Chemometric Optimization of QuEChERS Extraction Method for Polyphenol Determination in Beers by Liquid Chromatography with Ultraviolet Detection
- 257 Downloads
QuEChERS methodology is a new alternative for polyphenol analysis in foods and beverages. This extractive and clean up method includes several steps that should be optimized to accomplish a fast and efficient extraction. In this work, chemometrics tools were applied to optimize QuEChERS parameters for polyphenol extraction from beers. By means of D-optimal screening design, the most influential extraction parameters were defined, i.e., acetonitrile volume, acidity, PSA, and C18 amount. These parameters were optimized applying a central composite design with desirability function, establishing the following optimal conditions: 2.5 mL of acetonitrile as extraction volume, 0.5% v/v of formic acid for sample acidification, 40 mg PSA for d-SPE step, and 175 mg of C18. Method validation was carried out according to International Conference on Harmonization recommendations. Data calibration curves (0.10–10.00 mg L−1) fitted a linear regression model with determination coefficients (R2) ≥ 0.992. Repeatability (relative standard deviation, RSD) and intermediate precision (RSD) showed values ≤ 4.81% (n = 6) and ≤ 6.71% (n = 3), respectively. Recovery (n = 3) at three levels ranged from 93.98 to 119.92% (RDS ≤ 4.40%) and quantification limits ranged from 0.009 to 0.118 μg mL−1. Applying the optimized and validated method, 10 beer samples were analyzed. The principal phenolic acids found were t-ferulic acid, caffeic acid, p-coumaric acid, and p-hydroxybenzoic acid. Individually, t-ferulic acid showed the highest concentration in all samples presenting a content ranged from 0.01 ± 0.01 to 2.25 ± 0.02 μg mL−1. The proposed methodology proved to be fast, reliable, and efficient for the determination of polyphenols in beer.
KeywordsD-optimal Central composite design QuEChERS Chromatography
This work is part of Oscar Galarce-Bustos thesis to obtain the degree of Doctor in Science and Analytical Technology from the University of Concepcion, Chile. Authors want to thank to the National Commission of Scientific and Technological Research (CONICYT) of the Chilean Government for the doctoral scholarship granted.
This study was funded by the National Fund for Scientific and Technological Development (FONDECYT) project No. 1171857, by the National Fund for Scientific and Technological Equipment (FONDEQUIP) project No. 130209, and by the University of Concepcion.
Compliance with Ethical Standards
Conflict of Interest
Oscar Galarce-Bustos declares that he has no conflict of interest. Lissette Novoa declares that she has no conflict of interest. Jessy Pavon declares that she has no conflict of interest. Karem Henríquez-Aedo declares that she has no conflict of interest. Mario Aranda declares that he has no conflict of interest.
This article does not contain any studies with human participants or animals performed by any of the authors.
- Alonso García A, Cancho Grande B, Simal Gándara J (2004) Development of a rapid method based on solid-phase extraction and liquid chromatography with ultraviolet absorbance detection for the determination of polyphenols in alcohol-free beers. J Chromatogr A 1054:175–180. https://doi.org/10.1016/j.chroma.2004.07.092 CrossRefPubMedGoogle Scholar
- Bourdat-Deschamps M, Leang S, Bernet N, Daudin J-J, Nélieu S (2014) Multi-residue analysis of pharmaceuticals in aqueous environmental samples by online solid-phase extraction–ultra-high-performance liquid chromatography-tandem mass spectrometry: optimisation and matrix effects reduction by quick, easy, cheap, effective, rugged and safe extraction. J Chromatogr A 1349:11–23. https://doi.org/10.1016/j.chroma.2014.05.006 CrossRefPubMedGoogle Scholar
