ESR Spectroscopy for the Study of Oxidative Processes in Food and Beverages

  • Mogens L. Andersen
  • Leif H. Skibsted
Reference work entry


Radicals are intermediates in many reactions that deteriorate foods. The detection of radicals by electron spin resonance, ESR, can provide mechanistic and quantitative information about these reactions, which has led to ESR-based methods for early prediction of shelf life of foods and beverages. ESR is also used for monitoring irradiated foods, since the generated radicals are often quite stable. ESR can moreover give important information about oxidation mechanisms and microscopic physical structural aspects, which is useful for developing protective measures against oxidation in food.


ESR Food Oxidative stability Spin trapping Oxidation 


  1. 1.
    Andersen ML, Skibsted LH. Detection of early events in lipid oxidation by electron spin resonance spectroscopy. Eur J Lipid Sci Technol. 2002;104:65.CrossRefGoogle Scholar
  2. 2.
    Schaich KM. EPR methods for studying free radicals in foods. In: Morello MJ, Shahidi F, Ho C-T, editors. Free radicals in food. Chemistry, nutrition and health effects. ACS symposium series 807. Washington: American Chemical Society; 2002. p.12.Google Scholar
  3. 3.
    Andersen ML, Velasco J, Skibsted LH. Analysis of lipid oxidation by ESR spectroscopy. In: Kamal-Eldin A, Pokorny J, editors. Analysis of lipid oxidation. Champaign: AOCS Press; 2005. p. 12.Google Scholar
  4. 4.
    Shukla A. Electron spin resonance in food science. Boston: Academic; 2017.CrossRefGoogle Scholar
  5. 5.
    Mangion I, Liu Y, Reibarkh M, Williamson RT, Welch CJ. Using electron paramagnetic resonance spectroscopy to facilitate problem solving in pharmaceutical research and development. J Org Chem. 2016;81:6937.CrossRefGoogle Scholar
  6. 6.
    Weil JA, Bolton JR, Wertz JE. Electron paramagnetic resonance. New York: Wiley-Interscience; 1994.Google Scholar
  7. 7.
    Eaton GR, Eaton SS, Barr DP, Weber RT. Quantitative EPR. Wien: Springer-Verlag; 2010.CrossRefGoogle Scholar
  8. 8.
    Blakley RL, Henry DD, Morgan WT, Clapp WL, Smith CJ, Barr D. Quantitative electron paramagnetic resonance: The importance of matching the Q-factor of standards and samples. Appl Spectrosc. 2001;55:1375.CrossRefGoogle Scholar
  9. 9.
    Saifutdinov RG, Larina LI, Vakul’skaya TI, Voronkov MG. Electron paramagnetic resonance in biochemistry and medicine. New York: Kluwer Academic/Plenum Publishers; 2001.Google Scholar
  10. 10.
    Rodrigues-Filho UP, Vaz jr S, Felicissimo MP, Scarpellini M, Cardoso DR, Vinhas RCJ, Landers R, Schneider JF, McGarvey BR, Andersen ML, Skibsted LH. Heterometallic manganese/zinc-phytate complex as a model compound for metal storage in wheat grains. J Inorg Biochem. 2005;99:1973.CrossRefGoogle Scholar
  11. 11.
    Gonis J, Hewitt DG, Troup G, Hutton DR, Hunter CR. The chemical origin of free radicals in coffee and other beverages. Free Radic Res. 1995;23:393.CrossRefGoogle Scholar
  12. 12.
    Gallez G, Baudelet C, Debuyst R. Free radicals in licorice-flavored sweets can be detected noninvasively using low frequency electron paramagnetic resonance after oral administration to mice. J Nutr. 2000;130:1831.CrossRefGoogle Scholar
  13. 13.
    Hofman T, Bors W, Stettmaier K. CROSSPY. A radical intermediate of melanoidin formation in roasted coffee. In: Morello MJ, Shahidi F, Ho C-T, editors. Free radicals in food. Chemistry, nutrition and health effects. ACS symposium series 807. Washington: American Chemical Society; 2002. p.49.Google Scholar
  14. 14.
