica), goiaba (Psidium guajava) e pitanga (Eugenia uniflora L.). Todas as frutas apresentaram concentrações semelhantes de glicose e frutose, exceto a pitanga, que apresentou valores superiores. O conteúdo de ácidos cítrico, málico e tartárico foi quantificado; algumas frutas se destacaram pelo alto teor de ácidos orgânicos. Os dados gerados sobre a composição das frutas tropicais permitem estabelecer uma correlação entre o teor de carboidratos e as propriedades físicas das polpas das frutas, auxiliando no desenvolvimento de novos produtos.

Abstract The intrinsic characteristics of many tropical fruits cause high post-harvest losses and prevent their commercialization as fresh fruits. Information about their composition is crucial for defining processing conditions and identifying opportunities for product development. However, the analytical methods generally used to quantify sugars and organic acids are costly and time-consuming. Simultaneous analysis by Liquid Chromatography-Electrospray Ionization-Mass Spectrometry (LC-ESI-MS/MS) is a very sensitive and reproducible technique, allowing for accurate simultaneous multi-analyte quantitation in complex systems. Thus, a LC-ESI-MS/MS Multiple Reaction Monitoring (MRM) method was developed using reverse phase column for detecting and quantifying sugars and some organic acids in only 4 min, in selected fruits as following: araza (Psidium cattleianum L.), ciriguela (Spondias purpurea L.), mango (Mangifera indicaL.), guava (Psidium guajava L.) and pitanga (Eugenia uniflora L.). All fruits had a similar concentration of glucose and fructose, except for pitanga that presented higher values of both. The content of citric, malic and tartaric acids was quantitated; some fruits stood out by their high content of organic acids, for instance, araza was rich in citric acid. The newly generated data on the composition of tropical fruits allowed establishing a correlation between the carbohydrate content and the physical properties of the fruit pulps, assist in product development.

The widespread use of moxidectin (MOX), a parasiticide used in the sheep breeding, has induced the parasite resistance in Brazilian farms. As a consequence, the farmers often increase the dose and frequency of drug utilization, and disregards safety of meat or milk. In order to establish adequate therapeutic treatment it is necessary to know the pharmacokinetics of the drug in the animal's body. Thus, high performance liquid chromatography-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS) method was developed for the determination of MOX in serum lamb. Serum samples were treated with acetonitrile to precipitate proteins. A clean up by dispersive extraction in solid phase (SPE-d), using primary/secondary amine (PSA) and C18 sorbents, followed by freezing was performed. Method validation presented precision (coefficient of variation) and accuracy (recovery%) between 1.7-6.7 and 80.0-107.3%, respectively. The limit of quantification (LOQ) of the method was 2.0 ng mL-1 and a linear response was obtained over a range of 2.0 to 100 ng mL-1. This method was successfully applied to the determination of MOX in serum from suffolk lamb to evaluate the pharmacokinetic profile.

Foi determinada a migração de compostos residuais não voláteis e de inorgânicos provenientes do polietileno tereftalato (PET) pós-consumo reciclado, submetido a processos de descontaminação para produção de materiais destinados a contato com alimentos, bem como de material de embalagem multicamada contendo polietileno de alta densidade (HDPE) pós-consumo reciclado. Os ensaios foram realizados utilizando simulantes de alimentos. Os contaminantes orgânicos não voláteis do PET, determinados por cromatografia líquida-espectrometria de massas (UPLC-QqQ/MS), apresentaram redução significativa da migração como consequência da complexidade da tecnologia de descontaminação aplicada. No entanto, contaminantes não permitidos pelas legislações brasileira e europeia foram identificados, mesmo em amostras submetidas à tecnologia mais complexa. Os resultados do HDPE multicamadas mostraram maior número de contaminantes quando em comparação aos peletes reciclados. Os níveis de contaminantes inorgânicos, determinados por espectrometria de massa com fonte de plasma, se mostraram abaixo dos níveis recomendados. Estudos adicionais para identificar e quantificar as estruturas moleculares não identificadas neste estudo por UPLC-QqQ/MS são necessários para garantir a segurança do uso de material de embalagem pós-consumo reciclado.

