Analytical and Bioanalytical Chemistry

, Volume 410, Issue 15, pp 3483–3490 | Cite as

Quantification of hydroxycinnamic derivatives in wines by UHPLC-MRM-MS

  • Nayla Ferreira-LimaEmail author
  • Anna Vallverdú-QueraltEmail author
  • Emmanuelle Meudec
  • Lucie Pinasseau
  • Arnaud Verbaere
  • Marilde T. Bordignon-Luiz
  • Christine Le Guernevé
  • Véronique Cheynier
  • Nicolas Sommerer
Research Paper
Part of the following topical collections:
  1. Discovery of Bioactive Compounds


A UHPLC-MS/MS method was developed for the quantification of the main compounds involved in oxidation reactions occurring in white musts and wines such as hydroxycinnamic acids, their glutathione and cysteinylglycine adducts (GRP, GRP2, 5-(S-glutathionyl)-trans-caftaric acid, 2-(S-cysteinylglycyl)-trans-caftaric acid, and 2-(S-glutathionyl)-trans-caffeic acid), and reduced and oxidized glutathione (GSH, GSSG) in wine. Since oxidation is the main concern in white wine-making, directly affecting its quality, the developed method was then applied in a series of white wines made with different pre-fermentation treatments to limit oxidation at must stage. The glucose esters and/or glucosides of hydroxycinnamic acids were quantified as glucogallin equivalent. The developed method led to an overall improvement in the limits of detection (LODs) and quantification (LOQs) for all the compounds studied in comparison to other methods such as high-performance liquid chromatography with fluorescence detection (HPLC-FLD) or diode array UV detection (HPLC-DAD). LOD values ranged from 0.0002 to 0.0140 mg/L and LOQs from 0.0005 to 0.0470 mg/L. The recoveries ranged between 80 and 110% in wines, and the relative standard deviation (RSD) for precision intra- and inter-day was below 15%. The accuracy and intra- and inter-day precision met the acceptance criteria of the AOAC international norms. As far as we know, this study is the first report of quantification of GRP, 2-(S-cysteinylglycyl)-trans-caftaric acid, and 2-(S-glutathionyl)-trans-caffeic acid using these non-commercially available compounds as external standards. Those compounds represent a significant proportion of hydroxycinnamic acid derivatives in wines. The methodology described is suitable for the analysis of hydroxycinnamic derivatives in wines.


Wine analysis White wine oxidation GRP GRP isomers Mass spectrometry 



The authors gratefully acknowledge Coordenção de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) for the financial support of a doctoral sandwich program at Plateforme Polyphénols, UMR SPO, INRA, for N. Ferreira-Lima. Funding for this work was provided by the Instituto de Salud Carlos III, ISCIII (CIBEROBN). Financial support from GIS Infrastructures en Biologie Santé et Agronomie (IBiSA), Région Languedoc Roussillon, and INRA CNOC for funding of the UHPLC-MS and NMR equipment is also acknowledged.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflicts of interest.


