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

Author:
Legrum, Charlotte, Slabizki, Petra, Schmarr, Hans-Georg
Source:
Analytical and bioanalytical chemistry 2015 v.407 no.1 pp. 253-263
ISSN:
1618-2642
Subject:
Coccinellidae, Vitis vinifera, amino acids, biosynthesis, comprehensive two-dimensional gas chromatography, enantiomers, gas chromatography, mass spectrometry, monitoring, odor compounds, temperature, vegetables
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 achiral¹D column to the chiral²D column before starting the²D 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 in¹D. 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.
Agid:
1197553