Abstract
We have re-examined the problem of the interaction of melanins with metal ions. Metal ions are normal constituents of the pigment, but in some cases they can be related to pathologies, mainly at the level of the skin (Cu2+ and Fe3+) and of the central nervous system (Fe2+ and Mn2+). Our approach has been based on the mechanisms of adsorption on the particle surface, by the use of theoretical adsorption isotherms and kinetic models. Although this analysis doesn’t give detailed information on the specific sites involved, it is useful to better characterize the surface behaviour of the colloidal melanin. The results obtained demonstrate that the affinity of melanin for metal ions is very high, comparable to the most efficient materials employed in decontamination and recovery techniques. Moreover, our results demonstrate that three-parameters models, such as Langmuir-Freundlich, Redlich-Peterson and Tóth equations, fit the experimental data with great accuracy and that the adsorption follows pseudo-second-order kinetics.
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Abbreviations
- a :
-
Adsorption rate in the Elovich equation (mmol⋅g−1⋅min−1)
- a t :
-
Inverse of the adsorptive potential constant in the Tóth equation (dm3⋅mg−1)
- b :
-
Desorption constant in the Elovich equation (g⋅mmol−1)
- C :
-
Equilibrium concentration of ions in solution (mmol⋅dm−3)
- E :
-
Free energy of sorption (J⋅mmol−1)
- k 1 :
-
Pseudo-1° order rate constant
- k 2 :
-
Pseudo-2° order rate constant
- k p :
-
Rate constant for intraparticle diffusion
- K :
-
Constant in the Langmuir, Freundlich and Langmuir-Freundlich isotherms (dm3⋅mmol−1)
- K F :
-
Freundlich constant (dm3⋅g−1)
- K R :
-
Redlich-Peterson constant (g−1)
- K S :
-
Sips constant
- K 1 :
-
1° Temkin constant
- K 2 :
-
2° Temkin constant (dm3⋅mmol−1)
- q :
-
Amount of adsorbed ions (mmol⋅g−1)
- q 0 :
-
Monolayer adsorption capacity (mmol⋅g−1)
- q e :
-
Amount of adsorbed ions at equilibrium (mmol⋅g−1)
- q m :
-
Adsorption capacity (mmol⋅g−1)
- R :
-
Gas constant (J⋅mol−1⋅K−1)
- t :
-
Tóth heterogeneity coefficient
- T :
-
Absolute temperature (K)
- 1/n :
-
Freundlich heterogeneity index
- α :
-
Affinity coefficient (dm3⋅g−1)
- β :
-
Constant in the Dubinin-Radushkevich isotherm (mmol2⋅J−2)
- γ :
-
Heterogeneity coefficient
- ε :
-
Polany potential (J⋅mmol−1)
- τ :
-
Time (min)
References
Abou-Mesalam, M.M.: Sorption kinetics of copper, zinc, cadmium and nickel ions on synthetized silico-antimoniate ion exchanger. Colloids Surf. A 225, 85–94 (2003)
Adamson, A.W., Gast, A.P.: Physical Chemistry of Surfaces. Wiley-Interscience, New York (1997)
Allen, S.J., Gan, Q., Matthews, R., Johnson, P.A.: Comparison of optimised isotherm models from basic dye adsorption by kudzu. Biores. Technol. 88, 143–152 (2003)
Andrzejczyk, J., Buszman, E.: Interaction of Fe3+, Cu2+ and Zn2+ with melanin and melanoproteins from bovine eyes. Acta Biochim. Pol. 39, 85–88 (1992)
Bardani, L., Bridelli, M.G., Carbucicchio, M., Crippa, P.R.: Comparative Mössbauer and infrared analysis of iron-containing melanins. Biochim. Biophys. Acta 716, 8–15 (1982)
Bilińska, B.: On the structure of human hair melanins from an infrared spectroscopy analysis of their interactions with Cu2+ ions. Spectrochim. Acta A 57, 2525–2533 (2001)
Bridelli, M.G., Ciati, A., Crippa, P.R.: Binding of chemicals to melanins re-examined: Adsorption of some drugs to the surface of melanin particles. Biophys. Chem. 119, 137–145 (2006)
Buszman, E., Kwasniak, B., Dzierzewicz, Z., Wilczok, T.: Dinamics of metal ion-melanin complex formation. ESR and radiochemical studies. Studia Biophys. 122, 147–156 (1987)
Buszman, E., Kwasniak, B., Bogacz, A.: Binding capacity of metal ions to synthetic DOPA-melanins. Studia Biophys. 125, 143–153 (1988)
Choy, K.K.H., McKay, G., Porter, J.F.: Sorption of acid dyes from effluents using activated carbon. Res. Conserv. Recycl. 27, 57–71 (1999)
Cheung, C.W., Porter, J.F., McKay, G.: Sorption kinetic analysis for the removal of cadmium ions from effluents using bone char. Water Res. 35, 605–612 (2001)
Crippa, P.R., Giorcelli, C., Zeise, L.: Determination of surface characteristics and fractal dimensions of natural and synthetic eumelanins from nitrogen adsorption isotherms. Langmuir 19, 348–353 (2003)
Dastgheib, S.A., Rockstraw, D.A.: A model for the adsorption of single metal ion solutes in aqueous solution onto activated carbon produced from pecan shells. Carbon 40, 1843–1851 (2002)
