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Determination of aldehydes and ketones using derivatization with 2,4-dinitrophenylhydrazine and liquid chromatography–atmospheric pressure photoionization-mass spectrometry

2004; Elsevier BV; Volume: 1058; Issue: 1-2 Linguagem: Inglês

10.1016/j.chroma.2004.08.149

1873-3778

S.M. van Leeuwen, L Hendriksen, Uwe Kärst,

Analytical Chemistry and Chromatography

Atmospheric pressure photoionization-mass spectrometry (APPI-MS) is used for the analysis of aldehydes and ketones after derivatization with 2,4-dinitrophenylhydrazine (DNPH) and liquid chromatographic separation. In the negative ion mode, the [M − H]− pseudomolecular ions are most abundant for the carbonyls. Compared with the established atmospheric pressure chemical ionization (APCI)-MS, limits of detection are typically lower using similar conditions. Automobile exhaust and cigarette exhaust samples were analyzed with APPI-MS and APCI-MS in combination with an ion trap mass analyzer. Due to improved limits of detection, more of the less abundant long-chain carbonyls are detected with APPI-MS in real samples. While 2,4-dinitrophenylazide, a known reaction product of DNPH with nitrogen dioxide, is detected in APCI-MS due to dissociative electron capture, it is not observed at all in APPI-MS.