Comparison of Different Methods for Determining 5-hydroxymethylfurfural in Assessing the Quality of Honey from Greater Poland
Abstract
1. Introduction
2. Materials and Methods
2.1. Field of Research
2.2. Samples
2.3. Apparatus and Reagents
2.4. Procedures
2.4.1. Preparation of Solutions for HMF Determination
- Carrez I: 15 g of potassium hexacyanoferrate (II) trihydrate was dissolved in distilled water in a 100 mL volumetric flask.
- Carrez II: 30 g of zinc acetate dihydrate was dissolved in distilled water in a 100 mL volumetric flask.
- A 0.2% sodium bisulfate (IV) solution: 0.1 g sodium bisulfate (IV) was dissolved in distilled water in a 50 mL volumetric flask (prepared immediately before use).
- p-toluidine solution: 10 g of p-toluidine was dissolved in propan-2-ol in a 100 mL volumetric flask. The preparation of the solution must take place 24 h before use and can be used for up to three days.
- A 0.5% barbituric acid solution: 0.5 g of barbituric acid was dissolved in distilled water in a 100 mL volumetric flask.
2.4.2. The White Spectrophotometric Method
2.4.3. The Winkler Spectrophotometric Method
2.4.4. The LC-MS/MS Method
2.4.5. Validation of the LC-MS/MS Method
2.4.6. Preparation of Honey for Determinations by LC-MS/MS
3. Results and Discussion
3.1. Validation of the LC-MS/MS Method
3.2. Results Analysis
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
- Missio da Silva, P.; Gauche, C.; Gonanza, V.L.; Costa, O.A.C.; Fett, R. Honey: Chemical composition, stability and authenticity. Food Chem. 2016, 196, 309. [Google Scholar] [CrossRef] [PubMed]
- Samarghandian, S.; Farkhondeh, T.; Samini, F. Honey and health: A review of recent clinical research. Pharmacogn. Res. 2017, 9, 121. [Google Scholar] [CrossRef] [PubMed]
- Lee, Y.C.; Shlyankevich, M.; Jeong, H.K.; Douglas, J.S.; Surh, Y.J. Bioactivation of 5-hydroxymethyl-2-furaldehyde to an electrophilic and mutagenic allylic sulfuric acid ester. Biochem. Biophys. Res. Commun. 1995, 209, 996. [Google Scholar] [PubMed]
- Mizushina, Y.; Yagita, E.; Kuramochi, K.; Kuriyama, I.; Shimazaki, N.; Koiwai, O.; Uchiyama, Y.; Yomezawa, Y.; Sugawara, F.; Kobayashi, S.; et al. 5-(Hydroxymethyl)-2-furfural: A selective inhibitor of DNA polymerase λ and terminal deoxynucleotidyltransferase. Arch. Biochem. Biophys. 2008, 446, 69. [Google Scholar] [CrossRef] [PubMed]
- Morales, F.J. Hydroxymethylfurfural (HMF) and Related Compounds; Wiley: Hoboken, NJ, USA, 2008; Volume 135. [Google Scholar] [CrossRef]
- Li, M.M.; Wu, L.Y.; Zhao, T.; Huang, X.; Liu, Z.H.; Fan, X.L.; Xiao, C.R.; Gao, Y.; Ma, Y.B.; Chen, J.J.; et al. The protective role of 5-HMF against hypoxic injury. Cell Stress Chaperones 2011, 16, 267. [Google Scholar] [CrossRef]
- Li, M.M.; Wu, L.Y.; Zhao, T.; Wu, K.W.; Xiong, L.; Zhu, L.L.; Fan, M. The protective role of 5-hydroxymethyl-2-furfural (5-HMF) against acute hypobaric hypoxia. Cell Stress Chaperones 2011, 16, 529. [Google Scholar] [CrossRef] [PubMed]
- Shapla, U.M.; Solayman, M.; Alam, N.; Khalil, M.I.; Gan, S.H. 5-Hydroxymethylfurfural (HMF) levels in honey and other food products: Effects on bees and human health. Chem. Cent. J. 2018, 35, 1. [Google Scholar] [CrossRef] [PubMed]
