Extraction and derivatization in single drop coupled to MALDI-FTICR-MS for selective determination of small molecule aldehydes in single puff smoke

Abstract

Extraction and derivatization in single drop (EDSD) coupled to matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry (MALDI-FTICR-MS) was utilized to determine small molecular aldehydes (SMAs) in single puff smoke. A methanol solution of diphenylamine, 2,5-dihydroxybenzoic acid was used for extraction/derivatization of SMAs and a microdrop of the extraction solution containing the ionic derivatization products of SMAs could be directly deposited in the MALDI target to perform the measurement of SMAs in the cigarette smoke on puff level by MALDI-FTICR-MS. As a result, a consecutive operation of sample pre-treating and MALDI sample plate preparation was achieved. SMAs were derivatized by the reaction with diphenylamine and transformed a stable Schiff base bearing a quaternary ammonium group, and the sensitivity of analysis for SMAs was significantly improved. Good sample homogeneity in in-dot was achieved by adding diphenylamine into the solvent for EDSD and a satisfying repeatability (R.S.D. = 7.3% for formaldehyde, n = 5) of MALDI-FTICR-MS signals was obtained. This solvent- and reagent-minimized approach with an automatic potential provided a simple, rapid, and accurate procedure for the determination of SMAs in smoke.