Matrix effects observed during pesticides residue analysis in fruits by GC

The influence of the sample matrix in the CC-electron-capture detection analysis of the pesticides dimethoate, diazinon, chlorothalonil.. parathion methyl and fenitrothion in fruits samples has been studied. Experiments have been carried out where the pesticide responses in standard solutions prepared in selected solvent were compared with their response when present in apple, mango, papaya, banana, pineapple and melon extracts. The presence of matrix effects (MEs) and their extent were shown to be simultaneously influenced by several factors (matrix concentration, matrix type, pesticide concentration, analytical range). Pronounced MEs were observed particularly for dimethoate and diazinon in all matrices tested; in lower concentrations, all pesticides presented significant ME. The other pesticides presented variable ME. Higher ME enhancement was detected at lower pesticide concentration levels of and/or at higher matrix concentration solutions. The ME detected for fenitrothion, in the analytical range evaluated, were dependent on matrix type. For each pesticide, solvent and matrix-matched calibrations were compared for all fruit samples, and it could be concluded that quantitation based on standard solutions prepared in blank matrix extract (matrix-matched calibration) should be used to compensate the MEs and to obtain more accurate results for the pesticides studied.

Molecular mass distribution of dextran in Brazilian sugar and insoluble deposits of cachaca

The dextran molecular mass distribution profile in 77 sugar samples from Brazil and twelve insoluble deposits (alcoholic flocks) samples from sugared cachacas (Brazilian sugar cane spirit) is described in terms of number-average molecular mass M,,, weight-average molecular mass M(w), Z-average molecular mass M,, and polydispersity. The analyses were performed by size-exclusion chromatography, using a refractive index detector. In most of the sugar samples, it was possible to identify two major groups of dextrans with Mw averages of 5 x 10(6) and 5 x 10(4) Da. Based on the evaluated parameters, the dextran distribution profile is about the same in samples analyzed over five seasons, and, therefore, it is likely that the Brazilian product pattern will not change very much over the years. In insoluble deposits from sugared cachacas, dextrans with Mw values in the order of the 10(5) Da were the most frequent ones, being present in 58% of the samples. (c) 2008 Elsevier Ltd. All rights reserved.

Screening of volatile composition from portuguese multifloral honeys using headspace solid-phase microextraction-gas chromatography–quadrupole mass spectrometry

The volatile composition from four types of multifloral Portuguese (produced in Madeira Island) honeys was investigated by a suitable analytical procedure based on dynamic headspace solid-phase microextraction (HS-SPME) followed by thermal desorption gas chromatography–quadrupole mass spectrometry detection (GC–qMS). The performance of five commercially available SPME fibres: 100 μm polydimethylsiloxane, PDMS; 85 μm polyacrylate, PA; 50/30 μm divinylbenzene/carboxen on polydimethylsiloxane, DVB/CAR/PDMS (StableFlex); 75 μm carboxen/polydimethylsiloxane, CAR/PDMS, and 65 μm carbowax/divinylbenzene, CW/DVB; were evaluated and compared. The highest amounts of extract, in terms of the maximum signal obtained for the total volatile composition, were obtained with a DVB/CAR/PDMS coating fibre at 60 °C during an extraction time of 40 min with a constant stirring at 750 rpm, after saturating the sample with NaCl (30%). Using this methodology more than one hundred volatile compounds, belonging to different biosynthetic pathways were identified, including monoterpenols, C13-norisoprenoids, sesquiterpenes, higher alcohols, ethyl esters and fatty acids. The main components of the HS-SPME samples of honey were in average ethanol, hotrienol, benzeneacetaldehyde, furfural, trans-linalool oxide and 1,3-dihydroxy-2-propanone.