    Santanilla JD, Fritsch G, Müller-Warmuth W Z. Elektronenspinresonanz-Experimente an Roh- und Röstkaffeeproben. Lebensm Unters Forsch. 1981;172:81.Google Scholar
  15. 15.
    Schaich KM, Rebello CA. Extrusion chemistry of wheat flour proteins: I. Free radical formation. Cereal Chem. 1999;76:748.CrossRefGoogle Scholar
  16. 16.
    Nissen LR, Huynh-Ba T, Petersen MA, Bertelsen G, Skibsted LH. Potential use of electron spin resonance spectroscopy for evaluating the oxidative status of potato flakes. Food Chem. 2002;79:387.CrossRefGoogle Scholar
  17. 17.
    Fan DM, Hu B, Lin LF, Huang LL, Wang MF, Zhao JX, Zhang H. Rice protein radicals: Growth and stability under microwave treatment. RSC Adv. 2016;6:97825.CrossRefGoogle Scholar
  18. 18.
    Yordanov ND, Mladenova R. EPR study of free radicals in bread. Spectrochim Acta A. 2004;60:1395.CrossRefGoogle Scholar
  19. 19.
    Jensen SH, Østdal MRC, Andersen ML, Skibsted LH. Oxidative stability of whole wheat bread during storage. LWT - Food Sci Technol. 2011;44:637.CrossRefGoogle Scholar
  20. 20.
    Jehle D, Lund MN, Øgendal LH, Andersen ML. Characterisation of a stable radical from dark roasted malt in wort and beer. Food Chem. 2011;125:380.CrossRefGoogle Scholar
  21. 21.
    Hoff S, Lund MN, Petersen MA, Jespersen BM, Andersen ML. Quality of pilsner malt and roasted malt during storage. J Inst Brew. 2014;120:331.Google Scholar
  22. 22.
    Stapelfeldt H, Nielsen BR, Skibsted LH. Effect of heat treatment, water activity and storage temperature on the oxidative stability of whole milk powder. Int Dairy J. 1997;7:331.CrossRefGoogle Scholar
  23. 23.
    Stapelfeldt H, Nielsen KN, Jensen SK, Skibsted LH. Free radical formation in freeze-dried raw milk in relation to its alpha-tocopherol level. J Dairy Res. 1999;66:461.CrossRefGoogle Scholar
  24. 24.
    Kristensen D, Skibsted LH. Comparison of three methods based on electron spin resonance spectrometry for evaluation of oxidative stability of processed cheese. J Agric Food Chem. 1999;47:3099.CrossRefGoogle Scholar
  25. 25.
    Kristensen D, Orlien V, Mortensen G, Brockhoff P, Skibsted LH. Light-induced oxidation in sliced Havarti cheese packaged in modified atmosphere. Int Dairy J. 2000;10:95.CrossRefGoogle Scholar
  26. 26.
    Thomsen MK, Knudsen JC, Risbo J, Skibsted LH. Effect of lactose crystallization on the oxidative stability of infant formula Milchwissenschaft. 2003;58:406.Google Scholar
  27. 27.
    Nissen LR, Månsson L, Bertelsen G, Huynh-Ba T, Skibsted LH. Protection of dehydrated chicken meat by natural antioxidants as evaluated by electron spin resonance spectrometry. J Agric Food Chem. 2000;48:5548.CrossRefGoogle Scholar
  28. 28.
    Jensen PN, Danielsen B, Bertelsen G, Skibsted LH, Andersen ML. Storage stabilities of pork scratchings, peanuts, oatmeal and muesli: Comparison of ESR spectroscopy, headspace-GC and sensory evaluation for detection of oxidation in dry foods. Food Chem. 2005;91:25.CrossRefGoogle Scholar
  29. 29.
    Yanez J, Sevilla CL, Becker D, Sevilla MD. Low-temperature autoxidation in unsaturated lipids – an electron-spin-resonance study. J Phys Chem. 1987;91:487.CrossRefGoogle Scholar
  30. 30.
