Surface Siloxane-Modified Silica Materials Combined with Metal–Organic Frameworks as Novel MALDI Matrixes for the Detection of Low-MW Compounds

Surface siloxane (3-aminopropyl triethoxysilane hydrolyzates)-modified silica materials were used as "initiators", which resulted in the release and desorption of intact molecules adsorbed on the surface of a matrix. A covalently cross-linked MIL-53(Al) material was used to enhance the ionization of analytes. Herein, we have provided an efficient matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOF MS) matrix strategy, which responded to both ion and laser irradiation with low background interference in the low-molecular-weight (MW) region. The matrixes MIL-53(Al), SBA-15@APTES, SiO2@APTES, SBA-15@APTES@MOF, and SiO2@APTES@MOF were synthetized and used for the analysis of a series of low-MW compounds to verify the effectiveness of the strategies. Compared to conventional matrixes, the surface-modified SBA-15@APTES@MOF and SiO2@APTES@MOF had low background, high sensitivity, extensive applicability, good stability, and ultrahigh tolerance of salt concentrations. The detection limits of standard analytes were determined to range from 0.1 to 1 × 10–5 mg/mL for 16 amino acids as well as citric acid, reserpine, tetraethylammonium chloride, melamine, bisphenol A, and malachite green. These results could help in designing more efficient nanostructure-initiator materials and further promote the application of MALDI-TOF MS.