Comparative analysis of the volatile fraction from Annona cherimola Mill. cultivars by solid-phase microextraction and gas chromatography–quadrupole mass spectrometry detection

The analysis of volatile compounds in Funchal, Madeira, Mateus and Perry Vidal cultivars of Annona cherimola Mill. (cherimoya) was carried out by headspace solid-phase microextraction (HS-SPME) combined with gas chromatography–quadrupole mass spectrometry detection (GC–qMSD). HS-SPME technique was optimized in terms of fibre selection, extraction time, extraction temperature and sample amount to reach the best extraction efficiency. The best result was obtained with 2 g of sample, using a divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fibre for 30 min at 30 °C under constant magnetic stirring (800 rpm). After optimization of the extraction methodology, all the cherimoya samples were analysed with the best conditions that allowed to identify about 60 volatile compounds. The major compounds identified in the four cherimoya cultivars were methyl butanoate, butyl butanoate, 3-methylbutyl butanoate, 3-methylbutyl 3-methylbutanoate and 5-hydroxymethyl-2-furfural. These compounds represent 69.08 ± 5.22%, 56.56 ± 15.36%, 56.69 ± 9.28% and 71.82 ± 1.29% of the total volatiles for Funchal, Madeira, Mateus and Perry Vidal cultivars, respectively. This study showed that each cherimoya cultivars have 40 common compounds, corresponding to different chemical families, namely terpenes, esters, alcohols, fatty acids and carbonyl compounds and using PCA, the volatile composition in terms of average peak areas, provided a suitable tool to differentiate among the cherimoya cultivars.

Investigation of urinary volatile organic metabolites as potential cancer biomarkers by solid-phase microextraction in combination with gas chromatography-mass spectrometry

BACKGROUND: Non-invasive diagnostic strategies aimed at identifying biomarkers of cancer are of great interest for early cancer detection. Urine is potentially a rich source of volatile organic metabolites (VOMs) that can be used as potential cancer biomarkers. Our aim was to develop a generally reliable, rapid, sensitive, and robust analytical method for screening large numbers of urine samples, resulting in a broad spectrum of native VOMs, as a tool to evaluate the potential of these metabolites in the early diagnosis of cancer. METHODS: To investigate urinary volatile metabolites as potential cancer biomarkers, urine samples from 33 cancer patients (oncological group: 14 leukaemia, 12 colorectal and 7 lymphoma) and 21 healthy (control group, cancer-free) individuals were qualitatively and quantitatively analysed. Dynamic solid-phase microextraction in headspace mode (dHS-SPME) using a carboxenpolydimethylsiloxane (CAR/PDMS) sorbent in combination with GC-qMS-based metabolomics was applied to isolate and identify the volatile metabolites. This method provides a potential non-invasive method for early cancer diagnosis as a first approach. To fulfil this objective, three important dHS-SPME experimental parameters that influence extraction efficiency (fibre coating, extraction time and temperature of sampling) were optimised using a univariate optimisation design. The highest extraction efficiency was obtained when sampling was performed at 501C for 60min using samples with high ionic strengths (17% sodium chloride, wv 1) and under agitation. RESULTS: A total of 82 volatile metabolites belonging to distinct chemical classes were identified in the control and oncological groups. Benzene derivatives, terpenoids and phenols were the most common classes for the oncological group, whereas ketones and sulphur compounds were the main classes that were isolated from the urine headspace of healthy subjects. The results demonstrate that compound concentrations were dramatically different between cancer patients and healthy volunteers. The positive rates of 16 patients among the 82 identified were found to be statistically different (Po0.05). A significant increase in the peak area of 2-methyl3-phenyl-2-propenal, p-cymene, anisole, 4-methyl-phenol and 1,2-dihydro-1,1,6-trimethyl-naphthalene in cancer patients was observed. On average, statistically significant lower abundances of dimethyl disulphide were found in cancer patients. CONCLUSIONS: Gas chromatographic peak areas were submitted to multivariate analysis (principal component analysis and supervised linear discriminant analysis) to visualise clusters within cases and to detect the volatile metabolites that are able to differentiate cancer patients from healthy individuals. Very good discrimination within cancer groups and between cancer and control groups was achieved.

