Abstract The control of weeds in agriculture is mainly conducted with the use of synthetic herbicides. However, environmental and human health concerns and increased resistance of weeds to existing herbicides have increased the pressure on researchers to find new active ingredients for weed control which present low toxicity to non-target organisms, are environmentally safe, and can be applied at low concentrations. It is herein described the synthesis of glycerol-fluorinated triazole derivatives and evaluation of their phytotoxic and cytogenotoxic activities. Starting from glycerol, ten fluorinated triazole derivatives were prepared in four steps. The assessment of them on Lactuca sativa revealed that they present effects on phytotoxic and cytogenotoxic parameters with different degrees of efficiency. The compounds 4a, 4b, 4d, 4e, 4i, and 4j have pre-emergent inhibition behavior, while all the investigated compounds showed post emergent effect. Mechanism of action as clastogenic, aneugenic, and epigenetic were observed in the lettuce root meristematic cells, with alterations as stick chromosome, bridge, delay, c-metaphase, and loss. It is believed that glycerol-fluorinated triazole derivatives possess a scaffold that can be explored towards the development of new chemicals for the control of weed species.

The control of fungal species in agriculture is mainly conducted with the use of contact or systemic fungicides. However, environmental and human health concerns and increased resistance of fungal species to existing fungicides have increased the pressure on researchers to find new active ingredients for fungal control which present low toxicity to non-target organisms, are environmentally safe, and can be applied at very low concentrations. It is herein described the synthesis of eleven glycerol triazole containing compounds (ten of them fluorinated derivatives) and evaluation of their fungicidal activity. Eight out of eleven synthesized compounds are novel and all of the glycerol derivatives were characterized using infrared (IR), nuclear magnetic ressonance (NMR), and mass spectrometry (MS) techniques. Theoretical calculations were also carried out and the results are discussed. Starting from glycerol, the triazole derivatives were prepared in four steps. Evaluation of them against Colletrotricum gloesporioides showed that compound 1-((2,2-dimethyl-1,3 dioxolan-4-yl)methyl)-4-(2-fluorophenyl)-1H-1,2,3-triazole (4d) (ED50 = 59.14 µg mL-1) was slightly more active than commercial fungicide tebuconazole (61.35 µg mL-1). Compound 4d presented attractive physicochemical features for agrochemical purposes as revealed by the calculated physicochemical parameters. It is believed that glycerol-fluorinated triazole derivatives can be explored towards the development of new chemicals for the control of fungal species.

RESUMO: O objetivo deste estudo foi avaliar a composição e as atividades quimiopreventiva de câncer e antioxidante da semente, polpa e casca de uvas híbridas Maximo (IAC 138-22) colhidas em diferentes estágios de maturação. Os teores de compostos fenólicos totais, antocianinas e taninos foram determinados a partir dos extratos etanólicos. O conteúdo de fenólicos e taninos totais foi determinado pelo método de Folin-Ciocaulteau, e o teor de antocianinas totais foi determinado pelo método do pH diferencial. A atividade antioxidante foi avaliada por diferentes métodos químicos, e a viabilidade celular (macrófagos e melanomas), e atividade quimiopreventiva de câncer foi testada em culturas de células por ensaio de indução de quinona redutase, ensaio de atividade inibidora de NF-κB induzido por TNF-α e ensaio de atividade inibidora de aromatase. A uva híbrida apresentou alto teor de fenólicos nas sementes e na casca, teor que reduziu significativamente com o amadurecimento. Os resultados mostraram que o amadurecimento dos frutos afetou significativamente a composição e as atividades antioxidantes e quimiopreventivas de câncer. Com exceção do teor de antocianinas, os resultados mais significativos foram observados para as sementes verdes, com o estádio mais verde apresentando os melhores resultados. As sementes verdes apresentaram a maior atividade antioxidante, mesmo quando comparadas ao resveratrol livre. Na avaliação da atividade quimiopreventiva do câncer, as sementes verdes mostraram capacidade de inibir a atividade do NF-κB e da aromatase, fatores importantes para o estágio inicial do desenvolvimento do câncer. Além disso, nenhum extrato apresentou atividade citotóxica. Portanto, as sementes verdes desta uva apresentam resultados promissores dadas as fortes atividades antioxidantes e quimiopreventivas do câncer aqui confirmadas, sugerindo efeitos benéficos à saúde.

