Honey Phenolic Compound Profiling and Authenticity Assessment Using HRMS Targeted and Untargeted Metabolomics

Abstract

Honey consumption is attributed to potentially advantageous effects on human health due to its antioxidant capacity as well as anti-inflammatory and antimicrobial activity, which are mainly related to phenolic compound content. Phenolic compounds are secondary metabolites of plants, and their content in honey is primarily affected by the botanical and geographical origin. In this study, a high-resolution mass spectrometry (HRMS) method was applied to determine the phenolic profile of various honey matrices and investigate authenticity markers. A fruitful sample set was collected, including honey from 10 different botanical sources (n = 51) originating from Greece and Poland. Generic liquid–liquid extraction using ethyl acetate as the extractant was used to apply targeted and non-targeted workflows simultaneously. The method was fully validated according to the Eurachem guidelines, and it demonstrated high accuracy, precision, and sensitivity resulting in the detection of 11 target analytes in the samples. Suspect screening identified 16 bioactive compounds in at least one sample, with abscisic acid isomers being the most abundant in arbutus honey. Importantly, 10 markers related to honey geographical origin were revealed through non-targeted screening and the application of advanced chemometric tools. In conclusion, authenticity markers and discrimination patterns were emerged using targeted and non-targeted workflows, indicating the impact of this study on food authenticity and metabolomic fields.

Bioactive Molecules for Discriminating Robinia and Helianthus Honey: High-Performance Liquid Chromatography–Electron Spray Ionization–Mass Spectrometry Polyphenolic Profile and Physicochemical Determinations

“…It is related to plant protection against dryness and environmental stress. Abscisic acid has been found in many types of honey (heather, rapeseed, lime-tree, Robinia, Leptospermum and sunflower) in different amounts [ 12 , 53 , 54 ]. It was detected in high amounts (13.93–23.03 mg/kg) in the samples collected from the southern part of Romania; we observed that high temperature in the season, as well as dryness (lack of humidity), was a determinant for the quantified amounts, while samples collected from inside the Transylvania (hilly region, with more humidity; presented in Material and Methods section), presented lower amounts of abscisic acid (2.95–6.61 mg/kg).…”

Polyphenolic and Chemical Profiles of Honey From the Tara Mountain in Serbia

“…The generally accepted melissopalynological analysis, the examination of these parameters provides a more precise assessment of the botanical and geographical origins of the honey (15,22). A very useful tool for distinguishing honey samples is also statistical analysis (8,23,24). Considering taste to be crucial for honey consumption, sensory analysis is of great importance.…”

Thorough Investigation of the Phenolic Profile of Reputable Greek Honey Varieties: Varietal Discrimination and Floral Markers Identification Using Liquid Chromatography–High-Resolution Mass Spectrometry

“…All identified compounds showed high mass accuracy, below 2 mDa, isotoping fitting below 50 mSigma and retention time (tR) tolerance below 0.2 min. Especially for isokaempferide and tectochrysin, which were not included in our previous suspect screening workflow [ 12 ], their identification was accomplished by comparing experimental MS/MS fragments with MS/MS spectra found in the mass spectral library MassBank of North America. Additionally, differences between the experimental and predicted tR were considered.…”

“…Considering the discussed facts, we analyzed a total of 169 honey samples with different botanical origins, namely blossom ( n = 62) and the unifloral fir ( n = 10), oak ( n = 24), pine ( n = 39) and thyme ( n = 34) honeys to reveal botanical origin markers of Greek honey through their phenolic compound content. To achieve that, our recently developed ultra-high-performance liquid chromatography hybrid quadrupole time-of-flight mass spectrometry (UHPLC-q-TOF-MS) method [ 12 ] was verified, and the analyte target list was updated, including a total of 24 target phenolic compounds. Besides targeted metabolomics, suspect and non-targeted workflows were also utilized.…”