    Geoffrey M, Lambelet P, Richert P. Role of hydroxyl radicals and singlet oxygen in the formation of primary radicals in unsaturated lipids: a solid state electron paramagnetic resonance study. J Agric Food Chem. 2000;48:974.CrossRefGoogle Scholar
  31. 31.
    Troup GJ, Hutton DR, Hewitt DG, Hunter CR. Free radicals in red wine, but not in white?. Free Radic Res. 1994;20:63.CrossRefGoogle Scholar
  32. 32.
    Jongberg S, Lund MN, Østdal H, Skibsted LH. Phenolic antioxidant scavenging of myosin radicals generated by hypervalent myoglobin. J Agric Food Chem. 2012;60(48):12020.CrossRefGoogle Scholar
  33. 33.
    Rosen GM, Britigan BE, Halpern HJ, Pou S. Free radicals. Biology and detection by spin trapping. New York: Oxford University Press; 1999.Google Scholar
  34. 34.
    Pascual EC, Goodman BA, Yeretzian C. Characterization of free radicals in soluble coffee by electron paramagnetic resonance spectroscopy. J Agric Food Chem. 2002;50:6114.CrossRefGoogle Scholar
  35. 35.
    Andersen ML, Skibsted LH. Electron spin resonance spin trapping identification of radicals formed during aerobic forced aging of beer. J Agric Food Chem. 1998;46:1272.CrossRefGoogle Scholar
  36. 36.
    Thomsen MK, Jacobsen C, Skibsted LH. Mechanism of initiation of oxidation in mayonnaise enriched with fish oil as studied by electron spin resonance spectroscopy. Eur Food Res Technol. 2000;211:381.CrossRefGoogle Scholar
  37. 37.
    Jacobsen C, Hartvigsen K, Thomsen MK, Hansen LF, Lund P, Skibsted LH, Hølmer G, Adler-Nissen J, Meyer AS. Lipid oxidation in fish oil enriched mayonnaise: Calcium disodium ethylenediaminetetraacetate, but not gallic acid, strongly inhibited oxidative deterioration. J Agric Food Chem. 2001;49:1009.CrossRefGoogle Scholar
  38. 38.
    Thomsen MK, Vedstesen H, Skibsted LH. Quantification of radical formation in oil-in-water food emulsions by electron spin resonance spectroscopy. J Food Lipids. 1999;6:149.CrossRefGoogle Scholar
  39. 39.
    Uchida M, Ono M. Improvement for oxidative flavor stability of beer - role of OH-radical in beer oxidation. J Am Soc Brew Chem. 1996;54:198.Google Scholar
  40. 40.
    Uchida M, Suga S, Ono M. Improvement for oxidative flavor stability of beer - rapid prediction method for beer flavor stability by electron spin resonance spectroscopy. J Am Soc Brew Chem. 1996;54:205.Google Scholar
  41. 41.
    Takaoka S, Kondo H, Uchida M, Kawasaki Y. Improvement of beer flavor stability by applying ESR method to industrial plant. MBAA Tech Quart. 1998;35:157.Google Scholar
  42. 42.
    Franz O, Back W. Erfahrungen zur messung von freien Radikalen mittels Elektronenspinresonanz- Spektrometer in der Brauerei. Monatsschrift für Brauwissenschaft. 2002;55:8.Google Scholar
  43. 43.
    Andersen ML, Outtrup H, Skibsted LH. Potential antioxidants in beer assessed by ESR spin trapping. J Agric Food Chem. 2000;48:3106.CrossRefGoogle Scholar
  44. 44.
    Frederiksen AM, Festersen RM, Andersen ML. Oxidative reactions during early stages of beer brewing studied by electron spin resonance and spin trapping. J Agric Food Chem. 2008;56:8514.CrossRefGoogle Scholar
  45. 45.
    Hougaard AB, Arneborg N, Andersen ML, Skibsted LH. ESR spin trapping for characterization of radical formation in Lactobacillus acidophilus NCFM and Listeria innocua. J Microbiol Methods. 2013;94:205.CrossRefGoogle Scholar
  46. 46.