ABSTRACT: This study evaluated the composition and the cancer chemopreventive and antioxidant activities of the seed, skin, and pulp of Maximo hybrid grapes (IAC 138-22) harvested at different ripening stages. The content of total phenolic compounds and tannins were determined by the Folin-Ciocaulteau method, and total anthocyanins were determined using the differential pH method. Different chemical methods assessed the antioxidant activity. Cell viability (macrophage and melanoma skin cancer) and cancer chemopreventive activity were tested in cell lines by quinone reductase induction assay, TNF-α-induced NF-κB inhibitory activity assay, and aromatase inhibitory activity assay. The hybrid grape had high phenolic contents in both seeds and skin, significantly reduced upon ripening. The results showed that fruit ripening significantly affected both the composition and the antioxidant and cancer chemopreventive activities. Except for the anthocyanin content, the most significant results were observed for green seeds, with the greenest stage showing the best results. The green seeds showed the highest antioxidant activity, even when compared to free resveratrol. In the assessment of cancer chemopreventive activity, the green seeds showed the ability to inhibit N-FκB and aromatase activity, important factors for the early stage of cancer development. Besides, no extracts showed cytotoxicity. Therefore, this grape’s green seeds showed strong antioxidant and cancer chemopreventive activities confirmed herein, suggesting beneficial health effects.

ABSTRACT The objective was to investigate the total saponin and protodioscin concentrations and the cytotoxicity in vitro, of five samples of the plant Tribulus terrestris, commercially available in the metropolitan region of Vitória - Espirito Santo, Brazil, and to compare them with the aqueous extract of the plant. The chromatographic profile and quantification of protodioscin in commercial samples and plant extract were evaluated by LC-MS/MS. The percentage of total saponins were determined by the colorimetric method. Extracts and protodioscin cytotoxicity were analyzed by the MTT assay in three cell lineages: fibroblasts (L929), ovarian cancer (Ovcar3) and murine hepatoma (Hepa1c1c7). All extracts displayed high levels of total saponins (207.2 to 780.3 mg g-1 of dry extract). The chromatographic profile revealed a wide diversity of compounds, and the saponin protodioscin was detected in only two extracts. One extract displayed high cytotoxicity, with IC50 values of 157.0, 38.2 and 7.4 µg mL-1 for the Ovcar3, Hepa1c1c7 and L929 cell lines, respectively. The other extracts displayed cytotoxic effects only at concentrations equal to or greater than 125.0 µg mL-1. Surprisingly, the most cytotoxic extract displayed the highest protodioscin concentration. Therefore, it is suggested that these products be marketed with caution, and followed-up by a certified healthcare professional.

<p>The aim of this study was to investigate the presence of acephate, carbaryl, carbendazim, chlorpyrifos, dichlorvos, fenpropathrin, methamidophos and permethrin in conventionally and organically grown tomatoes from Espírito Santo, Brazil, between May 2012 and April 2013. QuEChERS sample preparation was used and analysis was performed by LC-MS/MS and GC-MS. The method validation showed good linearity (R > 0.99), precision (RSD < 13%) and accuracy (89 - 123%), and the limits of quantification were below 0.01 mg kg^-1 for all pesticides. The pesticides acephate, carbaryl (0.23 mg kg^-1; exceeding maximum residue levels), carbendazim, chlorpyriphos, dichlorvos, fenpropathrin (0.41 mg kg^-1; exceeding maximum residue levels), methamidophos and permethrin (0.51 mg kg^-1, exceeding maximum residue levels) were found in conventional tomatoes. In organic tomatoes, only one sample exhibited the presence of permethrin (0.21 mg kg^-1). Considering that the pesticides found are toxic and carcinogenic, and given the high incidence of irregularities, it is important to implement government actions to ensure consumer safety.</p>

