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High molecular weight compounds generated by roasting barley malt are pro-oxidants in metal-catalyzed oxidations

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Abstract

The roasting process and color development have been related to an increase of the antioxidant activity of roasted malts. However, roasting is also responsible for the development of high molecular compounds with a pro-oxidant effect, leading to increased levels of radicals in systems based on iron- and copper-catalyzed Fenton reactions. For this reason, the overall antioxidant and pro-oxidant properties of three malt types with different roasting degrees (pilsner, melano and black) were evaluated in a Fenton-based model beer system (5.8 % ethanol, v/v). Black malt exhibited 50 % lower radical quenching capacity compared with pale and melano malts, as determined by spin trapping and electron spin resonance detection. These differences were related to the degree of roasting and the development of high molecular weight browning compounds. High molecular weight compounds isolated from black malt wort (molecular mass in the range of 4 × 106 and 108 g mol−1) were responsible for an increase of radicals (approximately 40 %) in a Fenton reaction and were able to accelerate metal-catalyzed oxidation in a beer model, as shown by a decrease of almost 11 % of the dissolved oxygen. Although black malt was able to reduce the overall levels of radicals generated by the Fenton reaction, high molecular weight compounds had an opposite effect due to the reductive redox-cycling of the catalytic amounts of iron.

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Abbreviations

ESR:

Electron spin resonance

HMW:

High molecular weight

LMW:

Low molecular weight

MLD:

Melanoidins

MRPs:

Maillard reaction products

PBN:

N-tert-Butyl-α-phenylnitrone

ROS:

Reactive oxygen species

SEC:

Size-exclusion chromatography

TEMPO:

2,2,6,6-Tetramethylpiperidine 1-oxyl

References

  1. Coghe S, Gheeraert B, Michiels A, Delvaux FR (2006) Development of Maillard reaction related characteristics during malt roasting. J Inst Brew 112(2):148–156

    Article  CAS  Google Scholar 

  2. Coghe S, D’Hollander H, Verachtert H, Delvaux FR (2005) Impact of dark specialty malts on extract composition and wort fermentation. J Inst Brew 111(1):51–60

    Article  Google Scholar 

  3. Coghe S, Adriaenssens B, Leonard S, Delvaux FR (2004) Fractionation of colored Maillard reaction products from dark specialty malts. J Am Soc Brew Chem 62(2):79–86

    CAS  Google Scholar 

  4. Yahya H, Linforth RST, Cook DJ (2014) Flavour generation during commercial barley and malt roasting operations: a time course study. Food Chem 145:378–387

    Article  CAS  Google Scholar 

  5. Wang H-Y, Qian H, Yao W-R (2011) Melanoidins produced by the Maillard reaction: structure and biological activity. Food Chem 128(3):573–584

    Article  CAS  Google Scholar 

  6. Carvalho DO, Correia E, Lopes L, Guido LF (2014) Further insights into the role of melanoidins on the antioxidant potential of barley malt. Food Chem 160:127–133

    Article  CAS  Google Scholar 

  7. Magalhães PJ, Almeida SM, Carvalho AM, Gonçalves LM, Pacheco JG, Cruz JM, Guido LF, Barros AA (2011) Influence of malt on the xanthohumol and isoxanthohumol behavior in pale and dark beers: a micro-scale approach. Food Res Int 44(1):351–359

    Article  Google Scholar 

  8. Wunderlich S, Zürcher A, Back W (2012) Xanthohumol in brewing-impact of malt, xanthohumol dosage, wort and storage temperature. Brewing Sci 65(1–2):7–15

    Google Scholar 

  9. Pastoriza S, Rufián-Henares JA (2014) Contribution of melanoidins to the antioxidant capacity of the Spanish diet. Food Chem 164:438–445

    Article  CAS  Google Scholar 

  10. Langner E, Rzeski W (2014) Biological properties of melanoidins: a review. Int J Food Prop 17(2):344–353

    Article  CAS  Google Scholar 

  11. Samaras TS, Camburn PA, Chandra SX, Gordon MH, Ames JM (2005) Antioxidant properties of kilned and roasted malts. J Agric Food Chem 53(20):8068–8074

    Article  CAS  Google Scholar 

  12. Echavarría AP, Pagán J, Ibarz A (2012) melanoidins formed by Maillard reaction in food and their biological activity. Food Eng Rev 4(4):203–223

    Article  Google Scholar 

  13. Coghe S, Adriaenssens B, Leonard S, Delvaux FR (2003) Characterization of dark specialty malts: new insights in color evaluation and pro- and antioxidative activity. J Am Soc Brew Chem 61(3):125–132

    CAS  Google Scholar 

  14. Hoff S, Lund MN, Petersen MA, Jespersen BM, Andersen ML (2012) Influence of malt roasting on the oxidative stability of sweet wort. J Agric Food Chem 60(22):5652–5659

