ABSTRACT
Ultrasound-assisted extraction (UAE), cloud point extraction (CPE), and ultrasound back-extraction (UABE) techniques have been coupled for lixiviation, preconcentration, and cleanup of polybrominated diphenyl ethers (PBDEs) from milk samples for determination by gas chromatography-electron capture detection (GC-ECD). Physicochemical parameters that affect the efficiency of the extraction system were investigated using a design of experiments based on multivariate statistical tools, and considering the sample matrix along the development. The coupling of the leaching step, UAE, enhanced ca. 3.5 times the extraction efficiency of the former sample preparation methodology (CPE-UABE) leading to cleaner sample extracts suitable for GC analysis. Under optimum conditions, the proposed methodology exhibits successful performance in terms of linearity and precision, with recoveries in the range of 68-70% and LODs within the range 0.05-0.5 ng/g dry weight (d.w.). The proposed sample preparation methodology coupled three green analytical techniques. It expands the application frontiers of CPE for the analysis of biological samples by GC. The optimized methodology was used for determination of PBDEs in powder milk samples, from both commercial and human sources.
Subject(s)
Green Chemistry Technology/methods , Halogenated Diphenyl Ethers/analysis , Milk/chemistry , Sonication/methods , Animals , Chemical Fractionation , Chromatography, Gas/methods , Halogenated Diphenyl Ethers/chemistry , Halogenated Diphenyl Ethers/isolation & purification , Limit of Detection , Linear Models , Reproducibility of Results , Research DesignABSTRACT
A new molecularly imprinted polymer modified with restricted access material (a hydrophilic external layer), (MIP-RAM) was synthesized via polymerization in situ in an open fused silica capillary. This stationary phase was used as sorbent for in-tube solid phase microextraction (in-tube SPME) to determine parabens in breast milk samples by ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). Scanning electron micrographs (SEM) illustrate MIP surface modification after glycerol dimethacrylate (hydrophilic monomer) incorporation. The interaction between parabens and MIP-RAM was investigated by Fourier-transform infrared (FTIR) spectroscopy. The Scatchard plot for MIP-RAM presented two linear parts with different slopes, illustrating binding sites with high- and low-affinity. Endogenous compounds exclusion from the MIP-RAM capillary was demonstrated by in-tube SPME/LC-UV assays carried out with blank milk samples. The in-tube SPME/UHPLC-MS/MS method presented linear range from 10 ng mL(-1) (LLOQ) to 400 ng mL(-1) with coefficients of determination higher than 0.99, inter-assay precision with coefficient of variation (CV) values ranging from 2 to 15%, and inter-assay accuracy with relative standard deviation (RSD) values ranging from -1% to 19%. Analytical validation parameters attested that in-tube SPME/UHPLC-MS/MS is an appropriate method to determine parabens in human milk samples to assess human exposure to these compounds. Analysis of breast milk samples from lactating women demonstrated that the proposed method is effective.