Effectiveness of different solid-phase microextraction fibres for differentiation of selected Madeira island fruits based on their volatile metabolite profile: identification of novel compounds

A headspace solid-phase microextraction (HS-SPME) procedure based on five commercialised fibres (85 μm polyacrylate – PA, 100 μm polydimethylsiloxane – PDMS, 65 μm polydimethylsiloxane/divinylbenzene – PDMS/DVB, 70 μm carbowax/divinylbenzene – CW/DVB and 85 μm carboxen/polydimethylsiloxane – CAR/PDMS) is presented for the characterization of the volatile metabolite profile of four selected Madeira island fruit species, lemon (Citrus limon), kiwi (Actinidia deliciosa), papaya (Carica papaya L.) and Chickasaw plum (Prunus angustifolia). The isolation of metabolites was followed by thermal desorption gas chromatography–quadrupole mass spectrometry (GC–qMS) methodology. The performance of the target fibres was evaluated and compared. The SPME fibre coated with CW/DVB afforded the highest extraction efficiency in kiwi and papaya pulps, while in lemon and plum the same was achieved with PMDS/DVB fibre. This procedure allowed for the identification of 80 compounds, 41 in kiwi, 24 in plums, 23 in papaya and 20 in lemon. Considering the best extraction conditions, the most abundant volatiles identified in kiwi were the intense aldehydes and ethyl esters such as (E)-2-hexenal and ethyl butyrate, while in Chicasaw plum predominate 2-hexenal, 2-methyl-4-pentenal, hexanal, (Z)-3-hexenol and cyclohexylene oxide. The major compounds identified in the papaya pulp were benzyl isothiocyanate, linalool oxide, furfural, hydroxypropanone, linalool and acetic acid. Finally, lemon was shown to be the most divergent of the four fruits, being its aroma profile composed almost exclusively by terpens, namely limonene, γ-terpinene, o-cymene and α-terpinolene. Thirty two volatiles were identified for the first time in the fruit or close related species analysed and 14 volatiles are reported as novel volatile metabolites in fruits. This includes 5 new compounds in kiwi (2-cyclohexene-1,4-dione, furyl hydroxymethyl ketone, 4-hydroxydihydro-2(3H)-furanone, 5-acetoxymethyl-2-furaldehyde and ethanedioic acid), 4 in plum (4-hydroxydihydro-2(3H)-furanone, 5-methyl-2-pyrazinylmethanol, cyclohexylene oxide and 1-methylcyclohexene), 4 in papaya (octaethyleneglycol, 1,2-cyclopentanedione, 3-methyl-1,2-cyclopentanedione and 2-furyl methyl ketone) and 2 in lemon (geranyl farnesate and safranal). It is noteworthy that among the 15 volatile metabolites identified in papaya, 3-methyl-1,2-cyclopentanedione was previously described as a novel PPARγ (peroxisome proliferator-activated receptor γ) agonist, having a potential to minimize inflammation.

Vertical growth of mini watermelon according to the training height and plant density

A melancia é uma espécie tradicionalmente conduzida em campo no sistema rasteiro. As cultivares de frutos pequenos (1 a 3 kg), que adquirem melhores preços de mercado, vêm sendo cultivadas também em ambiente protegido, onde são conduzidas no sistema vertical, com poda de ramos e raleio de frutos. Essas práticas possibilitam aumentar o adensamento das plantas, a qualidade e a produtividade de frutos em comparação ao sistema rasteiro. Objetivou-se com este trabalho avaliar a influência de três alturas de condução (1,7; 2,2 e 2,7 m) e duas densidades de plantas (3,17 e 4,76 plantas m-2) sobre as características produtivas e qualitativas da mini melancia Smile cultivada em ambiente protegido. A poda da haste principal foi realizada aos 43, 55 e 66 dias após o transplante (DAT) para as alturas de condução de 1,7; 2,2 e 2,7 m, respectivamente. A massa seca dos ramos, dos pecíolos, das folhas e total foram afetados pela altura de condução, cujos maiores valores foram obtidos para as plantas conduzidas a 2,2 e 2,7 m de altura. A área foliar, a área foliar específica e o índice de área foliar não foram influenciados pela altura de condução das plantas. A altura de condução de 2,7 m elevou a produtividade total. Entretanto, a produtividade comercial, a massa média dos frutos e todas as características qualitativas não foram significativamente diferentes das obtidos pela altura de poda de 2,2 m. em relação à densidade de plantas, a melhor opção foi a de 4,76 plantas m-2, pois elevou a produtividade comercial em 37,4% sem reduzir a massa média dos frutos.

