A modified QuEChERS method was optimized for simultaneous extraction of 93 pesticides and 6 polycyclic aromatic hydrocarbons (PAHs) in cachaça. The procedure employed 20 mL of sample, 10 mL of dichloromethane, 1 g of NaCl, and 6 g of MgSO4. The methods were validated in accordance with pesticide tolerances set by the National Health Surveillance Agency of Brazil and government guidelines of Brazil and the European Union. The linearity of all curves was adequate, with calculated t r higher than the critical value, at the 95% confidence level. For pesticides, recoveries ranged between 86.7 and 118.2%, relative standard deviation (RSD) ≤ 20%, at least at two concentration levels, and limit of detection (LOD) and limit of quantitation (LOQ) were 2.5 and 10.0 μg L–1, respectively. For PAHs, recoveries ranged between 84.8 and 111.5%, RSD was between 6.2 and 27.3%, LOD and LOQ were 0.25 and 1.0 μg L–1, respectively. The combined standard uncertainty was lower than 50% of the relative expanded uncertainty value at concentration levels of greater relevance in both methods. Analyses of five commercial samples detected the presence of 9 pesticides (10.0–128.0 μg L–1) and 6 PAHs (2.0–4.0 μg L–1), indicating the need for a specific legislation for Brazilian cachaça.

In this work, a GC-MS/MS method was developed for the determination of anabolic-agent residues in bovine urine. The optimized sample preparation was as follows: enzymatic hydrolysis by β-glucuronidase-sulfatase enzyme from Helix pomatia for 16 h at 37.5 °C, liquid-liquid extraction with diethyl ether, solid-phase extraction with HLB and aminopropylsilane cartridges, and microwave-assisted derivatization using 25 μL of MSTFA/NHI/ethanethiol and full microwave power for 2 min. The method was validated according to Decision 657/2002/EC, Codex Alimentarius, and Manual da Garantia da Qualidade Analítica guidelines. The acceptability criteria for quantitative analysis were met for α-ethinylestradiol, α-nandrolone, β-estradiol, β-zearalanol, β-zearalenol, drostanolone, ethisterone, dienestrol, diethylstilbestrol, hexestrol, megestrol, methyltestosterone, and zearalenone. The analytes α-zearalenol, α-zearalanol, and norethandrolone were validated for qualitative analysis.

The compounds 3-oxofriedelane (1), 3beta-hydroxyfriedelane (2), 3,11-dioxofriedelane (3), 3,16-dioxofrie delane (4) and 3-oxo-12alpha-hydroxyfriedelane (5) were isolated from the hexane extract of Maytenus gonoclada Mart. (Celastraceae) leaves. Structural formula and the stereochemistry of the new pentacyclic triterpene 3-oxo-12alpha-hydroxyfriedelane (5) were established through (1)H and (13)C NMR and DEPT 135 spectral data including 2D experiments (HMBC, HMQC, COSY, and NOESY) and mass spectrometry (GC-MS).

A multiclass analytical method to determine pesticides and mycotoxins in beer-related matrices based on the dilute and shoot approach was optimized and validated according to the European guidelines SANTE/12682/2019 and EC/401/2006. Extraction used acidified acetonitrile at 1% (v/v) acetic acid, followed by horizontal shaking homogenization, centrifugation, freeze-out step for cleanup, another centrifugation, and injection into a high-performance liquid chromatography–tandem mass spectrometry system. Linearity, detection and quantification limits, accuracy, and measurement uncertainty were evaluated, and 201, 184, and 176 analytes were validated for malt, beer, and brewers’ spent grain, respectively. The limits of quantification ranged between 1 and 200 μg kg–1 and between 5 and 1000 μg kg–1 for beer and malt, respectively, and expanded uncertainties ranged between 9.7 and 50%, meeting the legislation requirements. A total of 40 samples have been analyzed thus far, and 36 of them exhibited the presence of some of the analyzed substances. The validated method is reliable and easy to apply for mycotoxin and pesticide determination in complex matrices.

An EI-GC/MS method for the determination of pesticide residues in vegetable matrices with high water content was validated using papaya samples. The validation of a multi-residue pesticide method was in agreement with national and international regulations enabling the Ministry of the Agriculture, Livestock and Food Supply of Brazil to cover a large number of matrices and pesticide residues in its monitoring and control programmes. The extraction used 60 mL of ethyl acetate and 30 g of sample previously processed. After extraction, clean-up of all the extracts was carried out by percolation through GBC cartridges. The samples were then injected in an EI-GC/MS system. Calibration curves were prepared in quadruplet by fortifying blank extracts with a standard solution containing all the pesticides studied at 0.000, 0.005, 0.010, 0.020, 0.030, 0.050, 0.080 and 0.100 mg kg(-1). For the recovery study, blank samples were fortified at 0.010, 0.020, 0.030, 0.050 and 0.080 mg kg(-1) and then submitted to the extraction procedure. The complete procedure was repeated over four different days by two analysts. The regression parameters of calibration curves were calculated for each validation day. Linearity, selectivity, specificity, robustness, limits of detection and quantification were also assessed. The uncertainty was estimated for each analyte at each spike level studied. The method had recoveries between 91% and 105% and precision results ≤ 20%. Limits of quantification were below or equal to the maximum residue limits (MRLs) regulated by Brazilian legislation. The MRLs of the selected pesticides are not regulated by CODEX Alimentarius. The results are also in agreement with SANCO/10684/2009.