Sulfonic acid functionalized hierarchical porous covalent organic frameworks as a SALDI-TOF MS matrix for effective extraction and detection of paraquat and diquat.

Design and construction of a matrix with specific adsorption on the target compounds can effectively reduce the detection limit of surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-TOF MS) analysis. Sulfonic acid functionalized hierarchical porous covalent organic frameworks (H-COF-SO3H) was synthesized by defect-structure and post-modification method, and then used as matrix and adsorbent for the determination of quaternary ammonium herbicides paraquat (PQ) and diquat (DQ). N2 adsorption-desorption experiments confirmed that H-COF-SO3H possesses hierarchical porosity with pore widths concentrated at 1.3,1.5, and 2.8 nm. The strong UV absorption at 200-450 nm and good thermal stability made H-COF-SO3H being a promising matrix without background interference. H-COF-SO3H can efficiently enrich PQ and DQ via electrostatic attraction, and the key role of -SO3H group on specific adsorption was confirmed by density functional theory (DFT) calculations. The limits of detection (LODs) for PQ and DQ with H-COF-SO3H enrichment were 0.5 and 0.1 ng·mL-1, respectively, which were 20 and 60 times higher than those without H-COF-SO3H enrichment, respectively. The spiked recoveries of PQ and DQ for the three food samples were 92.0-113.2% and 80.1-102.6% with RSDs of 2.2-9.2% and 2.0-8.7%, respectively. This work provides an analyte-oriented approach for fabricating SALDI-TOF MS matrix.