RESUMO
Fungi of the genus Trichoderma have been marketed for the management of diseases of crops. However, some Trichoderma species may produce toxic secondary metabolites and it should receive due attention to ensure human safety. In this study, we investigated the in vitro antagonistic potential of T. asperellum AU131 and T. longibrachiatum AU158 as microbial biocontrol agents (MBCAs) against Fusarium xylarioides and the associated antagonistic mechanism with bioactive substances. Swiss albino mice were used to evaluate the in vivo toxicity and pathogenicity of T. asperellum AU131 and T. longibrachiatum AU158 methanolic extracts and spore suspensions, respectively, in a preliminary safety assessment for use as biofungicides. Gas Chromatography-Mass Spectrometry (GC-MS) was used to profile volatile organic metabolites (VOCs) present in the methanolic extracts. The agar diffusion assay of the methanolic extracts from both T. asperellum AU131 and T. longibrachiatum AU158 were effective at a concentration of 200 µg/mL (1×107 spores/mL), causing 62.5%, and 74.3% inhibition, respectively. A GC-MS analysis of methanolic extracts from both bioagents identified 23 VOCs which classified as alcohols, acids, sesquiterpenes, ketones and aromatic compounds. The oral administration of methanolic extracts and spore suspensions of each Trichoderma species to female Swiss albino mice over 14 days did not show any significant signs of toxicity, mortality or changes to body weight. It can be concluded that the tested spore suspensions and methanolic extracts were not pathogenic or toxic, respectively, when administered to Swiss albino mice at various doses.
Assuntos
Trichoderma , Ágar/metabolismo , Animais , Antifúngicos/farmacologia , Feminino , Cromatografia Gasosa-Espectrometria de Massas , Humanos , Cetonas/metabolismo , Metanol/metabolismo , Camundongos , Modelos Animais , Trichoderma/metabolismoRESUMO
The intensive application of pesticides to increase crop production has resulted in contamination of the agricultural products. Due to their occurrence at trace levels and the complexity of food samples, analysis of pesticide residues requires selective and efficient sample preparation methods. For this purpose, an extraction method based on supercritical carbon dioxide and acetonitrile as entrainer solvent was developed for trace analysis of atrazine, diazinon, chlorothalonil, and deltamethrin pesticides in honey samples. A Box-Behnken experimental design was applied to optimize extraction variables including static extraction time (5-15 min), pressure (200-700 bar), and temperature (45-70°C). The optimum extraction conditions were found to be 11.5 min static extraction time, 252 bar, and 70°C. The proposed analytical method showed a good linearity (≥0.998), low limit of detection (0.005-0.009 mg/kg), and good extraction recovery (74-111%). The precision study of the proposed method at two concentration levels of each pesticides, 0.25 and 1.0 mg/kg was found to be in the ranges of 2.3-4.21% for intraday (n = 3) and 3.93-8.02% for interday precisions (n = 3). The developed method is promising for use in trace analysis of pesticides in complex food samples including honey.
Assuntos
Cromatografia com Fluido Supercrítico , Análise de Alimentos , Contaminação de Alimentos/análise , Mel/análise , Praguicidas/análise , Acetonitrilas/química , Dióxido de Carbono/química , Estrutura Molecular , Análise MultivariadaRESUMO
The excessive use of pesticides is a serious health problem due to their toxicity and bioaccumulation through the food chain. Due to the complexity of foods, the analysis of pesticides is challenging often giving large matrix effects and co-extracted compounds. To overcome this problem, a selective and "green" supercritical fluid extraction method was developed, using neat carbon dioxide as a solvent at pressures of up to 800 bars. A Box-Behnken response surface experimental design was used, with the independent variables of density (0.70-1.0 g mL-1), temperature (40-70 C), and volume (10-40 mL) of solvent, and the dependent variable of extracted amount of pesticides. The optimum extraction condition was found at the use of 29 mL of supercritical CO2 at 0.90 g mL-1 and 53C (corresponding to 372 bars of pressure). It was observed that increasing the density of CO2 significantly increased the extraction recovery of endrin and 2,4'-dichlorodiphenyldichloroethane. Matrix-matched calibration curves showed satisfactory linearity (R2 ≥ 0.994), and LODs ranged from 0.2 to 2.0 ng g-1. Precision was lower than 11% and recoveries between 80%-103%. Thus, the developed method could efficiently be used for trace analysis of pesticides in complex food matrices without the use of organic solvents.
