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Enantiodifferentiation of 1,2-propanediol in various wines as phenylboronate ester with multidimensional gas chromatography-mass spectrometry

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Abstract

Native concentrations and enantiomeric distribution of 1,2-propanediol in various wines were studied in order to evaluate its merits as a potential marker for aroma adulteration in wine. Heart-cut multidimensional gas chromatography coupled to mass spectrometry was applied to analyze 1,2-propanediol after salting-out of the polar phase, derivatization with phenyl boronic acid, and extraction with cyclohexane. The enantiomeric separation of the derivative was achieved with heptakis-(6-O-tert. butyl dimethylsilyl-2,3-di-O-acetyl)-β-cyclodextrin as the chiral selector. In all authentic wines studied, 1,2-propanediol showed a high enantiomeric ratio in favor of the (R)-enantiomer, proving its potential as a marker for the adulteration with flavor extracts based on industrial 1,2-propandiol as solvent. Usually, concentrations varied between 15 and 100 mg/L. Higher values (up to 170 mg/L) were found in wines made with high amounts of dry berries. However, despite the higher concentrations of 1,2-propanediol in such wines, no apparent influence on the enantiomeric distribution could be detected.

Detection of fraudulent aromatization of wines by enantiodifferentiation of 1,2-propanediol as its phenylboronate ester

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Acknowledgments

The authors are particularly thankful to Supelco (Sigma-Aldrich) for the supply of the ionic liquid GC column. They thank the donating institutions for reference wine samples (Staatsweingut mit Johannitergut, Neustadt an der Weinstraße, Germany; Haute école de viticulture et oenologie, Changins, Switzerland). The authors are thankful for wine samples from food and wine control authorities of the state of Rheinland-Pfalz, Germany. They also appreciate the support and fruitful discussions from colleagues, particularly Patricia Golombek, Harald Kelm (TU Kaiserslautern, Germany), and Reinhard Meusinger (TU Darmstadt, Germany). Furthermore, the financial support from the Ministerium für Umwelt, Landwirtschaft, Ernährung, Weinbau und Forsten (Rheinland-Pfalz, Germany) is gratefully acknowledged.

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Correspondence to Hans-Georg Schmarr.

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Langen, J., Fischer, U., Cavalar, M. et al. Enantiodifferentiation of 1,2-propanediol in various wines as phenylboronate ester with multidimensional gas chromatography-mass spectrometry. Anal Bioanal Chem 408, 2425–2439 (2016). https://doi.org/10.1007/s00216-016-9379-1

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