    Wang Y, Hougaard AB, Paulander W, Skibsted LH, Ingmer H, Andersen ML. Catalase expression is modulated by vancomycin and ciprofloxacin and influences free radical formation in bacterial cultures of Staphylococcus aureus. Appl Environ Microbiol. 2015;81:6393.CrossRefGoogle Scholar
  47. 47.
    Faure AM, Andersen ML, Nyström L. Ascorbic acid induced degradation of beta-glucan: Hydroxyl radicals as intermediates studied by spin trapping and electron spin resonance spectroscopy. Carbohydr Polym. 2012;87(3):2160.CrossRefGoogle Scholar
  48. 48.
    Cui LQ, Lahti PM, Decker EA. Evaluating electron paramagnetic resonance (EPR) to measure lipid oxidation lag phase for shelf-life determination of oils. J Am Oil Chem Soc. 2017;94:89.CrossRefGoogle Scholar
  49. 49.
    Velasco J, Andersen ML, Skibsted LH. Evaluation of oxidative stability of vegetable oils by monitoring the tendency of radical formation. A comparison of electron spin resonance spectroscopy with the Rancimat method and differential scanning calorimetry. Food Chem. 2004;85:623.CrossRefGoogle Scholar
  50. 50.
    Velasco J, Andersen ML, Skibsted LH. Electron spin resonance spin trapping for analysis of lipid oxidation in oils: Inhibiting effect of the spin trap alfa-phenyl-N-tert-butylnitrone on lipid oxidation. J Agric Food Chem. 2005;53:1328.CrossRefGoogle Scholar
  51. 51.
    Kristensen D, Andersen ML, Skibsted LH. Prediction of oxidative stability of raw milk using spin trapping electron spin resonance spectroscopy. Milchwissenschaft. 2002;57:255.Google Scholar
  52. 52.
    Bettin SM, Isique WD, Franco DW, Andersen ML, Knudsen S, Skibsted LH. Phenols and metals in sugar-cane spirits. Quantitative analysis and effect on radical formation and radical scavenging. Eur Food Res Technol. 2002;215:169.CrossRefGoogle Scholar
  53. 53.
    Carlsen CU, Andersen ML, Skibsted LH. Oxidative stability of processed pork. Assay based on ESRdetection of radicalsm. Eur Food Res Technol. 2001;213:170.CrossRefGoogle Scholar
  54. 54.
    Andrés AI, Møller JKS, Adamsen CE, Skibsted LH. High pressure treatment of dry-cured Iberian ham. Effect on radical formation, lipid oxidation and colour. Eur Food Res Technol. 2004;219:205.CrossRefGoogle Scholar
  55. 55.
    Yucel U, Elias RJ, Coupland JN. Solute distribution and stability in emulsion-based delivery systems: An EPR study. Journal of Colloid and Interface Science. 2012;377:105.CrossRefGoogle Scholar
  56. 56.
    Munk MB, Erichsen HR, Andersen ML. The effects of low-molecular-weight emulsifiers in O/Wemulsions on microviscosity of non-solidified oil in fat globules and the mobility of emulsifiers at the globule surfaces. J Colloid Interface Sci. 2014;419:134.CrossRefGoogle Scholar
  57. 57.
    Krudopp H, Sonnichsen FD, Steffen-Heins A. Partitioning of nitroxides in dispersed systems investigated by ultrafiltration, EPR and NMR spectroscopy. J Colloid Interface Sci. 2015;452:15.CrossRefGoogle Scholar
  58. 58.
    Herrmann W, Stösser R, Borchert H-H. ESR imaging investigations of two-phase systems. Magn Reson Chem. 2007;45:496.CrossRefGoogle Scholar
  59. 59.
    Yucel U, Elias URJ, Coupland JN. Effect of liquid oil on the distribution and reactivity of a hydrophobic solute in solid lipid nanoparticles. J Am Oil Chem Soc. 2013;90:819.CrossRefGoogle Scholar
  60. 60.