Migration of nonvolatile and inorganic residual compounds from post-consumer recycled polyethylene terephthalate (PET) submitted to cleaning processes for subsequent production of materials intended to food contact, as well as from multilayer packaging material containing post-consumer recycled high-density polyethylene (HDPE) was determined. Tests were carried out using food simulants. Nonvolatile organic contaminants from PET, determined by liquid chromatography-mass spectrometry (UPLC-QqQ/MS), showed significant migration reduction as consequence of the more complex cleaning technologies applied. However, contaminants not allowed by Brazilian and European Union regulations were identified even in deep cleaning samples. Results from multilayer HDPE showed a greater number of contaminants when compared to recycled pellets. Inorganic contaminants, determined by inductively coupled plasma mass spectrometry were below the acceptable levels. Additional studies for identification and quantitation of unknown molecules which were not possible to identify in this study by UPLC-QqQ/MS are required to ascertain the safety of using post-consumer recycled packaging material.

This is an overview of LC-MS techniques applied for macrolide determination in food, including sample preparation and method validation, as well as the policies adopted by international agencies regarding their presence in food. Techniques for the analysis of macrolides in food normally include solid phase or liquid-liquid extraction followed by HPLC. UHPLC presents advantages in running time, detectability and solvent consumption. Triple-quadrupoles are the most common analyzers in instruments used for the determination of contaminants in food, but time-of-flight and ion-trap spectrometers have been successfully applied for analyses focusing on the investigation of structural formula or the presence of degradation products.

The electrochemical behavior of N-nitrosothiazolidine carboxylic acid (NTAC) on gold and hanging mercury electrodes, using the cyclic and square wave voltammetries, was studied. Whereas NTAC suffer reduction in a single step on the mercury electrode, two peaks appears on the cyclic voltammograms on the gold electrode, one anodic peak overlaying the gold oxide process at 1.2 V and one cathodic peak at -0.41 V vs Ag/AgCl, KCl 3.0 mol L-1. The cathodic peak depends on the previous oxidation of NTAC at the electrode surface, presents irreversible and adsorption controlled characteristics and it is suitable for quantitative purposes.

Different agencies that supply validation guidelines worldwide establish almost the same parameters to be evaluated in the validation process of bioanalytical methods. However, they recommend different procedures, as well as establish different acceptance criteria. The present review delineates and discusses the stages involved in the validation procedures of bioanalytical methods designed for determining veterinary residues in food, explaining the main differences in the guidelines established for this purpose by the main regulatory agencies in the world.

Neste trabalho foi desenvolvido um método para a determinação de hexaclorobenzeno, lindano, heptaclor, heptaclor epóxido, aldrin, dieldrin, endrin, DDT e DDE em folhas de Mikania laevigata, Maytenus ilicifolia e Cordia verbenacea, empregando a Cromatografia Gasosa acoplada a Espectrometria de Massas (GC-MS). A extração dos pesticidas foi realizada por extração sólido-líquido (SLE), seguida de limpeza por extração em fase sólida (Florisil e silica-gel). A quantificação foi realizada usando o GC-MS no modo SIM. A recuperação média variou de 70 a 124%. A precisão inter-ensaio de uma amostra fortificada com 200 ng g-1 de cada pesticida variou de 1,0 a 7,3%. Os limites de quantificação variaram de 3,0 a 30 ng g-1 e estão abaixo dos limites máximos de resíduos (MLR) estabelecidos para os pesticidas sob estudo. O método foi empregado para analisar amostras de Mikania laevigata, Maytenus ilicifolia e Cordia verbenacea de um campo experimental de Paulínia, SP, Brasil. As amostras apresentaram contaminação com dieldrin acima do MRL estabelecido pela Farmacopéia Européia (50 ng g-1).

A method using Gas Chromatography coupled to Mass Spectrometry (GC-MS) for the determination of hexachlorobenzene, lindane, heptachlor, heptachlor epoxide, aldrin, dieldrin, endrin, 4,4'-DDT and 4,4'-DDE in leaves of Mikania laevigata, Maytenus ilicifolia and Cordia verbenacea was developed. Extraction of the pesticides was carried out by solid-liquid extraction (SLE), followed by clean-up in solid phase mixed cartridge (Florisil and silica-gel). Quantification was performed using GC-MS in the selected ion monitoring mode. Mean recovery rates of 70 to 124% were obtained. The inter-assay precision of a sample fortified with 200 ng g-1 of each pesticide was in the range of 1.0 to 7.3%. The quantitation limits ranged from 3.0 to 30 ng g-1 and were below the Maximum Residue Limit (MRL) for all the pesticides under study. The method was employed to analyze samples of Mikania laevigata, Maytenus ilicifolia and Cordia verbenacea from an experimental field in Paulínia, SP, Brazil. The samples presented contamination with dieldrin above the MRL established by the European Pharmacopoeia (50 ng g-1).