Assuntos
Dióxido de Carbono/química , Cromatografia com Fluido Supercrítico/métodos , Análise de Alimentos/métodos , Cebolas/química , Resíduos de Praguicidas/isolamento & purificação , Solventes/química , Diclorodifenildicloroetano/isolamento & purificação , Endrin/isolamento & purificação , Análise Fatorial , Contaminação de Alimentos , Humanos , Limite de Detecção , TemperaturaRESUMO
3-Methyl-1,2,3-butanetricarboxylic acid (MBTCA) is a secondary organic aerosol and can be used as a unique emission marker of biogenic emissions of monoterpenes. Seasonal variations and differences in vegetation cover around the world may lead to low atmospheric MBTCA concentrations, in many cases too low to be measured. Hence, an important tool to quantify the contribution of terrestrial vegetation to the loading of secondary organic aerosol may be compromised. To meet this challenge, a dispersive liquid-liquid microextraction (DLLME) method, known for the extraction of hydrophobic compounds, was extended to the extraction of polar organic compounds like MBTCA without compromising the efficiency of the method. The extraction solvent was fine-tuned using tri-n-octyl phosphine oxide as additive. A multivariate experimental design was applied for deeper understanding of significant variables and interactions between them. The optimum extraction conditions included 1-octanol with 15% tri-n-octyl phosphine oxide (w/w) as extraction solvent, methanol as dispersive solvent, 25% NaCl dissolved in 5 mL sample (w/w) acidified to pH 2 using HNO3, and extraction time of 15 min. A limit of detection of 0.12 pg/m3 in air was achieved. Furthermore, unique complexation behavior of MBTCA with iron(III) was found when analyzed with ultra-high-performance liquid chromatography coupled with electrospray ionization-quadrupole time-of-flight mass spectrometry (UHPLC-ESI-QToF). A comprehensive overview of this complexation behavior of MBTCA was examined with systematically designed experiments. This newly discovered behavior of MBTCA will be of interest for further research on organometallic photooxidation chemistry of atmospheric aerosols. Graphical abstract a) Additive assisted DLLME and MBTCA complexes with Fe(III), b) A good quality figure is attached in ppt format to facilitate editable objects.
RESUMO
A rapid, efficient, and new solvent terminated dispersive liquid-liquid microextraction technique coupled with HPLC was developed for selective extraction and analysis of s-triazine herbicides from environmental water samples. Important parameters influencing the extraction process including type and volume of extraction and disperser solvent, extraction time, sample pH, ionic strength, and extraction temperature were successfully optimized. Under the optimal conditions, there are excellent linear relationships between the analytical results and concentration in the range of 10-400 mg/L for atrazine, propazine, prometryn, and terbutryn. LOD and LOQ ranged from 0.60 to 2.33 µg/L and 2.0 to 7.7 µg/L, respectively. Performance of the analytical technique was evaluated by carrying out the repeatability and reproducibility analyses that were ranged from 2.86 to 5.66% and 4.64 to 5.89% for 100 µg/L of each target analyte, respectively. The proposed method has been successfully applied to the analysis of real water samples and acceptable relative recoveries over the range of 65.93-101.46%, with RSDs ≤ 8.80%, were obtained. The overall results have been compared with the literature values. Thus, the method developed could efficiently be used for selective extraction of the target analytes from complex matrices, particularly environmental waters.