Chemical fingerprinting strategies based on comprehensive two-dimensional gas chromatography combined with gas chromatography-olfactometry to capture the unique signature of Piemonte peppermint essential oil (Mentha x piperita var Italo-Mitcham)

Elena Gabetti, Barbara Sgorbini, Federico Stilo, Carlo Bicchi, Patrizia Rubiolo, Franco Chialva, Stephen E. Reichenbach, Valentina Bongiovanni, Chiara Cordero, Andrea Cavallero

Research output: Contribution to journalArticlepeer-review

Abstract

Accurate, reliable, and informative mapping of untargeted and targeted components across many samples is here performed by combining off-line GC-Olfactometry (GC-O) and comprehensive two-dimensional gas chromatography (GC×GC) coupled to time-of-flight mass spectrometry with variable ionization energy (TOF MS featuring Tandem Ionization™). In particular, untargeted and targeted (UT) features patterns are processed by chromatographic fingerprinting, giving differential priority to potent odorants’ retention-times regions. Distinguishing peppermint essential oil (EO) from Piedmont (Italy - Mentha × piperita L. var. Italo-Mitcham - Menta di Pancalieri EO), with its unique sensory fingerprint (i.e., freshness and long-lasting sweetness), from high-quality peppermint EOs produced in other areas poses a great challenge. Chromatographic UT fingerprinting provided a great chemical dimensionality by mapping more than 350 peak-regions at 70 eV and 135 at 12 eV. From them, 95 components were identified and responses compared to available literature. Then, potent odorants, detected by GC-O using the aroma extraction dilution analysis (AEDA), were tracked over the chromatographic space and tentatively identified. With the highest flavor dilution (FD), 1,8-cineole (eucalyptus, fresh, camphoraceous); menthone (minty, herbaceous); and menthofuran (minty, musty, petroleum-like) were highlighted. Responsible for creamy and coumarinic notes were the diasteroisomers of (3,6)-dimethyl-4,5,6,7-tetrahydrobenzo[b]-furan-2(3H)-one (i.e., menthofurolactones), detected in higher relative abundance in Pancalieri EOs. By prioritizing the investigation of volatiles on higher LogFD retention regions, including 131 untargeted/targeted features, Pancalieri EOs were separately clustered from United States samples. Besides pre-targeted analytes, additional untargeted features were post-processed for identification within marker chemicals. Myrtenyl methyl ether, ethyl 3-methyl butanoate, propyl-2-methylbutanoate, and (E)-2-hexenal were putatively identified. Of the “unknown – knowns” with diagnostic roles, all metadata were collected including low energy spectra at 12 eV, which were found to be highly complementary to 70 eV spectra.

Original languageEnglish (US)
Article number462101
JournalJournal of Chromatography A
Volume1645
DOIs
StatePublished - May 24 2021

Keywords

  • Comprehensive two-dimensional gas chromatography
  • Gas chromatography-olfactometry
  • Mentha x piperita essential oil
  • Template matching
  • Time-of-flight mass spectrometry featuring tandem ionization
  • UT fingerprinting
  • aroma profile

ASJC Scopus subject areas

  • Analytical Chemistry
  • Biochemistry
  • Organic Chemistry

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