- Wed, M.A.A.; Sraa, A.-M.; Rahaf, M.H.A.; Badriah, S.l.-F.; Hamed, A.G.; Al-Shehri, B.M.A.; Bajaber, M.A.; Khan, K.A.; Alrooqi, M.M.; Modawe, G.A.; et al. Biochemical Reactions and Their Biological Contributions in Honey. Molecules 2022, 27, 4719. [Google Scholar] [CrossRef] [PubMed]
- Tichonow, A.I.; Bondarenko, L.A.; Jarnych, T.G.; Szpyczak, O.S.; Kowal, W.M.; Skrypnik-Tichonow, R.I. Natural honey in medicine and pharmacy. In Origin, Properties, Application, Medicinal Preparations; Sadecki Bartnik: Nowy Sącz County, Poland, 2017; ISBN 978-83-61904-13-7. [Google Scholar]
- Khalil, M.I.; Sulaiman, S.A.; Gan, S.H. High 5-hydroxymethylfurfural concentrations are found in Malaysian honey samples stored for more than one year. Food Chem. Toxicol. 2010, 48, 2388. [Google Scholar] [CrossRef]
- The Council of the European Union. Council Directive 2001/110/EC of 20 December 2001: Relating to honey. Off. J. Eur. Communities 2001, L10, 47–52. [Google Scholar]
- Gokmen, V.; Acar, O.C.; Serpne, A.; Morales, A.F.J. Effect of leaving agents and sugars on the formation of hydroxymethylfurfural in cookies during baking. Eur. Food Res. Technol. 2008, 226, 1031. [Google Scholar] [CrossRef]
- Turhan, K. Effects of thermal treatment and storage on hydroxymethylfurfural (hmf) content and diastase activity of honeys collected from middle Anatolia on Turkey. Innov. Chem. Biol. 2009, 23, 233. [Google Scholar] [CrossRef] [PubMed]
- Mironescu, M.; Fratila, L.; Hupert, A.; Mironescu, I.D. Obtaining and Characterization of Starch-Based Edible Films Incorporating Honey. Propolis Bee Bread. Acta Univ. Cibiniensis 2019, 23, 193. [Google Scholar]
- Zhao, L.; Chen, J.; Su, J.; Li, L.; Hu, S.; Li, B.; Zhang, X.; Xu, Z.; Chen, T. In vitro antioxidant and antiproliferative activities of 5-hydroxymethylfurfural. J. Agric. Food Chem. 2013, 61, 10604. [Google Scholar] [CrossRef] [PubMed]
- Zappala, M.; Fallico, B.; Arena, E.; Verzera, A. Methods for the determination of HMF in honey: A comparison. Food Control 2005, 16, 273. [Google Scholar] [CrossRef]
- Bogdanov, S. Harmonized Methods of the European Honey Commission. International Honey Commission. 2009. Available online: www.bee-hexagon.net (accessed on 20 January 2024).
- Ajlouni, S.; Sujirapinyokul, P. Hydroxymethyl-furfuraldehyde and amylase contents in Australian honey. Food Chem. 2010, 119, 1000. [Google Scholar] [CrossRef]
- Teixido, E.; Santos, F.J.; Puignou, L.; Galceran, M.T. Analysis of 5-hydroxymethylfurfural in foods by gas chromatography-mass spectrometry. J. Chromatogr. A 2006, 1135, 85. [Google Scholar] [CrossRef]
- Rizelioa, V.M.; Gonzaga, L.V.; Campelo Borges, G.S.; Micke, G.A.; Fetta, R.; Oliveira Costa, A.C. Development of a fast MECK method for determination of 5-HMF in honey samales. Food Chem. 2012, 133, 1640. [Google Scholar] [CrossRef]
- Reyes-Sales, E.O.; Manzanilla-Cano, J.A.; Barcelo-Quintal, M.H.; Juarez-Mendoza, D.; Reyes-Sales, M. Direct Electrochemical Determination of Hydroxymethylfurfural (HMF) and its Application to Honey Samples. Anal. Lett. 2007, 39, 161. [Google Scholar] [CrossRef]
- Stankowski, W. Wielkopolska; OCLC 830198134; WsiP: Maxwell, CA, USA, 1999; ISBN 83-02-07148-X. [Google Scholar]
- Constantin, O.E.; Kukurová, K.; Dasko, L.; Stanciuc, N.; Ciesarová, Z.; Croitoru, C.; Râpeanu, G. Effect of Thermal Processing on Simultaneous Formation of Acrylamide and Hydroxymethylfurfural in Plum Purée. Pol. J. Food Nutr. Sci. 2019, 69, 179. [Google Scholar] [CrossRef]
