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Enantiodifferentiation of 3-sec-butyl-2-methoxypyrazine in different species using multidimensional and comprehensive two-dimensional gas chromatographic approaches

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Abstract

With respect to the current hypothesis that natural amino acids may serve as starting material for the biosynthesis of alkyl-methoxypyrazines, the enantiomeric distribution of the potent aroma compound 3-sec-butyl-2-methoxypyrazine (SBMP) was determined in various species using heart-cut multidimensional gas chromatography (H/C MDGC) or comprehensive two-dimensional gas chromatography (GC × GC). Complementary to an earlier described separation on octakis-(6-O-methyl-2,3-di-O-pentyl)-γ-cyclodextrin used as chiral stationary phase, we found a reversal of the elution order of SBMP enantiomers on heptakis-(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin, providing further confirmation options for that type of analysis. Optimization of the enantioseparation of SBMP in a single-oven H/C enantio-MDGC system involved the use of a dual-jet cryo modulator for trapping of analytes transferred from the achiral 1D column to the chiral 2D column before starting the 2D enantioseparation with an independent temperature ramp. For the enantiodifferentiation by enantio-GC × GC, the modulation period had to be significantly shortened to avoid loss of chiral resolution gained in 1D. H/C MDGC with mass spectrometric detection (MS) using selected ion monitoring (SIM) was sufficient for parts per billion level analysis, whereas H/C MDGC-MS/MS or GC × GC time-of-flight (TOF) MS were necessary for parts per trillion level analysis. In various vegetables, lady beetles and Vitis vinifera species analyzed, only (S)-SBMP was detected, supporting the hypothesis of natural amino acids serving as starting material for the biosynthesis of alkyl-methoxypyrazines.

Harmonia axyridis analyzed using headspace solid phase microextraction and enantio-GC × GC-TOF-MS

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Acknowledgments

The authors are particularly thankful to Supelco (Sigma-Aldrich) and CTC Analytics for the supply of SPME fibers as well as the ionic liquid GC column (Supelco). C. Legrum is grateful for the Ph.D. scholarship of the “Graduiertenförderung des Landes Rheinland Pfalz”. Furthermore, financial support from the Ministerium für Umwelt, Landwirtschaft, Ernährung, Weinbau und Forsten (Rheinland-Pfalz, Germany) is gratefully acknowledged.

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Authors and Affiliations

  1. Dienstleistungszentrum Ländlicher Raum (DLR) Rheinpfalz, Kompetenzzentrum Weinforschung, Breitenweg 71, 67435, Neustadt an der Weinstraße, Germany

    Charlotte Legrum, Petra Slabizki & Hans-Georg Schmarr

  2. Fachbereich Chemie, Fachrichtung Lebensmittelchemie und Toxikologie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Straße 52, 67663, Kaiserslautern, Germany

    Charlotte Legrum

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  1. Charlotte Legrum
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  2. Petra Slabizki
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Correspondence to Hans-Georg Schmarr.

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This paper is dedicated to Dr. Konrad (Koni) Grob (Zürich, Switzerland) on the occasion of his 65th birthday.

Published in the topical collection Multidimensional Chromatography with guest editors Torsten C. Schmidt, Oliver J. Schmitz, and Thorsten Teutenberg.

Charlotte Legrum and Hans-Georg Schmarr contributed equally to this work.

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Legrum, C., Slabizki, P. & Schmarr, HG. Enantiodifferentiation of 3-sec-butyl-2-methoxypyrazine in different species using multidimensional and comprehensive two-dimensional gas chromatographic approaches. Anal Bioanal Chem 407, 253–263 (2015). https://doi.org/10.1007/s00216-014-8061-8

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