    Hansen E, Lauridsen L, Skibsted LH, Moawad RK, Andersen ML. Oxidative stability of frozen pork patties: Effect of fluctuating temperature on lipid oxidation. Meat Sci. 2004;68:185.CrossRefGoogle Scholar
  61. 61.
    Yucel U, Elias RJ, Coupland JN. Localization and reactivity of a hydrophobic solute in lecithin and caseinate stabilized solid lipid nanoparticles and nanoemulsions. J Colloid Interface Sci. 2013;394:20.CrossRefGoogle Scholar
  62. 62.
    Berton-Carabin CC, Coupland JN, Elias RJ. Effect of the lipophilicity of model ingredients on their location and reactivity in emulsions and solid lipid nanoparticles. Colloids Surf A Physicochem Eng Asp. 2013;431:9.CrossRefGoogle Scholar
  63. 63.
    Zhou Y-T, Yin J-J, Lo YM. Application of ESR spin label oximetry in food science. Magn Reson Chem. 2011;49:S105.CrossRefGoogle Scholar
  64. 64.
    Andersen AB, Risbo J, Andersen ML, Skibsted LH. Oxygen permeation through an oil-encapsulating glassy food matrix studied by ESR line broadening using a nitroxyl spin probe. Food Chem. 2000;70:499.CrossRefGoogle Scholar
  65. 65.
    Svagan AJ, Koch CB, Hedenqvist MS, Nilsson F, Glasser G, Baluschev S, Andersen ML. Liquid-core nanocellulose-shell capsules with tunable oxygen permeability. Carbohydr Polym. 2016;136:292.CrossRefGoogle Scholar
  66. 66.
    Stefanova R, Vasilev NV, Spassov SL. Irradiation of food, current legislation framework, and detection of irradiated foods. Food Anal Methods. 2010;3:225.CrossRefGoogle Scholar
  67. 67.
    Rosenthal I. Analytical applications of electron spin resonance spectroscopy in food science. In: Mossoba MM, editor. Spectral methods in food analysis. Instrumentation and applications. New York: Marcel Dekker; 1999. p. 125.Google Scholar
  68. 68.
    Arvanitoyannis IS, Stratakos A, Mente E. Impact of irradiation on fish and seafood shelf life: a comprehensive review of applications and irradiation detection. Crit Rev Food Sci Nutr. 2009;49:68.CrossRefGoogle Scholar
  69. 69.
    Arvanitoyannis IS, Stratakos A, Tsarouhas P. Irradiation applications in vegetables and fruits: A review. Crit Rev Food Sci Nutr. 2009;49:427.CrossRefGoogle Scholar
  70. 70.
    Ahn JJ, Akram K, Kim HK, Kwon JH. Electron spin resonance spectroscopy for the identification of irradiated foods with complex ESR signals. Food Anal Methods. 2013;6:301.CrossRefGoogle Scholar
  71. 71.
    EN 1786:1996. Detection of irradiated food containing bone. Method by ESR spectroscopy. Brussels: European Committee for Standardization; 1996.Google Scholar
  72. 72.
    EN 1787:2000. Detection of irradiated food containing cellulose. Method by ESR spectroscopy. Brussels: European Committee for Standardization; 2000.Google Scholar
  73. 73.
    EN 13708:2001. Foodstuffs – detection of irradiated food containing crystalline sugar. Method by ESR spectroscopy. Brussels: European Committee for Standardization; 2001.Google Scholar
  74. 74.
    Vrielinck H, De Cooman H, Callens F, Sagstuen E. Radiation chemistry of solid-state carbohydrates using EMR. In: Lund A, Shiotani M, editors. Applications of EPR in radiation research. New York, Springer International Publishing; 2014. p. 189. Google Scholar
  75. 75.
    Wencka M, Wichlacz K, Kasprzyk H, Lijewski S, Hoffmann SK. Free radicals and their electron spin relaxation in cellobiose. X-band and W-band ESR and electron spin echo studies. Cellulose. 2007;14:183.CrossRefGoogle Scholar

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© Springer International Publishing AG, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Food ScienceUniversity of CopenhagenFrederiksberg CDenmark

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