- Tomczyk, M.; Zaguła, G.; Puchalski, C.; Dżugan, M. Transfer of some toxic metals from soil to honey depending on bee habitat conditions. Acta Univ. Cibiniensis 2020, 24, 49. [Google Scholar] [CrossRef]
- Debska, J.; Kot-Wasik, A.; Namiesnik, J. Determination of nonsteroidal antiinflammatory drugs in water samples using liquid chromatography coupled with diode-array detector and mass spectrometry. J. Sep. Sci. 2005, 28, 2419. [Google Scholar] [CrossRef] [PubMed]
- Anklam, E. A review of the analytical methods to determine the geographical and botanical origin of honey. Food Chem. 1998, 63, 549. [Google Scholar] [CrossRef]
Pseudo Molecular Ion [M + 1]+ | DP [V] | MRM | CE [V] | CPX [V] |
---|---|---|---|---|
127 | 46 | 127 → 109 * | 15 | 8 |
127 | 81 | 127 → 81 | 23 | 6 |
127 | 53 | 127 → 53 | 31 | 8 |
Linearity Range | Curve Equation | Correlation Coefficient | LOD [μg/mL] | LOQ [μg/mL] |
---|---|---|---|---|
From LOQ to 0.5 μg/mL | y = 2 × 107 × x + 35,595 | 0.9992 | 0.0005 | 0.001 |
Concentration [μg/mL] | Measurement Uncertainty [μg/mL] |
---|---|
0.001 | 7.6 × 10−5 |
0.0025 | 2.16 × 10−4 |
0.005 | 5.5 × 10−4 |
0.010 | 7.97 × 10−4 |
0.025 | 2.13 × 10−3 |
0.050 | 2.59 × 10−3 |
0.100 | 5.16 × 10−3 |
0.250 | 1.32 × 10−2 |
0.500 | 2.72 × 10−2 |
Honey Sample Number | HMF Presence (LC-MS/MS) | HMF Presence (White) | HMF Presence (Winkler) |
---|---|---|---|
1 | + | + | − |
2 | + | − | + |
3 | + | + | + |
4 | + | + | + |
5 | + | + | + |
6 | + | + | + |
7 | + | + | + |
Honey Sample Number | HMF Quantity [mg/kg] ± SD (LC-MS/MS) | HMF Quantity [mg/kg] ± SD (White) | HMF Quantity [mg/kg] ± SD (Winkler) |
---|---|---|---|
1 | 3.4 ± 0.2 | 15.0 ± 0.0 | 0.0 ± 0.0 |
2 | 2.7 ± 0.4 | 0.0 ± 0.0 | 3.7 ± 0.1 |
3 | 3.7 ± 0.2 | 4.5 ± 0.0 | 8.8 ± 1.6 |
4 | 2.6 ± 0.1 | 1.5 ± 0.0 | 3.7 ± 2.5 |
5 | 2.7 ± 0.2 | 1.5 ± 0.0 | 5.1 ± 1.3 |
6 | 3.0 ± 0.2 | 23.5 ± 1.7 | 23.4 ± 0.1 |
7 | 3.6 ± 0.2 | 28.5 ± 1.5 | 20.2 ± 1.4 |
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Zembrzuska, J.; Pakulski, Ł.; Karbowska, B.; Bartoszewicz, J.; Janeba-Bartoszewicz, E.; Selech, J.; Kurczewski, P. Comparison of Different Methods for Determining 5-hydroxymethylfurfural in Assessing the Quality of Honey from Greater Poland. Sustainability 2024, 16, 4568. https://doi.org/10.3390/su16114568
Zembrzuska J, Pakulski Ł, Karbowska B, Bartoszewicz J, Janeba-Bartoszewicz E, Selech J, Kurczewski P. Comparison of Different Methods for Determining 5-hydroxymethylfurfural in Assessing the Quality of Honey from Greater Poland. Sustainability. 2024; 16(11):4568. https://doi.org/10.3390/su16114568
Chicago/Turabian StyleZembrzuska, Joanna, Łukasz Pakulski, Bożena Karbowska, Jarosław Bartoszewicz, Edyta Janeba-Bartoszewicz, Jarosław Selech, and Przemysław Kurczewski. 2024. "Comparison of Different Methods for Determining 5-hydroxymethylfurfural in Assessing the Quality of Honey from Greater Poland" Sustainability 16, no. 11: 4568. https://doi.org/10.3390/su16114568
APA StyleZembrzuska, J., Pakulski, Ł., Karbowska, B., Bartoszewicz, J., Janeba-Bartoszewicz, E., Selech, J., & Kurczewski, P. (2024). Comparison of Different Methods for Determining 5-hydroxymethylfurfural in Assessing the Quality of Honey from Greater Poland. Sustainability, 16(11), 4568. https://doi.org/10.3390/su16114568