A miniaturized stir bar sorptive dispersive microextraction method for the determination of bisphenols in follicular fluid using a magnetic covalent organic framework.

ABSTRACT

BACKGROUND: Bisphenols, particularly bisphenol A (BPA), are the primary monomers used as additives in the manufacturing of many consumer products. The exposure to these compounds is related to endocrine-disrupting and reproductive effects, among others. For this reason, the development of analytical methods for their determination in biological matrixes is needed to monitor the population exposure to these compounds. Their quantification at ovarian level (i.e., follicular fluid) is interesting for the assessment of the bisphenol content to draw conclusions about infertility problems. However, the background does not meet all requirements by focusing mainly on BPA. RESULTS: In this work, a miniaturized stir bar sorptive dispersive microextraction (mSBSDME) approach has been developed for the determination of BPA and eight analogues in follicular fluid. In the proposed method, the sample is previously cleaned-up using a zirconia-based solid-phase extraction cartridge, removing proteins and phospholipids, and then subjected to the mSBSDME for the preconcentration of the analytes. For this purpose, a magnetic covalent organic framework was used as sorbent. A Plackett-Burman design was applied to select the significant variables affecting the mSBSDME. Afterwards, the only significant variable (i.e., sorbent amount) was optimized. Under the optimized conditions, the proposed method was properly validated, and satisfactory analytical parameters in terms of linearity (up to 50 ng mL-1), enrichment factors (8.5-14.3), limits of detection in the low ng mL-1 range, and precision (relative standard deviations below 11.5 %) were obtained. Finally, the method was successfully applied to five samples, detecting BPA and other two analogues. SIGNIFICANCE: This method expands the potential applicability of the mSBSDME to other low-availability complex matrixes, which would otherwise be difficult to analyze. Moreover, it offers a valuable tool for monitoring the female population's exposure to bisphenols with the final aim of evaluating if infertility problems of women might be associated to the exposure to these highly endocrine disrupting compounds.