Article (Scientific journals)
Vacuum-assisted HS-SPME/GC×GC-MS to enhance the volatile chromatographic fingerprint of commercial dark chocolate
Cozzolino, Rosaria; Eggermont, Damien; Malorni, Livia et al.
2026In Analytica Chimica Acta, 1385, p. 345015
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Keywords :
Chocolate; Comprehensive two-dimensional gas chromatography (GC×GC); Solid-phase microextraction (SPME); Vacuum-assisted headspace (Vac–HS)–SPME; Volatile organic compounds (VOCs); Comprehensive two-dimensional gas chromatography; GC×GC; Head-space solid-phase microextraction; Headspace solid phase microextraction; Solid-phase microextraction; Vacuum-assisted headspace –solid-phase microextraction; Volatile organic compound; Volatile organics; Analytical Chemistry; Environmental Chemistry; Biochemistry; Spectroscopy
Abstract :
[en] Background: This study explored the potential of vacuum-assisted headspace solid-phase microextraction (Vac–HS–SPME) coupled with two-dimensional gas chromatography mass spectrometry for the evaluation of the volatile profiles of dark chocolate samples. Comparative analyses between Vac- and classic HS-SPME sampling were performed at different sampling times. To simulate the release of volatile compounds during human consumption and the possible synergistic effect with Vac, experiments were carried out at the physiological temperature (37 °C) on powdered chocolate alone and with the addition of salty water as surrogate saliva. Results: Overall, Vac–HS–SPME showed higher extraction efficiencies of the overall profile, and based on the area of nine key odorant volatiles compared to classic HS-SPME. The addition of salty water showed an increased extraction yield comparable to the effect of vacuum. When the addition of salty water was then under Vac–HS–SPME conditions, the increase in extraction yield was proportionally higher. The different combined conditions, i.e., salty water or not, and HS-SPME and Vac–HS–SPME were compared in a complete untargeted way, exploiting the structured information provided by the two-dimensional plot generated using comprehensive two-dimensional gas chromatography (GC × GC) coupled to a quadrupole mass spectrometer. Additionally, the volatile profiles of the dark chocolates tested were compared selecting nine key aroma compounds. Novelty: This work explored for the first time the combined effect of vacuum and the addition of salty water simulating saliva on the overall volatile profile. The two-dimensional plots generated by GC × GC were treated as chromatographic fingerprints, building for the first time what we called an “improvement plot” showing the zone of increment corresponding to specific chemical classes.
Disciplines :
Chemistry
Food science
Author, co-author :
Cozzolino, Rosaria;  Institute of Food Science, National Council of Research, Avellino, Italy
Eggermont, Damien  ;  Université de Liège - ULiège > TERRA Research Centre
Malorni, Livia;  Institute of Food Science, National Council of Research, Avellino, Italy
Purcaro, Giorgia  ;  Université de Liège - ULiège > Département GxABT > Chemistry for Sustainable Food and Environmental Systems (CSFES)
Language :
English
Title :
Vacuum-assisted HS-SPME/GC×GC-MS to enhance the volatile chromatographic fingerprint of commercial dark chocolate
Publication date :
01 February 2026
Journal title :
Analytica Chimica Acta
ISSN :
0003-2670
eISSN :
1873-4324
Publisher :
Elsevier B.V.
Volume :
1385
Pages :
345015
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
ISPA-CNR - National Research Council. Institute of Sciences of Food Production
Available on ORBi :
since 05 February 2026

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