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2015 | 60 | 3 | 475-481

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The acid-catalyzed interaction of melanin with nitrite ions. An EPR investigation


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The interaction of synthetic dihydroxyphenylalanine (DOPA) melanin (DM) with nitrite ions, NO2−, in the pH 3.6–7.0 range, has been investigated using electron paramagnetic resonance (EPR). We found that especially at pH <5.5 (from ca. 5.5 to 3.6) the reaction of DM with nitrite generated large quantities of new melanin radicals, which implies the involvement of nitrous acid, HNO2, in the radical formation process. Measurements carried out at constant pH of 3.6 showed that the melanin signal increased together with nitrite concentration, reaching a plateau level which was more than fourfold larger compared to the initial signal amplitude observed in a nitrite-free buffer of the same pH. The effects of nitrite and DM concentrations on the melanin-free radical content were also investigated. It is proposed that the radicals are generated by one electron oxidation of melanin ortho-hydroquinone groups to ortho-semiquinones by HNO2 or related nitrogen oxides such as NO2• radicals. The possible involvement of nitric oxide (•NO) and peroxynitrite (ONOO−) in DM oxidation was also examined. In air-free solutions, nitric oxide per se did not generate melanin radicals; however, in the presence of oxygen a marked increase in the melanin EPR signal intensity was observed. This result is interpreted in terms of the generation of radicals via the oxidation of DM by peroxynitrite. Our findings suggest that melanin can function as a natural scavenger of nitrous acid and some nitrous acid-derived species. This property may be relevant to physiological functions of melanin pigments in vivo.











Physical description


1 - 7 - 2015
1 - 10 - 2014
30 - 1 - 2015
6 - 8 - 2015


  • Department of Medical Physics and Biophysics, Faculty of Physics and Applied Computer Science, AGH-University of Science and Technology, 30 Mickiewicza Ave., 30-059 Krakow, Poland, Tel.: +48 12 617 4454, Fax: +48 12 634 0010
  • Laboratory of Pharmacology and Chemistry, National Institute of Environmental Health Sciences (NIH), P. O. Box 12233, Research Triangle Park, North Carolina 27709, U.S.A.
  • Laboratory of Pharmacology and Chemistry, National Institute of Environmental Health Sciences (NIH), P. O. Box 12233, Research Triangle Park, North Carolina 27709, U.S.A.


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