A rapid and sensitive online restricted access molecularly imprinted solid-phase extraction method coupled to a liquid chromatography-mass spectrometry (LC-MS) system for simultaneous determination of serum bile acids as well as their taurine and glycine conjugates was developed. Reversible liver damage of workers exposed to volatile organic solvents can be investigated based on the level of the analyzed molecules. A restricted access molecularly imprinted polymer coated with bovine serum albumin (RAMIP-BSA) was synthesized and used as the extraction phase. The column switching liquid chromatography system was able to exclude about 100% of the macromolecules and extract/separate nine bile acids from blood human serum samples, in a total time of 40 minutes. The developed method was validated based on the Food and Drug Administration (FDA) guidelines, being linear for all the analytes in their respective analytical ranges (coefficients of determination higher than 0.99), with limits of detection (LOD) and quantification (LOQ) ranging from 2.0 to 5.7 μg L⁻¹ and from 10.0 to 25.0 μg L⁻¹, respectively. Suitable results for precision (relative standard deviation ranged from 3.2 to 14.5% and 0.7 to 14.8%, respectively for intra and inter-assay) and accuracy (relative error ranged from −14.8 to 14.2%; −13.8 to 14.3%) were obtained. The validated analytical method was applied to determine bile acids in serum samples of five workers occupationally exposed to volatile organic solvent, demonstrating its applicability in the assessment of these toxicants.

Pesticides constitute a category of chemical products intended specifically for the control and mitigation of pests. With their constant increase in use, the risk to human health and the environment has increased proportionally due to occupational and environmental exposure to these compounds. The use of these chemicals is associated with several toxic effects related to acute and chronic toxicity, such as infertility, hormonal disorders and cancer. The present work aimed to study the metabolic profile of individuals occupationally exposed to pesticides, using a metabolomics tool to identify potential new biomarkers. Metabolomics analysis was carried out on plasma and urine samples from individuals exposed and non-exposed occupationally, using liquid chromatography coupled with mass spectrometry (UPLC-MS). Non-targeted metabolomics analysis, using principal component analysis (PCA), partial least squares discriminant analysis (PLS-DA) or partial least squares discriminant orthogonal analysis (OPLS-DA), demonstrated good separation of the samples and identified 21 discriminating metabolites in plasma and 17 in urine. The analysis of the ROC curve indicated the compounds with the greatest potential for biomarkers. Comprehensive analysis of the metabolic pathways influenced by exposure to pesticides revealed alterations, mainly in lipid and amino acid metabolism. This study indicates that the use of metabolomics provides important information about complex biological responses.