An improved method for the analysis of 2-aminoacetophenone in wine based on headspace solid-phase microextraction and heart-cut multidimensional gas chromatography with selective detection by tandem mass spectrometry

- A simple, selective, sensitive and robust method for the analysis of 2- aminoacetophenone.
- Deterioration of 2-aminoacetophenone over time changes its response.
- Proton-exchange of deuterated 2-aminoacetophenone in alkaline solutions.

Heart-cut multidimensional gas chromatography coupled to selective mass spectrometric detection (H/C MDGC-MS-MS) was shown to be a suitable combination for analysis of the key component for the wine off-flavor named “atypical aging off-flavor” (german: “Untypische Alterungsnote”, UTA), 2-aminoacetophenone (2-AAP). Headspace solid phase microextraction (HS-SPME) was applied as an easy to automate sample preparation step suiting routine control situations. During method development two critical aspects were found, of which one is the chemical degradation of the neat substance, leading to signal reduction and a false response behavior. A second aspect is the pH stability of the deuterated isotopologue 1-(2-aminophenyl)-2,2,2-trideuterio-ethanone (2-AAP-d3) used for quantification via a stable isotope dilution assay. Despite an earlier suggestion to increase the extractable amount of 2-AAP and its isotopic standard in the headspace, alkalization of 2-AAP-d3 containing aqueous samples were found to be critical. In such a milieu a deuterium exchange can then cause erroneous quantitative results. The method proposed in our study thus uses native wine pH conditions and proved to be suitable for routine control with respect to the detection of the “atypical aging off-flavor” in wine at concentration levels below its sensory threshold of about 1 μgL−1. Good linearity was obtained in the calibrated range from 0.1-8 μgL−1 (y = 1,2338x + 0,1029, R = 0,9985) with limits of detection or quantification being 0.01 and 0.14 μg/L, respectively.