Foi estabelecido um método cromatográfico rápido e simples para a determinação de riboflavina em leite bovino, na presença de tetraciclinas. Para tanto, as proteínas foram precipitadas com ácido tricloroacético e a separação realizada por CLAE em fase reversa com detector de fluorescência. Foi utilizada uma coluna C8 com eluição isocrática e fase móvel acetato de sódio 0,1 mol L-1, cloreto de cálcio 35 mmol L-1, EDTA 25 mmol L-1: metanol (65:35 v/v). O método foi validado mediante avaliação dos seguintes parâmetros: linearidade (0,9980), faixa linear (0,50 a 1,30 µg mL-1), precisão intra e inter-ensaio (RSD < 0,5%), exatidão (recuperação 92%) e limites de detecção e de quantificação (0,75 µg mL-1 e 0,22 µg mL-1, respectivamente). O método foi aplicado na análise de leite integral e desnatado, mostrando-se robusto na presença de substâncias fluorescentes como as tetraciclinas, e quando comparado com o método espectrofluorimétrico, não revelou diferença significativa (p < 0,05) entre os resultados obtidos.

An easy and simple chromatographic method for the determination of riboflavin in bovine milk in the presence of tetracyclines was established. For this, the proteins were precipitated with trichloroacetic acid and the separation was carried out by reversed-phase HPLC with fluorescence detection. A C8 column was used with isocratic flow using a mobile phase consisting of 0.1 mol L-1 sodium acetate, 35 mmol L-1calcium chloride and 25 mmol L-1 EDTA : methanol (65:35 v/v). The method was validated by means of the following parameters: linearity (0.9980), linear range (0.50 - 1.30 µg mL-1), intra- and inter-assay precision (RSD < 0.5%), accuracy (recovery 92%), and detection and quantitation limits (0.75 µg mL-1 and 0.22 µg mL-1, respectively). The method was applied for analysis of full cream and skimmed milk, showing robustness in the presence of tetracyclines, and when compared with a spectrofluorimetric method showed no significant difference (p < 0.05) between the results obtained.

The susceptibility of Drosophila melanogaster to carbofuran and the use of this organism in biomonitoring residues of the insecticide in cabbage was evaluated. Under the conditions of the bioassay, residues-film bioassay in Petri dish, carbofuran degraded depending on the temperature and time of exposure. Bioassays conducted with D. melanogaster showed that its toxicity increases with temperature (20 to 35 °C). LC50 values, calculated as a function of temperature, ranged from 3.6 to 10.5 mg/g body weight (bw) for males and from 2.9 to 8.7 mg/g bw for females. The formulated product Furadan® G was applied on cabbage (Brassica oleracea, var. capitata) and the residues of carbofuran were determined by bioassay. The determination limit of the bioassay was 0.1 mg/kg and the method presented reproducibility with coefficient variation of 17 %. The validation of the bioassay by high performance liquid chromatography confirms the viability of the bioassay with D. melanogaster in monitoring the residues of carbofuran in cabbage.

RESUMO: Neste artigo de revisão são abordados aspectos de legislação relacionados ao uso seguro de componentes de materiais de embalagem plástica para alimentos. São apresentados os sistemas de regulamentação adotados no Brasil, Estados Unidos da América, União Européia e MERCOSUL.

ABSTRACT: Legislative aspects concerning approval for the safe use of plastic packaging for food contact are discussed in this review paper. The regulatory approaches adopted in Brazil, the United States of America, the European Community and the Common Market of South American Countries (MERCOSUL) are described.

RESUMO: Embalagens plásticas para alimentos contendo poli(tereftalato de etileno (PET) foram submetidas a diversas condições de aquecimento. Oligômeros foram identificados por cromatografia líquida de alta eficiência acoplada à espectrometria de massas, quantificados e usados como parâmetro de avaliação da estabilidade térmica do PET. Pequenas variações foram verificadas na distribuição dos oligômeros unicamente nas amostras aquecidas a 230 °C, o que sugere estabilidade térmica do PET nas condições de aquecimento utilizadas. Os resultados obtidos indicam que o uso do polímero é adequado para utilização como material de embalagem para alimentos a serem aquecidos em fornos convencionais ou de microondas.

ABSTRACT: Polyethylene terephthalate (PET) food packaging materials were submitted to different heating conditions. Oligomers were identified by high performance liquid chromatography coupled to mass spectrometry, quantified and used as parameter for the evaluation of thermal stability of the polymer. Small changes in oligomer distribution were observed only for samples heated at 230 °C, suggesting that PET is stable at the heating conditions employed. The results also suggest that the polymer is suitable as food packaging material intended for use in conventional and microwave ovens.