ZIF-based boronic acid functionalized metal-organic frameworks for the enrichment of cis-diol-containing luteolin from food samples prior to HPLC.

Zeolite imidazole framework-based boronic acid-functionalized metal-organic frameworks (ZIF-67@PDA@BA-Zr-MOFs) were developed as an adsorbent for solid phase extraction (SPE) of luteolin (LTL) from peanut shell samples. Herein, ZIF-67 as a support matrix, polydopamine (PDA) as a coating to introduce amino and hydroxyl groups on the matrix surface to fix metal-organic frameworks (MOFs), zirconium tetrachloride (ZrCl4) as a precursor, terephthalic acid (TPA), and 3-carboxyphenylboronic acid (3-CPBA) as the mutual organic building blocks, and 3-CPBA was also a boronate affinity functional monomer. The effects of synthesis conditions, SPE conditions, selectivity, competitivity, reproducibility, and reusability were evaluated in detail. Under the optimal conditions, the maximum adsorption capacity is 71.4 mg g-1. The utility of ZIF-67@PDA@BA-Zr-MOFs as an adsorbent for SPE of LTL is supported by the presence of the abundant pore structure, as well as the boronate affinity sites facilitated the rapid binding of the adsorbent to the template. The concentration of the extracted LTL was determined by the high-performance liquid chromatography-ultraviolet (HPLC-UV), with calibration plots being linear in the concentration range 0.05-100 mg L-1 and a limit of detection (LOD) of 0.035 mg L-1. The method was applied to determine the LTL in peanut shell samples and recovered the target analyte in the range 85.6% to 99.2% (the standard deviations are less than 3.3%, n = 3). In addition, we incorporated boronate affinity and MOFs material into an SPE system to provide a promising strategy to detect other cis-diol-containing analytes in the complex matrix.