Caracterização físico-química de frutos de maracujazeiro-amarelo submetidos à iluminação artificial, irrigação e sombreamento

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Acúmulo e exportação de macronutrientes pelo híbrido de melancia Tide

O objetivo do presente trabalho foi determinar o acúmulo e exportação de macronutrientes pela cultura da melancia, híbrido Tide. O experimento foi conduzido no município de Borborema - SP. As amostragens de plantas foram realizadas aos 15, 30, 45, 60 e 75 dias após transplantio (DAT), para determinação da massa seca e do acúmulo e exportação dos nutrientes (N, P, K, Ca, Mg e S). O acúmulo de massa seca foi lento até os 30 DAT, intensificando-se a partir deste período e atingindo, no final do ciclo, a contribuição média da parte vegetativa de 31% e dos frutos de 69%. Até 30 DAT, o acúmulo de nutrientes também foi pequeno, não ultrapassando 2% do total. Com a frutificação, houve forte incremento na quantidade de nutrientes acumulados. O período de maior demanda para N, Ca e Mg foi de 45 a 60 DAT e para P, K e S de 60 a 75 DAT. do total acumulado, a parte vegetativa foi responsável por 29,6% e os frutos com 70,4%. A ordem decrescente dos nutrientes acumulados pela cultura foi: K>N>Ca>Mg>P>S. Para a produtividade alcançada de 40 t ha-1 observou-se a seguinte exportação de nutrientes pelos frutos: 106,4 kg ha-1 de N, 11,1 kg ha-1 de P, 118,0 kg ha-1 de K, 4,3 kg ha-1 de Ca, 6,8 kg ha-1 de Mg e 6,0 kg ha-1 de S.

Physical and chemical characterization of yellow mangosteen fruits

O trabalho teve como objetivo a caracterização físico-química de frutos de mangostão amarelo (Garcinia xanthochymus Hook). Seis amostras de 25 frutos cada foram colhidas em plantas de mangostão amarelo do Banco Ativo de Germoplasma da Universidade Estadual Paulista e caracterizadas pela avaliação de diâmetro e altura, peso, percentagem e número de sementes por fruto, percentagem de casca, percentagem de polpa, sólidos solúveis (SS), acidez titulável (AT), vitamina C e relação SS/AT. O mangostão amarelo tem boas qualidades tecnológicas e é uma fonte intermediária de vitamina C com conteúdo médio de 120,33 mg/100g de fruta fresca.

Armazenamento de botões florais para produção de sementes de abóbora com polinização manual

O objetivo deste trabalho foi verificar a influência do armazenamento de botões florais masculinos por diferentes períodos, na produção e qualidade de sementes de abóbora cultivar Piramoita. O experimento foi desenvolvido no período de agosto a dezembro de 2005. O delineamento experimental utilizado foi em blocos ao acaso, com quatro repetições e cinco tratamentos: polinização manual com flor aberta no dia (zero dia de armazenamento) e polinização manual com botões armazenados em geladeira (7 ºC) por 1, 2, 3 e 4 dias. Quanto maior o período de armazenamento dos botões florais masculinos, menor a produção (número e massa) de sementes por fruto e a massa média do fruto. Também há uma perda de vigor e germinação das sementes quando se aumenta o período de armazenamento dos botões florais, reduzindo sua qualidade.

