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Melanin-Based Coatings as Lead-Binding Agents

DOI: 10.1155/2012/361803

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Abstract:

Interactions between metal ions and different forms of melanin play significant roles in melanin biochemistry. The binding properties of natural melanin and related synthetic materials can be exploited for nonbiological applications, potentially including water purification. A method for investigating metal ion-melanin interactions on solid support is described, with lead as the initial target. 2.5?cm discs of the hydrophobic polymer PVDF were coated with synthetic eumelanin from the tyrosinase-catalyzed polymerization of L-dopa, and with melanin extracted from human hair. Lead (Pb2+) binding was quantified by atomic absorption spectroscopy (flame mode), and the data was well fit by the Langmuir model. Langmuir affinities ranged from to ?M?1. At the maximum capacity observed, the synthetic eumelanin coating bound ~9% of its mass in lead. Binding of copper (Cu2+), zinc (Zn2+), and cadmium (Cd2+) to the synthetic-eumelanin-coated discs was also investigated. Under the conditions tested, the Langmuir affinities for Zn2+, Cd2+, and Cu2+ were 35%, 53%, and 77%, respectively, of the Langmuir affinity for Pb2+. The synthetic-eumelanin-coated discs have a slightly higher capacity for Cu2+ on a per mole basis than for Pb2+, and lower capacities for Cd2+ and Zn2+. The system described can be used to address biological questions and potentially be applied toward melanin-based water purification. 1. Introduction While the term “melanin” is widely recognized by the general public, our understanding of the bioorganic chemistry of melanins is far less advanced than for other biopolymers. However, there have been recent advances in the understanding of melanin structure, function, and properties [1, 2], as well as in the development of well-defined synthetic mimics [3, 4] and melanin-based materials [5, 6]. Melanins display extensive molecular recognition chemistry, with the ability to bind a wide range of organic and inorganic species. The interaction of melanins with metal ions plays a particularly large role in their biochemistry [7]. Current research suggests that the black-to-brown pigment eumelanin is formed via supramolecular assembly, and metal ions may be integral components of this assembly process [7, 8]. In human melanocytes, eumelanin is produced along with pheomelanin, a chemically distinct yellow-to-red pigment, in organelles known as melanosomes. Melanosomes are thought to play a role in calcium homeostasis [9]. Interactions between metals and melanin have been proposed to play a role in the development of melanoma [10] and may be leveraged for

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