Abstract
Zinc protoporphyrin IX (ZnPP), the major red pigment in hams dry-cured without nitrates/nitrites, is an efficient photosensitizer, which upon absorption of visible light forms short-lived excited singlet state (1ZnPP*) and by intersystem crossing yields the very reactive triplet-excited state (3ZnPP*). Using nano-second laser flash photolysis and transient absorption spectroscopy NADH, ascorbic acid, hemin and dehydroascorbic acid were each found to be efficient quenchers of 3ZnPP*. The deactivation followed, in homogeneous dimethyl sulfoxide (DMSO) or DMSO:water (1:1) solutions, second-order kinetics. The rate constant for ascorbic acid and NADH for reductive quenching of 3ZnPP* was at 25 °C found to be 7.5 ± 0.1 × 104 L mol−1 s−1 and 6.3 ± 0.1 × 105 L mol−1 s−1, respectively. The polyphenols catechin and quercetin had no effect on 3ZnPP*. The quenching rate constant for oxidative deactivation of 3ZnPP* by dehydroascorbic acid and hemin was at 25 °C: 1.6 ± 0.1 × 105 L mol−1 s−1 and 1.47 ± 0.1 × 109 L mol−1 s−1, respectively. Oxidized glutathione did not act as an oxidative quencher for 3ZnPP*. After photoexcitation of ZnPP to 1ZnPP*, fluorescence was only found to be quenched by the presence of hemin in a diffusion-controlled reaction. The efficient deactivation of 3ZnPP* and 1ZnPP* by the metalloporphyrin (hemin) naturally present in meat may accordingly inherently protect meat proteins and lipids against ZnPP photosensitized oxidation.
Similar content being viewed by others
References
Wakamatsu J, Nishimura T, Hattori A (2004) A Zn-porphyrin complex contributes to bright red color in Parma ham. Meat Sci 67:95–100
Wakamatsu J, Ito T, Nishimura T, Hattori A (2007) Direct demonstration of the presence of zinc in the acetone-extractable red pigment from Parma ham. Meat Sci 76:385–387
Wakamatsu J, Odagiri H, Nishimura T, Hattori A (2009) Quantitative determination of Zn protoporphyrin IX, heme and protoporphyrin IX in Parma ham by HPLC. Meat Sci 82:139–142
Sakata R, Morita H, Norimatsu T, Niu J (1999) Characteristics of a red pigment in Parma ham. Jpn J Swine Sci 36:124–129
Adamsen CE, Moller JKS, Hismani R, Skibsted LH (2004) Thermal and photochemical degradation of myoglobin pigments in relation to colour stability of sliced dry-cured Parma ham and sliced dry-cured ham produced with nitrite salt. Eur Food Res Technol 218:403–409
Wiehe A, Stollberg H, Runge S, Paul A, Senge MO, Roder B (2001) PDT-related photophysical properties of conformationally distorted palladium(II) porphyrins. J Porphyr Phthalocyanines 5:853–860
Darwent JR, Douglas P, Harriman A, Porter G, Richoux MC (1982) Metal phthalocyanines and porphyrins as photosensitizers for reduction of water to hydrogen. Coord Chem Rev 44:83–126
Fernandez JM, Bilgin MD, Grossweiner LI (1997) Singlet oxygen generation by photodynamic agents. J Photochem Photobiol B-Biol 37:131–140
Parra V, Viguera J, Sanchez J, Peinado J, Esparrago F, Gutierrez JI, Andres AI (2010) Modified atmosphere packaging and vacuum packaging for long period chilled storage of dry-cured Iberian ham. Meat Sci 84:760–768
Cava R, Ladero L, Gonzalez S, Carrasco A, Ramirez MR (2009) Effect of pressure and holding time on colour, protein and lipid oxidation of sliced dry-cured Iberian ham and loin during refrigerated storage. Innov Food Sci Emerg Technol 10:76–81
Campus M, Flores M, Martinez A, Toldra F (2008) Effect of high pressure treatment on colour, microbial and chemical characteristics of dry cured loin. Meat Sci 80:1174–1181
Cilla I, Martinez L, Beltran JA, Roncales P (2006) Dry-cured ham quality and acceptability as affected by the preservation system used for retail sale. Meat Sci 73:581–589
Andres AI, Moller JKS, Adamsen CE, Skibsted LH (2004) High pressure treatment of dry-cured Iberian ham. Effect on radical formation, lipid oxidation and colour. Eur Food Res Technol 219:205–210
Honikel KO (2008) The use and control of nitrate and nitrite for the processing of meat products. Meat Sci 78:68–76