Épocas de poda na produção de figos verdes 'Roxo de Valinhos' em sistema orgânico na região oeste do Paraná

O objetivo deste trabalho foi verificar o efeito da época de poda sobre o crescimento e a produção da figueira 'Roxo de Valinhos', cultivada na região oeste do Paraná, sob sistema orgânico, para a produção de figos-verdes. O delineamento utilizado foi em blocos ao acaso, com quatro blocos e seis tratamentos - épocas de poda: abril, maio, junho, julho, agosto e setembro. em cada parcela, constituída de três plantas úteis, foram coletados dados no ciclo de produção de 2007/2008. As variáveis fenológicas, comprimento final médio dos ramos, produção por mês (número e massa média de frutos por planta e produtividade estimada, entre os meses de outubro a fevereiro), produção acumulada, produtividade estimada acumulada e massa fresca média dos frutos. Houve diferenças na produção entre as épocas de poda; plantas podadas em julho e agosto apresentaram as maiores produções, escalonadas entre os meses de dezembro a fevereiro, com pico de produção em janeiro.

Combination of t(t)over-bar cross section measurements and constraints on the mass of the top quark and its decays into charged Higgs bosons

We combine measurements of the top quark pair production cross section in p (p) over bar collisions in the l + jets, ll, and tau l final states ( where l is an electron or muon) at a center of mass energy of root s = 1.96 TeV in 1 fb(-1) of data collected with the D0 detector. For a top quark mass of 170 GeV/c(2), we obtain sigma(t (t) over bar) = 8.18(-0.87)(+0.98) pb in agreement with the theoretical prediction. Based on predictions from higher order quantum chromodynamics, we extract a mass for the top quark from the combined t (t) over bar cross section, consistent with the world average of the top quark mass. In addition, the ratios of t (t) over bar cross sections in different final states are used to set upper limits on the branching fractions B(t -> H(+)b -> tau(+) vb) and B(t -> H(+)b -> c (s) over barb) as a function of the charged Higgs boson mass.

Precise Measurement of the Top Quark Mass in the Dilepton Channel at D0

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Dano de frio em limas-ácidas Tahiti, colhidas em diferentes épocas e submetidas a tratamentos térmicos e bioquímicos

O estudo objetivou o estabelecimento de um método efetivo e satisfatório do controle do dano de frio em limas-ácidas. Os frutos colhidos no município de Boa Vista-RR, 140 e 150 dias após a floração, apresentaram valores médios de 7,9 e 8,2 ºBrix; 6,3 e 6,0 mL de ácido cítrico.100mL de polpa-1 e pH de 2,8 e 3,0, respectivamente, nas duas colheitas. Após cada colheita, os frutos foram levados ao laboratório de Fitotecnia/UFRR, onde foram selecionados, limpos e submetidos aos tratamentos: T1 - controle; T2, T3 e T4 - condicionamento a 35ºC, por 6, 12 e 24 horas, respectivamente; T5 - aquecimento intermitente a 20ºC, por 8 horas, após 5 e 10 dias a 1ºC; T6 - aquecimento intermitente a 20ºC, por 8 horas, após 10 e 20 dias a 1ºC; T7 - ethephon a 1.500 mg.L-1; T8 - ethephon a 3.000 mg.L-1. Os tratamentos T9 ao T16, diferenciaram-se dos tratamentos T1 a T8, apenas, na data da colheita (10 dias após a primeira). O experimento foi avaliado a cada 15 dias, durante 75 dias, a 1 ± 0,5 ºC e 92 ± 5 % de UR, quanto ao dano de frio, aspecto visual, perda de massa fresca, sólidos solúveis (SS), acidez titulável (AT), SS/AT (ratio - RT), clorofila total e ácido ascórbico. O atraso na colheita não proporcionou efeito significativo algum. Todos os tratamentos, à exceção do controle e do aquecimento intermitente aos 10 e 20 dias, foram eficientes no controle do dano de frio. No entanto, o tratamento químico e o condicionamento térmico aceleraram precocemente o metabolismo dos frutos, principalmente no que concerne à perda de massa fresca e ao aspecto visual. O maior teor de clorofila total e de ácido ascórbico, bem como o melhor aspecto visual, a não-incidência de podridões e a menor perda de massa fresca foram detectadas nos frutos submetidos ao aquecimento intermitente aos 5 e 10 dias. Os SS, AT e RT estavam dentro dos padrões de qualidade e não variaram estatisticamente entre os tratamentos.