Abstract
Sulforaphane (SFN) is a natural isothiocyanate compound widely abundant in cruciferous vegetables with multiple bioactive functions. However, traditional analytical methods for the extraction and determination of SFN are cumbersome, time-consuming, and low sensitivity with large amounts of organic solvents. Herein, novel magnetic COF-on-COFs (MB-COFs) were fabricated using Fe3O4 as a magnetic core and COFs-1 grown with COFs-2 as a shell, and they were used as efficient adsorbents of magnetic dispersive solid-phase extraction for rapid quantification of SFN in cruciferous vegetables by combining with HPLC-MS/MS. At the optimal ratio of COFs-1 to COFs-2, MB-COFs had a spherical cluster-like structure and a rough surface, with a sufficient magnetic response for rapid magnetic separation (1 min). Due to the introduction of Fe3O4 and COFs-2, MB-COFs exhibited outstanding extraction efficiencies for SFN (92.5-97.3%), which was about 18-72% higher than that of the bare COFs. Moreover, MB-COFs showed good adsorption capacity (Qm of 18.0 mg/g), rapid adsorption (5 min) and desorption (30 s) to SFN, and favorable reusability (≥7 cycles) by virtue of their unique hierarchical porous structure. The adsorption kinetic data were well fitted by the pseudo-second-order, Ritchie-second-order, intra-particle diffusion, and Elovich models, while the adsorption isotherm data were highly consistent with the Langmuir, Temkin, and Redlich-Peterson models. Finally, under the optimized conditions, the developed method showed a wide linear range (0.001-0.5 mg/L), high sensitivity (limits of quantification of 0.18-0.31 μg/L), satisfactory recoveries (82.2-96.2%) and precisions (1.8-7.9%), and a negligible matrix effect (0.82-0.97). Compared to previous methods, the proposed method is faster and more sensitive and significantly reduces the use of organic solvents, which can achieve the efficient detection of large-scale samples in practical scenarios. This work reveals the high practical potential of MB-COFs as adsorbents for efficient extraction and sensitive analysis of SFN in cruciferous vegetables.