Rewiring cis-2-butene-1,4-dial mediated urinary metabolomics fingerprints of short-term exposure to furan.

Furan represents one of the dietary-sourced persistent organic pollutants and thermal processing contaminants. Given its widespread occurrence in food and various toxicological effects, accurately assessing furan exposure is essential for informing public health risks. Furan is metabolized to a reactive primary product, cis-2-butene-1,4-dial (BDA) upon absorption. Some of the resulting BDA-derived metabolites have been proposed as potential exposure biomarkers of furan. However, the lack of quantification for recognized and feasible furan biomarkers has hampered the development of internal exposure risk assessment of furan. In this study, we employed reliable non-targeted metabolomics techniques to uncover urinary furan metabolites and elucidate their chemical structures. We characterized 8 reported and 11 new furan metabolites derived from the binding of BDA with glutathione (GSH), biogenic amines, and/or amino acids in the urine of male rats subjected to varying doses of furan. Notably, a mono-GSH-BDA adduct named cyclic GSH-BDA emerged as a highly prospective specific biomarker of furan exposure, as determined by an ultrahigh-performance liquid chromatography-tandem mass spectrometry method. Cyclic GSH-BDA demonstrated a robust mass spectrometry ion response intensity and exhibited evident time- and dose response. Additionally, we conducted a comprehensive profiling of the kinetics of potential furan biomarkers over time to capture the metabolic dynamics of furan in vivo. Most urinary furan metabolites reached peak concentrations at either the first (3 h) or second (6 h) sampling time point and were largely eliminated within 36 h following furan treatment. The present study provides novel insights into furan metabolism and sheds light on the biomonitoring of furan exposure.

Extraction of Pb(II) from wheat samples via dual-frequency ultrasound-assisted enzymatic digestion and the mechanisms of its interactions with wheat proteins.

A novel dual-frequency ultrasound-assisted enzymatic digestion (DUED) technique was used to extract Pb(II) from certified reference materials (CRMs) of wheat flour. Following this, the interactions of Pb(II) with wheat proteins were investigated to provide evidence for the selection of enzyme species. The results showed that the simultaneous use of α-amylase and flavourzyme resulted in the recovery of 97.9% of Pb(II) in 6 min under a 40 kHz ultrasonic bath combined with a 20 kHz ultrasonic probe. The exopeptidase activity of the flavourzyme was found to be the main contributor to the extraction of Pb(II) from the CRMs. Additionally, the proposed method exhibited a low detection limit (8.2 ng/g) and high recoveries of real samples (93.4%-112.2%) with RSD less than 7.33%. Furthermore, the oxygen-containing groups of wheat proteins, the nitrogen-containing groups of albumins and globulins, and the sulfur-containing groups of gliadins and glutenins were found to offer coordination sites for Pb(II).