Structure-Assisted Boronic Acid Implanted Mesoporous Metal–Organic Frameworks for Specific Extraction of cis-Diol Molecules

cis-Diol-containing molecules, an essential type of compounds in living organisms, have attracted intensive research interest from various fields. The analysis of cis-diol-containing molecules is still suffering from some drawbacks, including low abundance and abundant interference. Metal–organic frameworks (MOFs) have proven to be an ideal sorbent for sample preparation. However, most of the reported MOFs are mainly restricted to a microporous regime (pore size <2 nm), which greatly limits the application. Herein, a facile strategy is established to construction of boronate affinity MOFs via the postsynthetic ligand-exchange process. Owing to the fact that the ligand-exchange process was assisted by the structural integrity of the primitive metal–organic framework and the great compatibility of click chemistry, the obtained EPBA-PCN-333(Fe) is able to realize the maximum maintaining the porosity and crystallinity of the parent material. Several intriguing features of EPBA-PCN-333(Fe) (e.g., excellent selectivity, efficient diffusion, good accessibility, and size exclusion effect) are experimentally demonstrated via a series of cis-diol-containing molecules with different molecular sizes (small molecules, glycopeptides, and glycoproteins). The binding performance of EPBA-PCN-333(Fe) is evaluated by employing catechol as the test molecule (binding capacity: 0.25 mmol/g, LOD: 200 ng/mL). Finally, the real-world applications of EPBA-PCN-333(Fe) were demonstrated by the detection of nucleosides of human urine samples.