Froncisz, W., Sarna, T., Hyde, J.S.: Cu2+ probe of metal-ion binding sites in melanin using Electron Paramagnetic Resonance spectroscopy. I. Synthetic melanins. Arch. Biochem. Biophys. 202, 289–303 (1980)
Gregg, S.J., Sing, K.S.W.: Adsorption, surface area and porosity. Academic, San Diego (1982)
Ho, Y.S.: Review of second-order models for adsorption systems. J. Hazard. Mater. B 136, 681–689 (2006)
Ho, Y.S., McKay, G.: The kinetics of sorption of divalent metal ions onto sphagnum moss peat. Water Res. 34, 735–742 (2000)
Hong, L., Liu, Y., Simon, J.D.: Binding of metal ions to melanin and their effects on the aerobic reactivity. Photochem. Photobiol. 80, 477–481 (2004)
Larsson, B., Tjälve, H.: Studies on the melanin-affinity of metal ions. Acta Physiol. Scand. 104, 479–484 (1978)
Lin, S.-H., Juang, R.-S.: Heavy metal removal from water by sorption using surfactant-modified montmorillonite. J. Hazard. Mater. B92, 315–326 (2002)
Liu, Y., Simon, J.D.: Isolation and biophysical studies of natural eumelanins: applications of imaging technologies and ultrafast spectroscopy. Pigment Cell Res. 16, 606–618 (2003)
Liu, Y., Hong, L., Kempf, V.R., Wakamatsu, K., Ito, S., Simon, J.D.: Ion exchange and adsorption of Fe(III) by Sepia melanin. Pigment Cell Res. 17, 262–269 (2004)
Low, M.J.D.: Kinetics of chemisorption of gases on solids. Chem. Rev. 60, 267–312 (1960)
Lydén, A., Larsson, B.S., Lindquist, N.G.: Melanin affinity of manganese. Acta Pharmacol. Toxicol. 55, 133–138 (1984)
McKay, G.: Adsorption of dyestuffs from aqueous solution using activated carbon. III. Intraparticle diffusion processes. J. Chem. Technol. Biotechnol. 33A, 196–204 (1983)
Onyango, M.S., Kojima, Y., Aoyi, O., Bernardo, E.C., Matsuda, H.: Adsorption equilibrium modelling and solution chemistry dependence of fluoride removal from water by trivalent cation exchanged zeolite F-9. J. Colloid Interface Sci. 279, 341–350 (2004)
Perić, J., Trgo, M., Vukojević Medvidović, N.: Removal of zinc, copper and lead by natural zeolite—a comparison of adsorption isotherms. Water Res. 38, 1893–1899 (2004)
Prota, G.: Melanins and Melanogenesis. Academic, San Diego (1992)
Samokhvalov, A., Liu, Y., Simon, J.D.: Characterization of the Fe(III)-binding site in Sepia eumelanin by resonance Raman confocal microspectroscopy. Photochem. Photobiol. 80, 84–88 (2004)
Sarna, T., Duleba, A., Korytowski, W., Swartz, H.: Interaction of melanin with oxygen. Arch. Biochem. Biophys. 200, 140–148 (1980)
Stainsack, J., Mangrich, A.S., Maia, C.M.B.F., Machado, V.G., dos Santos, J.C.P., Nakagaki, S.: Spectroscopic investigation of hard and soft metal binding sites in synthetic melanin. Inorg. Chim. Acta 356, 243–248 (2003)
Stępien, K.B., Dworzanski, J.P., Imielski, S.: Study of chloroquine binding to melanins by pyrolysis-gas chromatography and electron spin resonance spectroscopy. J. Anal. Appl. Pyrolysis 9, 297–307 (1986)
Szpoganicz, B., Gidanian, S., Kong, P., Farmer, P.: Metal binding by melanins: studies of colloidal dihydroxyindole-melanin and its complexation by Cu(II) and Zn(II) ions. J. Inorg. Biochem. 89, 45–53 (2002)
Tóth, J.: Calculation of the BET-compatible surface area from any type 1 isotherms measured above the critical temperature. J. Colloid Interface Sci. 225, 378–383 (2000)
Zajac, G.W., Gallas, J.M., Cheng, J., Eisner, M., Moss, S.C., Alvarado-Swaisgood, A.E.: The fundamental unit of synthetic melanin: a verification by tunnel microscopy of X-ray scattering results. Biochim. Biophys. Acta 1199, 271–278 (1994)
Zecca, L., Gallorini, M., Schunemann, V., Trautwein, A.X., Gerlach, M., Riederer, P., Vezzoni, P., Tampellini, D.: Iron, neuromelanin and ferritin content in the substantia nigra of normal subjects at different ages: consequences for iron storage and neurodegenerative processes. J. Neurochem. 76, 1766–1773 (2001)
Zecca, L., Tampellini, D., Gatti, A., Crippa, P.R., Eisner, M., Sulzer, D., Ito, S., Fariello, R., Gallorini, M.: The neuromelanin of human substantia nigra and its interaction with metals. J. Neural Transm. 109, 663–672 (2002)
Zucca, F.A., Giaveri, G., Gallorini, M., Alberini, A., Toscani, M., Pezzoli, G., Lucius, R., Wilms, H., Sulzer, D., Ito, S., Wakamatsu, K., Zecca, L.: The neuromelanin of human Substantia nigra: physiological and pathogenic aspects. Pigment Cell Res. 17, 610–617 (2004)
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Bridelli, M.G., Crippa, P.R. Theoretical analysis of the adsorption of metal ions to the surface of melanin particles. Adsorption 14, 101–109 (2008). https://doi.org/10.1007/s10450-007-9059-8
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DOI: https://doi.org/10.1007/s10450-007-9059-8