HPLC combined with multiple mass spectrometry (MSn): an alternative for the structure elucidation of compounds and artefacts found in smog chamber samples

Ion trap multiple mass spectrometry combined with high-performance liquid chromatography (online HPLC-MSn) was used to identify carbonyl compounds and artefacts found in air samples of 2-3 L taken during the OH-radical reaction study of cis-3-acetyl-2,2-dimethylcyclobutylethanal (pinonal) or cis-3-acetyl-2,2-dimethylcyclobutylcarbaldehyde (nor-pinonal) in a smog chamber. Carbonyls were transformed into 2,4-dinitrophenylhydrazones. Detection of low picogram quantities was possible. Twenty-eight compounds could be identified based on the presence of structure characteristic fragments, a developed fragmentation scheme, comparison of retention times and a library of MSn spectra of selected carbonyls. Furthermore, the additional elucidation of the sub-structures of sixteen unknowns was possible. Details about the structure elucidation procedure and the formation of the observed fragments are presented.