The objective of this study was to monitor 11 organophosphorus pesticides in samples of papaya, bell pepper, and banana, commercialized in the metropolitan area of Vitória (ES, Brazil). The pesticides were determined by an optimized and validated method using high performance liquid chromatography with tandem mass spectrometry (HPLC-MS/MS). All three samples exhibited a matrix effect for most of the pesticides, mainly with signal suppression, and therefore the calibration curves were produced in matrices. Linearity revealed coefficients of determination (r2) greater than 0.9895 for all pesticides and recovery results ranged from between 76% and 118% with standard deviation no greater than 16%. Precision showed relative standard deviation values lower than 19% and HorRat values lower than 0.7, considering all pesticides. Limits of quantification were less than 0.01 mg/kg for all pesticides. Regarding analysis of the samples (50 of each), none of the pesticides exceeded the maximum residue limit determined by Brazilian legislation.

Protium heptaphyllum (Aubl) Marchand, Burseraceae, is popularly used as an analgesic and anti-inflammatory agent. However, the cellular mechanism of action remains unknown. This study aims to evaluate the chemical composition of P. heptaphyllum resin and cytotoxicity on a breast cancer cell line (MCF-7). The chemical composition of the resin was determined by Gas Chromatography coupled to a Mass Spectrometer. The cytotoxicity was evaluated using an MTT assay. Annexin V-FITC, caspase-3, Angiotensin Converting Enzyme activity and Tumor Necrosis Factor alpha (TNF- α) assays were performed to evaluate apoptosis and inflammatory events. The resin consisted of triterpenes, such as α- and β-amyrin. Cytotoxicity was only observed in fractions enriched with α- and β-amyrin. The resin and fractions elicited antiproliferative activity, increased activity of caspase-3 and ACE, and a decrease in the TNF-α level. Altogether, the resin and fractions enriched with α- and β-amyrin promoted cytotoxicity and apoptosis.

O (E)-2-nonenal é considerado um importante off-flavor da cerveja, sendo relacionado ao sabor de cerveja envelhecida. Neste estudo, um novo método para determinação de (E)-2-nonenal em cerveja usando microextração em fase sólida do headspace e cromatografia a gás acoplada à espectrometria de massa (HS-SPME-GC-MS) foi desenvolvido e aplicado em amostras de cerveja brasileira. As extrações foram realizadas utilizando a fibra CAR/PDMS (carboxen/polidimetilsiloxano), com 15 minutos de tempo de equilíbrio e 90 minutos de exposição da fibra a 50 °C. O método foi linear na faixa de 0,02 e 4,0 μg.L-1, com coeficiente de correlação de 0,9994. Os limites de detecção e quantificação foram 0,01 e 0,02 μg.L-1, respectivamente. Foram obtidos 96,5% de recuperação e 4% de variação entre replicatas de amostras de cerveja fortificadas com 2,0 μg.L-1 de (E)-2-nonenal. O método desenvolvido foi considerado simples, eficiente e altamente sensível para a determinação deste analito, sendo facilmente aplicado no controle de qualidade das cervejarias. O (E)-2-nonenal foi encontrado em todas as amostras de cervejas analisadas com níveis entre 0,17 to 0,42 μg.L-1.

