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Modified proton transfer reaction mass spectrometry (PTR-MS) operating conditions for in vitro and in vivo analysis of wine aroma. | LitMetric

Modified proton transfer reaction mass spectrometry (PTR-MS) operating conditions for in vitro and in vivo analysis of wine aroma.

J Mass Spectrom

Centre des Sciences du Goût et de l'Alimentation (CSGA), AgroSup Dijon, CNRS, INRA, Université Bourgogne Franche-Comté, F-21000, Dijon, France.

Published: January 2018

AI Article Synopsis

Article Abstract

With proton transfer reaction-mass spectrometry standard operating conditions, analysis of alcoholic beverages is an analytical challenge. Ethanol reacts with the primary ion H O leading to its depletion and to formation of ethanol-related ions and clusters, resulting in unstable ionization and in significant fragmentation of analytes. Different methods were proposed but generally resulted in lowering the sensitivity and/or complicating the mass spectra. The aim of the present study was to propose a simple, sensitive, and reliable method with fragmentation as low as possible, linearity within a realistic range of volatile organic compounds concentrations, and applicability to in vivo dynamic aroma release (nosespace) studies of wines. For in vitro analyses, a reference flask containing a hydro-alcoholic solution (10% ethanol) was permanently connected to the PTR-MS inlet in order to establish ethanol chemical ionization conditions. A low electric field strength to number density ratio E/N (80 Td) was used in the drift-tube. A stable reagent ion distribution was obtained with the primary protonated ethanol ion C H OH accounting for more than 80% of the ionized species. The ethanol dimer (C H OH) H accounted for only 10%. Fragmentation of some aroma molecules important for white wine flavor (various esters, linalool, cis-rose oxide, 2-methylpropan-1-ol, 3-methylbutan-1-ol, and 2-phenylethanol) was studied from same ethanol content solutions connected alternatively with the reference solution to the instrument inlet. Linear dynamic range and limit of detection (LOD) were determined for ethyl hexanoate. Fragmentation of the protonated analytes was limited to a few ions of low intensity, or to specific fragment ions with no further fragmentation. Association and/or ligand switching reactions from ethanol clusters were only significant for the primary alcohols. Interpretation of the mass spectra was straightforward with easy detection of diagnostic ions. These results made this ethanol ionization method suitable for direct headspace analyses of model wines and to their nosespace analyses.

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http://dx.doi.org/10.1002/jms.4036DOI Listing

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