  1. 1.
    Artero A, Artero A, Tarín JJ, Cano A. The impact of moderate wine consumption on health. Maturitas. 2015;80:3–13.CrossRefPubMedGoogle Scholar
  2. 2.
    Singleton VL, Timberlake CF, Lea AGH. The phenolic cinnamates of white grapes and wine. J Sci Food Agric. 1978;29(4):403–10.CrossRefGoogle Scholar
  3. 3.
    Singleton VL, Zaya J, Trousdale E, Salgues M. Caftaric acid in grapes and conversion to a reaction product during processing. Vitis. 1984;23(2):113–20.Google Scholar
  4. 4.
    Singleton VL, Salgues M, Zaya J, Trousdale E. Caftaric acid disappearance and conversion to products of enzymatic oxidation in grape must and wine. Am J Enol Vitic. 1985;36(1):50–6.Google Scholar
  5. 5.
    Cheynier VF, Trousdale EK, Singleton VL, Salgues MJ, Wylde R. Characterization of 2-S-glutathionyl caftaric acid and its hydrolysis in relation to grape wines. J Agric Food Chem. 1986;34(2):217–21.CrossRefGoogle Scholar
  6. 6.
    Salgues M, Cheynier V, Gunata Z, Wylde R. Oxidation of grape juice 2-S-glutathionyl caffeoyl tartaric acid by Botrytis cinerea laccase and characterization of a new substance: 2,5-di-S-glutathionyl caffeoyl tartaric acid. J Food Sci. 1986;51(5):1191–4.CrossRefGoogle Scholar
  7. 7.
    Cheynier VF, Van Hulst MWJ. Oxidation of trans-caftaric acid and 2-S-glutathionyl caftaric acid model solutions. J Agric Food Chem. 1988;36(1):10–5.CrossRefGoogle Scholar
  8. 8.
    Cejudo-Bastante MJ, Perez-Coello MS, Hermosín-Gutiérrez I. Identification of new derivatives of 2-S-glutathionylcaftaric acid in aged white wines by HPLC-DAD-ESI-MSn. J Agric Food Chem. 2010;58(21):11483–92.CrossRefPubMedGoogle Scholar
  9. 9.
    Ferreira-Lima N, Vallverdú-Queralt A, Meudec E, Mazauric JP, Sommerer N, Bordignon-Luiz MT, et al. Synthesis, identification, and structure elucidation of adducts formed by reactions of hydroxycinnamic acids with glutathione or cysteinylglycine. J Nat Prod. 2016;79(9):2211–22.CrossRefPubMedGoogle Scholar
  10. 10.
    Vallverdú-Queralt A, Verbaere A, Meudec E, Cheynier V, Sommerer N. Straightforward method to quantify GSH, GSSG, GRP, and hydroxycinnamic acids in wines by UPLC-MRM-MS. J Agric Food Chem. 2015;63(1):142–9.CrossRefPubMedGoogle Scholar
  11. 11.
    FDA, Food and Drug Administration. U. S. Department of Health and Human Services, Center for Drug Evaluation and Research. In: Bioanalytical Method Validation. FDA. 2013;1–28. Available at: Accessed 02 Nov 2016.
  12. 12.
    Baderschneider B, Winterhalter P. Isolation and characterization of novel benzoates, cinnamates, flavonoids, and lignans from Riesling wine and screening for antioxidant activity. J Agric Food Chem. 2001;49(6):2788–98.CrossRefPubMedGoogle Scholar
  13. 13.
    Alberts P, Applications of liquid chromatography–tandem mass spectrometry to wine analysis: targeted analysis and compound identification. In: PhD thesis, Stellenbosch University, Stellenbosch, South Africa. 2012. Accessed Nov 2016.
  14. 14.
    Janeš L, Lisjak K, Vanzo A. Determination of glutathione content in grape juice and wine by high-performance liquid chromatography with fluorescence detection. Anal Chim Acta. 2010;674(2):239–42.CrossRefPubMedGoogle Scholar
  15. 15.
    Porgalı E, Büyüktuncel E. Determination of phenolic composition and antioxidant capacity of native red wines by high performance liquid chromatography and spectrophotometric methods. Food Res Int. 2012;45(1):145–54.CrossRefGoogle Scholar
  16. 16.
    Anastasiadi M, Pratsinis H, Kletsas D, Skaltsounis AL, Haroutounian SA. Bioactive non-colored polyphenols content of grapes, wines and vinification by-products: evaluation of the antioxidant activities of their extracts. Food Res Int. 2010;43(3):805–13.CrossRefGoogle Scholar
  17. 17.
    Silva CL, Pereira J, Wouter VG, Giró C, Câmara JSA. Fast method using a new hydrophilic-lipophilic balanced sorbent in combination with ultra-high performance liquid chromatography for quantification of significant bioactive metabolites in wines. Talanta. 2011;86(30):82–90.CrossRefPubMedGoogle Scholar
  18. 18.
    Cheynier V, Rigaud J, Moutounet M. Oxidation kinetics of trans-caffeoyltartrate and its glutathione derivatives in grape musts. Phytochemistry. 1990;29(6):1751–3.CrossRefGoogle Scholar
  19. 19.
    Sonni F, Clark AC, Prenzler PD, Riponi C, Scollary GR. White wine antioxidant action of glutathione and the ascorbic acid/glutathione pair in a model. J Agric Food Chem. 2011;59(8):3940–9.CrossRefPubMedGoogle Scholar
  20. 20.
    Danilewicz JC. Reactions involving iron in mediating catechol oxidation in model wine. Am J Enol Vitic. 2013;64(1):316–24.CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2017

Authors and Affiliations

  • Nayla Ferreira-Lima
    • 1
    • 2
    Email author
  • Anna Vallverdú-Queralt
    • 1
    Email author
  • Emmanuelle Meudec
    • 1
  • Lucie Pinasseau
    • 1
  • Arnaud Verbaere
    • 1
  • Marilde T. Bordignon-Luiz
    • 2
  • Christine Le Guernevé
    • 1
  • Véronique Cheynier
    • 1
  • Nicolas Sommerer
    • 1
  1. 1.Plateforme Polyphénols, SPO, INRA, Montpellier SupAgroUniversité de MontpellierMontpellierFrance
  2. 2.Departamento de Ciência e Tecnologia de Alimentos CAL/CCAUniversidade Federal de Santa CatarinaFlorianópolisBrazil

Personalised recommendations