Numata M, Wakamatsu J (2009) Natural red pigment and food product and food material containing the pigment. Application number: 11/797,543, patent number: 7507428, USA
Buettner GR (1993) The pecking order of free-radicals and antioxidants—Lipid-peroxidation, alpha-tocopherol, and ascorbate. Arch Biochem Biophys 300:535–543
Danish Food Composition Databank—ed.7.01 (2010) National food institute, technical University of Denmark. http://www.foodcomp.dk/v7/fvdb_details.asp?FoodId=0923. Accessed 23 June 2010
Jensen MA, Elving PJ (1984) Nicotinamide adenine-dinucleotide (Nad +)—Formal potential of the Nad + Nad. Couple and Nad. Dimerization rate. Biochim Biophys Acta 764:310–315
Wu GY, Fang YZ, Yang S, Lupton JR, Turner ND (2004) Glutathione metabolism and its implications for health. J Nutr 134:489–492
Jones DP, Coates RJ, Flagg EW, Eley JW, Block G, Greenberg RS, Gunter EW, Jackson B (1992) Glutathione in foods listed in the National-Cancer-Institutes health habits and history food frequency questionnaire. Nutr Cancer Int J 17:57–75
Koppenol WH (1993) A thermodynamic appraisal of the radical sink hypothesis. Free Radic Biol Med 14:91–94
Compton DL, Laszlo JA (2002) Direct electrochemical reduction of hemin in imidazolium-based ionic liquids. J Electroanal Chem 520:71–78
Lakowicz JR (1983) Principles of fluorescence spectroscopy. Plenum Press, New York
van de Weert M (2010) Fluorescence quenching to study protein-ligand binding: common errors. J Fluoresc 20:625–629
Elias H, Chou MH, Winkler JR (1988) Electron-transfer kinetics of Zn-substituted cytochrome-c and its Ru(NH3)5(Histidine-33) derivative. J Am Chem Soc 110:429–434
Tremain SM, Kostic NM (2002) Molten-globule and other conformational forms of zinc cytochrome c. Effect of partial and complete unfolding of the protein on its electron-transfer reactivity. Inorg Chem 41:3291–3301
Zemel H, Hoffman BM (1981) Long-range triplet-triplet energy-transfer within metal-substituted hemoglobins. J Am Chem Soc 103:1192–1201
Feitelson J, Barboy N (1986) Triplet-state reactions of zinc protoporphyrins. J Phys Chem 90:271–274
Tsukahara K, Okada M, Asami S, Nishikawa Y, Sawai N, Sakurai T (1994) Photoinduced electron-transfer reactions of zinc and magnesium myoglobins. Coord Chem Rev 132:223–228
Lin JS, Chen YC, Chen CC, Luo LY, Diau EWG, Liu TF (2006) Fluorescence dynamics of zinc protoporphyrin in solution and inside anodized aluminum oxide (AAO) nano-channel arrays. J Chin Chem Soc 53:1405–1412
Benedini R, Raja V, Parolari G (2008) Zinc-protoporphyrin IX promoting activity in pork muscle. Lwt-Food Sci Technol 41:1160–1166
Williams NH, Yandell JK (1982) Outer-sphere electron-transfer reactions of ascorbate anions. Aust J Chem 35:1133–1144
Karyakin AA, Ivanova YN, Karyakina EE (2003) Equilibrium (NAD(+)/NADH) potential on poly(Neutral Red) modified electrode. Electrochem Commun 5:677–680
Bard AJ, Faulkner LR (1080) Electrochemical methods—Fundamental and application. John Wiley & Sons, New York
Jorgensen LV, Skibsted LH (1998) Flavonoid deactivation of ferrylmyoglobin in relation to ease of oxidation as determined by cyclic voltammetry. Free Radic Res 28:335–351
Conant JB, Tongberg CO (1930) The oxidation-reduction potentials of hemin and related substances. I. The potentials of various hemins and hematins in the absence and presence of pyridine. J Bioll Chem 86:0733–0741
Schafer FQ, Buettner GR (2001) Redox environment of the cell as viewed through the redox state of the glutathione disulfide/glutathione couple. Free Radic Biol Med 30:1191–1212
Acknowledgments
This research is supported by The Danish Research Council for Technology and Production.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Becker, E.M., Cardoso, D.R. & Skibsted, L.H. Quenching of excited states of red-pigment zinc protoporphyrin IX by hemin and natural reductors in dry-cured hams. Eur Food Res Technol 232, 343–349 (2011). https://doi.org/10.1007/s00217-010-1392-6
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00217-010-1392-6