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Supercritical fluid chromatography coupled to high-resolution tandem mass spectrometry: an innovative one-run method for the comprehensive assessment of chocolate quality and authenticity

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Abstract

To assess chocolate quality and authenticity comprehensively, a combination of various analytical procedures is involved, thereby making the process time-consuming and costly. Thus, we investigated the potential of ultra-high performance supercritical fluid chromatography coupled to quadrupole-time of flight mass spectrometry (UHPSFC-QTOF-MS) as an alternative to “classic” methods. By combining hexane and aqueous extracts from sequential extraction, a single 8-min analytical run enabled us (i) to determine cocoa butter equivalents (CBEs) and milk fat content based on the detection of selected triacylglycerols, (ii) to calculate dry non-fat cocoa solids based on determined theobromine and caffeine content, and (iii) to profile contained sugars. To obtain the most comprehensive information about sample composition, the MS method comprised a full MS scan for non-target screening and several time-scheduled targeted MS/MS functions (“parallel reaction monitoring”) optimized according to the possible concentration ranges of the analytes. For 40 different chocolate samples, our results and those obtained by using standard methods (LC-UV for non-fat cocoa solids, and GC-FID for CBEs) were in good agreement. Compared to the conventional approach for chocolate quality and authenticity control, the presented SFC-MS method is a fast, cost-effective, and efficient alternative, and only samples suspicious for the presence of CBE should be referred to the standard GC-FID method for exact CBE quantification. In the study, also some challenges offered by SFC-MS have been addressed.

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Abbreviations

ABPR:

Automated back pressure regulator

APCI:

Atmospheric pressure ionization

AmF:

Ammonium formate

BPI:

Base peak intensity

CB:

Cocoa butter

CBE:

Cocoa butter equivalent

Cf:

Caffeine

CRM:

Certified reference material

DNCS:

Dry non-fat cocoa solids

ELSD:

Evaporative light-scattering detector

ESI:

Electrospray

FA:

Formic acid

FID:

Flame ionization detector

GC:

Gas chromatography

HP:

High performance

HR:

High resolution

IpOH:

Propan-2-ol

Lac:

Lactose

LC:

Liquid chromatography

LOQ:

Limit of quantification

MeCN:

Acetonitrile

MeOH:

Methanol

MS:

Mass spectrometry

MS/MS:

Tandem mass spectrometry

NARP:

Non-aqueous reversed phase

PLS:

1-Palmitoyl-2-linoleoyl-3-stearoyl-glycerol

PO:

Palmitoyl-oleoyl-glycerol

POO:

1,2-Dioleoyl-3-palmitoyl-glycerol

POP:

1,3-Dipalmitoyl-2-oleoyl-glycerol

POS:

1-Palmitoyl-2-oleoyl-3-stearoyl-glycerol

PSB:

1-Palmitoyl-2-stearoyl-3-butyryl-glycerol

QTOF:

Quadrupole-time of flight

RID:

Refractometric detector

RP:

Reversed phase

RSD:

Relative standard deviation

SFC:

Supercritical fluid chromatography

SLS:

1,3-Distearoyl-2-linoleoyl-glycerol

SO:

Oleoyl-stearoyl-glycerol

SOO:

1,2-Dioleoyl-3-stearoyl-glycerol

SOS:

1,3-Distearoyl-2-oleoyl-glycerol

Suc:

Sucrose

TAG:

Triacylglycerol

Tb:

Theobromine

TDCS:

Total dry cocoa solids

TPDG:

1,2,3-Tripentadecanoyl-glycerol

UHP:

Ultra-high performance

UV:

Ultraviolet

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Funding

This work was supported by METROFOOD-CZ research infrastructure project (MEYS Grant No: LM2018100) including access to its facilities.

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Authors and Affiliations

  1. Faculty of Food and Biochemical Technology, Department of Food Analysis and Nutrition, University of Chemistry and Technology, Technicka 3, Prague 6, 166 28, Prague, Czech Republic

    Michaela Rektorisova, Vojtech Hrbek, Monika Tomaniova & Jana Hajslova

  2. Czech Agriculture and Food Inspection Authority, Za Opravnou 6, 150 00, Prague 5, Prague, Czech Republic

    Petr Cuhra

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  1. Michaela Rektorisova
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  2. Vojtech Hrbek
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  3. Monika Tomaniova
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  4. Petr Cuhra
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Contributions

Michaela Rektorisova: conceptualization, methodology, validation, formal analysis, investigation, data curation, writing—original draft, writing—review and editing, project administration; Vojtech Hrbek: methodology and writing—review and editing; Monika Tomaniova: resources, writing—review and editing, and funding acquisition; Petr Cuhra: formal analysis and resources; Jana Hajslova: conceptualization, resources, writing—review and editing, supervision, and funding acquisition.

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Correspondence to Jana Hajslova.

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Rektorisova, M., Hrbek, V., Tomaniova, M. et al. Supercritical fluid chromatography coupled to high-resolution tandem mass spectrometry: an innovative one-run method for the comprehensive assessment of chocolate quality and authenticity. Anal Bioanal Chem 414, 6825–6840 (2022). https://doi.org/10.1007/s00216-022-04246-6

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