NH₂NH-MOF: a reaction matrix for the specific determination of small aldehydes by MALDI-MS

Efficient determination of aldehydes by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is hampered mainly by the low mass and unstable nature of analytes. In the present work, we propose a combined strategy of a reactive metal–organic framework (MOF) matrix for the derivatization and detection of aldehydes. A novel reactive MOF matrix (NH₂NH-MOF) was synthesized in two steps. First, NR₃⁺-MOF was synthesized via Cu²⁺ and the quaternary amine ligand 4,4′-bipyridinium, 1,1″-(1,2-ethanediyl)bis-, dibromide (PyEtBr). Then, -NHNH₂ was introduced to NR₃⁺-MOF through electrostatic adsorption between the -NR₃⁺ and -HSO₃⁻ of 4-hydrazinylbenzenesulfonic acid to synthesize NH₂NH-MOF. The acid–base chemistry of NH₂NH-MOF led to uniform cocrystallization of the aldehyde-matrix mixtures and helped to achieve the detection of low-weight aldehydes with good relative standard deviations (RSDs = 0.07–12.35%). It was confirmed that this strategy can accurately quantify formaldehyde, valeraldehyde, and benzaldehyde with good linearity (r > 0.97). Furthermore, this strategy was applied to quantitatively detect benzaldehyde in wastewater, thus showing potential applications in environmental pollutant detection.