    Article  CAS  Google Scholar 

  15. Kunz T, Strähmel A, Cortés N, Kroh LW, Methner FJ (2013) Influence of intermediate maillard reaction products with enediol structure on the oxidative stability of beverages. J Am Soc Brew Chem 71(3):114–123

    CAS  Google Scholar 

  16. Vanderhaegen B, Neven H, Verachtert H, Derdelinckx G (2006) The chemistry of beer aging—a critical review. Food Chem 95(3):357–381

    Article  CAS  Google Scholar 

  17. Guido LF, Fortunato NA, Rodrigues JA, Barros AA (2003) Voltammetric assay for the aging of beer. J Agric Food Chem 51(14):3911–3915

    Article  CAS  Google Scholar 

  18. Andersen ML, Skibsted LH (1998) Electron spin resonance spin trapping identification of radicals formed during aerobic forced aging of beer. J Agric Food Chem 46(4):1272–1275

    Article  CAS  Google Scholar 

  19. Andersen ML, Outtrup H, Skibsted LH (2000) Potential antioxidants in beer assessed by ESR spin trapping. J Agric Food Chem 48(8):3106–3111

    Article  CAS  Google Scholar 

  20. Morales FJ (2005) Assessing the non-specific hydroxyl radical scavenging properties of melanoidins in a Fenton-type reaction system. Anal Chim Acta 534(1):171–176

    Article  CAS  Google Scholar 

  21. Nøddekær TV, Andersen ML (2007) Effects of Maillard and caramelization products on oxidative reactions in lager beer. J Am Soc Brew Chem 65(1):15–20

    Google Scholar 

  22. EBC (2003) Analytica EBC. Fachverlag Hans Carl, Nürnberg

    Google Scholar 

  23. Rødtjer A, Skibsted LH, Andersen ML (2006) Antioxidative and prooxidative effects of extracts made from cherry liqueur pomace. Food Chem 99(1):6–14

    Article  Google Scholar 

  24. Nelson DP, Kiesow LA (1972) Enthalpy of decomposition of hydrogen peroxide by catalase at 25 degrees C (with molar extinction coefficients of H2O2 solutions in the UV). Anal Biochem 49(2):474–478

    Article  CAS  Google Scholar 

  25. Nunes CA, Alvarenga VO, de Souza Sant’Ana A, Santos JS, Granato D (2015) The use of statistical software in food science and technology: advantages, limitations and misuses. Food Res Int 75:270–280

    Article  Google Scholar 

  26. Cämmerer B, Chodakowski K, Gienapp C, Wohak L, Hartwig A, Kroh L (2012) Pro-oxidative effects of melanoidin–copper complexes on isolated and cellular DNA. Eur Food Res Technol 234(4):663–670

    Article  Google Scholar 

  27. Čechovská L, Konečný M, Velíšek J, Cejpek K (2012) Effect of maillard reaction on reducing power of malts and beers. Czech J Food Sci 30(6):548–556

    Google Scholar 

  28. Jehle D, Lund MN, Øgendal LH, Andersen ML (2011) Characterisation of a stable radical from dark roasted malt in wort and beer. Food Chem 125(2):380–387

    Article  CAS  Google Scholar 

  29. Cortes N, Kunz T, Suarez AF, Hughes P, Methner FJ (2010) Development and correlation between the organic radical concentration in different malt types and oxidative beer stability. J Am Soc Brew Chem 68(2):107–113

    CAS  Google Scholar 

  30. Danilewicz JC (2013) Reactions involving iron in mediating catechol oxidation in model wine. Am J Enol Viticult 64(3):316–324

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was funded by FEDER through the Operational Programme for Competitiveness Factors—COMPETE and by National Funds through FCT—Foundation for Science and Technology under the projects UID/QUI/50006/2013 and NORTE-07-0124-FEDER-000069. DC wishes to acknowledge FCT for his PhD studentship (SFRH/BD/79939/2011).

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Authors and Affiliations

  1. REQUIMTE/LAQV - Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre 687, 4169-007, Porto, Portugal

    Daniel O. Carvalho & Luís F. Guido

  2. The Niels Bohr Institute, University of Copenhagen, Universitetsparken 5, 2100, København Ø, Denmark

    Lars H. Øgendal

  3. Department of Food Science, University of Copenhagen, Rolighedsvej 30, 1958, Frederiksberg C, Denmark

    Mogens L. Andersen

Authors
  1. Daniel O. Carvalho
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  2. Lars H. Øgendal
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  3. Mogens L. Andersen
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  4. Luís F. Guido
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Corresponding author

Correspondence to Luís F. Guido.

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Carvalho, D.O., Øgendal, L.H., Andersen, M.L. et al. High molecular weight compounds generated by roasting barley malt are pro-oxidants in metal-catalyzed oxidations. Eur Food Res Technol 242, 1545–1553 (2016). https://doi.org/10.1007/s00217-016-2655-7

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  • DOI: https://doi.org/10.1007/s00217-016-2655-7

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