Hydrophilic Covalent Organic Frameworks Coated Steel Sheet As a Mass Spectrometric Ionization Source for the Direct Determination of Zearalenone and Its Derivatives

Zearalenone has attracted worldwide attention due to its toxic properties and threat to public health. A rapid determination method for zearalenone and its derivatives by hydrophilic covalent organic frameworks coated steel sheet (HCOFCS) combined with ambient mass spectrometry (AMS) was developed. The HCOFCS behaved as both a tip for solid-phase microextraction and a solid substrate for electrospray ionization mass spectrometry (ESI-MS). To evaluate the HCOFCS-ESI-MS method, five zearalenone and its derivatives in milk samples were determined, including zearalenone (ZEA), α-zearalenol (α-ZEL), β-zearalenol (β-ZEL), α-zearalanol (α-ZAL), and β-zearalanol (β-ZAL). After the extraction procedure, the HCOFCS was directly added with a high voltage for ESI-MS, and the analysis could be completed within 1 min. The developed method showed good linearity in the range 0.1-100 μg/L with a coefficient of determination (R²) > 0.9991. The limits of detection (LODs) and limits of quantitation (LOQs) ranged from 0.05 to 0.1 and 0.2 to 0.3 μg/L, respectively. The results demonstrated that the HCOFCS combined with ESI-MS can be used for the rapid and sensitive determination of trace ZEA and its derivatives in milk samples with satisfactory recoveries from 80.58% to 109.98% and reproducibility with relative standard deviations (RSDs) no more than 11.18%. Furthermore, HCOFCS showed good reusability, which could reuse at least 10 extraction cycles with satisfactory adsorption performance.