(E)-2-nonenal is considered an important off-flavor of beer, related to the flavor of beer staling. In this study, a new method for determination of (E)-2-nonenal in beer using headspace solid-phase microextraction and gas chromatographic coupled mass spectrometry (HS-SPME-GC-MS) was developed and applied in Brazilian beer samples. The extractions were carried out in CAR-PDMS (carboxen-polydimethylsiloxane) fiber and the best results were found with 15 minutes of equilibrium and 90 minutes of extraction at 50 °C. The method was linear in the range from 0.02 to 4.0 μg.L-1 with correlation coefficient of 0.9994. The limits of detection and quantification were 0.01 and 0.02 μg.L-1, respectively. 96.5% of recovery and 4% precision (RSD) were obtained in the fortification of beer samples with 2.0 μg.L-1 of (E)-2-nonenal. The developed method proved to be simple, efficient and highly sensitive to the determination of this analyte being easily applied in the quality control of the brewery. (E)-2-nonenal was found in all beer samples analyzed with levels between 0.17 and 0.42 μg.L-1.

The objective of this research was to determine the levels of enrichment of vitamins B1, B2, B6 and B3 in different types and brands of enriched cookies. The chromatographic separation was performed in a C18 column with gradient elution and UV detection at 254 and 287 nm. The results show that only 5 of the 24 brands evaluated are in accordance with the Brazilian legislation with respect to the vitamin content declared on the labels. However, consumption of approximately 100-150 g of most of the brands supplies the recommended dietary intake for children and adults of the vitamins evaluated.

The aim of the present study was determining the main organic acids in pulp and juices, as well as evaluating their stability, after opening the package, by liquid chromatography in a C18 column with isocratic elution and UV detection. In açaí pulp tartaric, malic and citric acids were found. Cashew samples presented all of the organic acids evaluated, besides high concentrations of ascorbic and malic acids. Acerola pulp had the highest ascorbic acid concentration. A small decrease in organic acid content during storage was observed. Malic and citric acids seem to be more stable than tartaric and ascorbic acids.

Vitamin C stability and concentration was evaluated in isotonic beverages and B group vitamins (B1, B2, B3, B5 and B6) in power beverages. The amount of vitamins was found to be above of that declared on the labels, even after the shelf life had been exceeded. A small decrease in the amount of B group vitamins was observed during the shelf life of the products. In the case of vitamin C this decrease was slightly higher. The present research shows the need of increased quality control and inspection.

A rápida perecibilidade dos peixes provoca perdas na industrialização e comercialização desse alimento. No presente trabalho, avaliou-se a eficiência da utilização de gelo clorado para ampliar a vida-de-prateleira de carpa capim (Ctenopharyngodon idella). Foram realizadas contagens de microrganismos aeróbios mesófilos e psicrotróficos na carne, e determinada a concentração de bases voláteis totais e o pH da carne de carpas armazenadas inteiras, sob refrigeração (3±1ºC), cobertas com gelo sem cloro ou clorado (5ppm), ao longo de 20 dias. O cloro reduziu significativamente (p<0,05) as populações de microrganismos aeróbios mesófilos e psicrotróficos, o pH e os valores iniciais das bases voláteis totais (BVT) na carne de carpa capim. Os valores de BVT foram baixos e tiveram pouca variação ao longo da armazenagem. Os resultados demonstraram que a vida-de-prateleira de carpa capim pode ser aumentada em aproximadamente 3 dias utilizando cloro no gelo de armazenagem; bem como, que os parâmetros pH e bases voláteis totais não são bons indicadores para avaliar a deterioração desse peixe.

The rapid spoilage of fishes causes economical losses in the processing and marketing of these products. In the present study, the efficiency of chlorinated ice to increase grass carp (Ctenopharyngodon idella) shelf life was evaluated. Mesophilic and psychrotrophic bacteria count, total volatile basic nitrogen (TVBN) and pH were evaluated in the flesh of grass carp stored refrigerated (3±1ºC) for 20 days, covered with chlorinated (5ppm) or non-chlorinated ice. Chlorine significantly reduced (p<0,05) mesophilic and psychrotrophic bacteria count in the flesh, as well as pH and the initial values of TVBN. TVBN values were low and did not exhibit great changes over the storage time. Results showed that grass carp shelf life could be extended around 3 days by using chlorinated ice. Besides, pH and TVBN values were considered unsuitable to assess grass carp spoilage.