Imprinted covalent organic frameworks solid-phase microextraction fiber for in vivo monitoring of acidic per- and polyfluoroalkyl substances in live aloe.

Per- and polyfluoroalkyl substances (PFASs) can lead to risks associated with animal and human health through the transfer along food chains. It is confirmed that PFASs can be transported to each part of plants after taken up by the roots. To better elucidate the underlying mechanisms for such exposure, it is highly valuable to develop analytical capabilities for in vivo monitoring of PFASs in live plants. In this work, a novel imprinted covalent organic frameworks (CMIP) solid-phase microextraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry was developed with low limits of detection for six acidic PFASs (0.1-0.3 ng g-1) and used for in vivo monitoring in live aloe. The CMIP coating shows good precision (RSD of intra and inter ≤9.6 % and 10.2 %, respectively) and possesses much higher extraction efficiency than the commercial coatings. After cultivating aloe in soil spiked PFASs, the in vivo assays gave a wealth of information, including steady-state concentrations, translocation factors, elimination rate constants, and half-life of PFASs. The in vivo tracing method for live plants can provide much needed and unique information to evaluate the risk of PFASs, which are very important for the safety of agriculture production.

Synthesis of a cysteine functional covalent organic framework via facile click reaction for the efficient solid phase extraction of substituted p-phenylenediamine-derived quinones.

N,N'-Substituted p-phenylenediamine quinones (PPD-Qs) are the emerging toxicant, which transform from the rubber tire antioxidant N,N'-substituted p-phenylenediamines (PPDs). Because of their potential toxic and widespread occurrence in the environment, PPD-Qs have received great attention. However, efficiently extracting PPD-Qs from complex samples is still a challenge. Herein, a cysteine functional covalent organic framework (Cys-COF) designed according to the "donor-acceptor" sites of hydrogen bonding of PPD-Qs was synthesized via click reaction and then used as solid-phase extraction (SPE) adsorbent. Cys-COF can form the seven-member ring adsorption structure with PPD-Qs via hydrogen bonding. The adsorption mechanism was tentatively revealed by density functional theory (DFT). After optimizing the Cys-COF-SPE parameters, PPD-Qs were efficiently extracted from water, soil, sediment, and fish, followed by detection using ultra-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The Cys-COF-SPE-UHPLC-MS/MS method exhibited ideal linearity (R2 ≥ 0.9932), high relative recoveries (80.4-111 %), and low limits of detection (0.0001-0.0013 ng mL-1). In addition, the bioconcentration kinetics in goldfish provides a feasible platform to investigate the toxicity and accumulated ability of PPD-Qs.