- Chiva-Blanch G, Urpi-Sarda M, Rotchés-Ribalta M, Zamora-Ros R, Llorach R, Lamuela-Raventós RM, Estruch R, Andrés-Lacueva C (2011) Determination of resveratrol and piceid in beer matrices by solid-phase extraction and liquid chromatography–tandem mass spectrometry. J Chromatogr A 1218:698–705. https://doi.org/10.1016/j.chroma.2010.12.012 CrossRefPubMedGoogle Scholar
- Delgado-Zamarreño MM, Pérez-Martín L, Bustamante-Rangel M, Carabias-Martínez R (2012) A modified QuEChERS method as sample treatment before the determination of isoflavones in foods by ultra-performance liquid chromatography–triple quadrupole mass spectrometry. Talanta 100:320–328. https://doi.org/10.1016/j.talanta.2012.07.070 CrossRefPubMedGoogle Scholar
- Eriksson L, Johansson E, Kettaneh-Wold N, Wikstrom C, Wold S (2008) Design of experimental: principles and applications, 3rd edn. MKS Umetrics, MalmoGoogle Scholar
- Fernandes PJ, Barros N, Câmara JS (2013) A survey of the occurrence of ochratoxin A in Madeira wines based on a modified QuEChERS extraction procedure combined with liquid chromatography–triple quadrupole tandem mass spectrometry. Food Res Int 54:293–301. https://doi.org/10.1016/j.foodres.2013.07.020 CrossRefGoogle Scholar
- Fernández de Córdova ML, Medina AR (2014) Chapter 29 - analytical methods for determination of polyphenols in beer. In: Preedy V (ed) Processing and impact on antioxidants in beverages. Academic Press, San Diego, pp 289–299. https://doi.org/10.1016/B978-0-12-404738-9.00029-5 CrossRefGoogle Scholar
- Ferreira SLC, Bruns RE, da Silva EGP, dos Santos WNL, Quintella CM, David JM, de Andrade JB, Breitkreitz MC, Jardim ICSF, Neto BB (2007) Statistical designs and response surface techniques for the optimization of chromatographic systems. J Chromatogr A 1158:2–14. https://doi.org/10.1016/j.chroma.2007.03.051 CrossRefPubMedGoogle Scholar
- Fontana AR, Bottini R (2014) High-throughput method based on quick, easy, cheap, effective, rugged and safe followed by liquid chromatography-multi-wavelength detection for the quantification of multiclass polyphenols in wines. J Chromatogr A 1342:44–53. https://doi.org/10.1016/j.chroma.2014.03.044 CrossRefPubMedGoogle Scholar
- Herrero A, Ortiz MC, Sarabia LA (2013) D-optimal experimental design coupled with parallel factor analysis 2 decomposition a useful tool in the determination of triazines in oranges by programmed temperature vaporization–gas chromatography–mass spectrometry when using dispersive-solid phase extraction. J Chromatogr A 1288:111–126. https://doi.org/10.1016/j.chroma.2013.02.088 CrossRefPubMedGoogle Scholar
- International Conference on Harmonisation (ICH) (2005) Harmonised tripartite guideline: validation of analytical procedures: text and methodology Q2 (R1)Google Scholar
- Lehotay SJ, Son KA, Kwon H, Koesukwiwat U, Fu W, Mastovska K, Hoh E, Leepipatpiboon N (2010) Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables. J Chromatogr A 1217:2548–2560. https://doi.org/10.1016/j.chroma.2010.01.044 CrossRefPubMedGoogle Scholar
- Quifer-Rada P, Vallverdú-Queralt A, Martínez-Huélamo M, Chiva-Blanch G, Jáuregui O, Estruch R, Lamuela-Raventós R (2015) A comprehensive characterisation of beer polyphenols by high resolution mass spectrometry (LC–ESI-LTQ-Orbitrap-MS). Food Chem 169:336–343. https://doi.org/10.1016/j.foodchem.2014.07.154 CrossRefPubMedGoogle Scholar
- Silva CL, Haesen N, Câmara JS (2012) A new and improved strategy combining a dispersive-solid phase extraction-based multiclass method with ultra high pressure liquid chromatography for analysis of low molecular weight polyphenols in vegetables. J Chromatogr A 1260:154–163. https://doi.org/10.1016/j.chroma.2012.08.082 CrossRefPubMedGoogle Scholar