Dual-Ion-Mode MALDI MS Detection of Small Molecules with the O–P,N-Doped Carbon/Graphene Matrix

It is challenging to realize a dual-ion mode of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) for detecting small molecules. Herein, graphene coated by porous amorphous carbon with P–O surface group and codoped by phosphorus and nitrogen (O–P,N-C/G) was synthesized from an aerogel formed by phytic acid, polyaniline, and electrochemically exfoliated graphene. The carbon material synthesized has the feature of large surface area (583 m2/g), good electrical conductivity, strong UV absorption, heteroatom doping, and surface functional groups suitable for laser- induced desorption/ionization. It was employed as a novel matrix suitable for both positive-ion and negative-ion modes in MALDI-TOF MS for the analysis of various small molecules including amino acids, small peptides, saccharides, drugs, and environmental pollutants, significantly outperforming control materials and a traditional CHCA (α-cyano-4-hydroxycinnamic acid) or 2,5-dihydroxybenzoic (DHB) matrix. Remarkably, the detection limit of the anticancer drugs (5-fluorouracil and ellagic acid) reaches 50 pmol. In addition, nice MALDI-TOF MS images can be mapped to detect mixed amino acids corresponding to homogeneous distribution of ion intensity. The monosaccharides and disaccharides can be distinguished by using the new matrix. Last but not least, it can be used to quantitatively detect glucose in human serum and soft drinks (glucose/fructose, 203.1 mM) without adding standards.