Spectroscopic investigation of hard and soft metal binding sites in synthetic melanin
Understanding the interaction of metal ions with melanin structures is essential to know some intricate functions of this kind of compounds in the living systems. The coordination chemistry of vanadyl oxycation, VO(II), and copper, Cu(II), in a synthetic l-dopa melanin (SM) was investigated using el...
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Published in | Inorganica Chimica Acta Vol. 356; pp. 243 - 248 |
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Main Authors | , , , , , |
Format | Journal Article |
Language | English |
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Elsevier B.V
03.12.2003
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Abstract | Understanding the interaction of metal ions with melanin structures is essential to know some intricate functions of this kind of compounds in the living systems. The coordination chemistry of vanadyl oxycation, VO(II), and copper, Cu(II), in a synthetic
l-dopa melanin (SM) was investigated using electron paramagnetic resonance (EPR), Fourier transform infrared (FT IR) and ultraviolet–visible (UV–Vis) spectroscopy. The EPR and FT IR spectra indicated axially coordinated VO(II) ions bound to catecholate functional groups, and a fraction of the Cu(II) ions in a square planar structure partially coordinated to carboxylate functional groups. The resolved EPR perpendicular super hyperfine splitting constant,
A
N⊥, and the Cu(II) complex EPR parallel parameters
g
‖ and
A
‖ values indicated two magnetically equivalent nitrogen atoms in a plane with the coordination sphere, CuN
2O
2. The ultraviolet–visible (UV–Vis) spectra of solid samples indicate supramolecular structure constitution for the synthesized VO(II)SM and Cu(II)SM complexes.
The spectroscopic data (EPR, FT IR) indicated axial coordinated VO(II) ions bound to catecholate functional groups of the melanin structures, and square planar structure with part of the Cu(II) ions coordinated to carboxylated groups and two nitrogen atoms in a plane with the coordination sphere, CuN
2O
2. The UV–Vis spectra indicate supramolecular structure constitution for the synthesized VO(II)SM and Cu(II)SM complexes. |
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AbstractList | Understanding the interaction of metal ions with melanin structures is essential to know some intricate functions of this kind of compounds in the living systems. The coordination chemistry of vanadyl oxycation, VO(II), and copper, Cu(II), in a synthetic
l-dopa melanin (SM) was investigated using electron paramagnetic resonance (EPR), Fourier transform infrared (FT IR) and ultraviolet–visible (UV–Vis) spectroscopy. The EPR and FT IR spectra indicated axially coordinated VO(II) ions bound to catecholate functional groups, and a fraction of the Cu(II) ions in a square planar structure partially coordinated to carboxylate functional groups. The resolved EPR perpendicular super hyperfine splitting constant,
A
N⊥, and the Cu(II) complex EPR parallel parameters
g
‖ and
A
‖ values indicated two magnetically equivalent nitrogen atoms in a plane with the coordination sphere, CuN
2O
2. The ultraviolet–visible (UV–Vis) spectra of solid samples indicate supramolecular structure constitution for the synthesized VO(II)SM and Cu(II)SM complexes.
The spectroscopic data (EPR, FT IR) indicated axial coordinated VO(II) ions bound to catecholate functional groups of the melanin structures, and square planar structure with part of the Cu(II) ions coordinated to carboxylated groups and two nitrogen atoms in a plane with the coordination sphere, CuN
2O
2. The UV–Vis spectra indicate supramolecular structure constitution for the synthesized VO(II)SM and Cu(II)SM complexes. |
Author | Stainsack, Jonas Nakagaki, Shirley Machado, Vanderlei G. Mangrich, Antonio S. Maia, Claudia M.B.F. dos Santos, Julio C.P. |
Author_xml | – sequence: 1 givenname: Jonas surname: Stainsack fullname: Stainsack, Jonas organization: Departamento de Quı́mica, UFPR, Centro Politécnico, Univ. Federal do Parana, Jardim das Américas, LABEPR, C.P. 19081, CEP 81531-990 Curitiba, PR, Brazil – sequence: 2 givenname: Antonio S. surname: Mangrich fullname: Mangrich, Antonio S. email: mangrich@quimica.ufpr.br organization: Departamento de Quı́mica, UFPR, Centro Politécnico, Univ. Federal do Parana, Jardim das Américas, LABEPR, C.P. 19081, CEP 81531-990 Curitiba, PR, Brazil – sequence: 3 givenname: Claudia M.B.F. surname: Maia fullname: Maia, Claudia M.B.F. organization: Departamento de Quı́mica, UFPR, Centro Politécnico, Univ. Federal do Parana, Jardim das Américas, LABEPR, C.P. 19081, CEP 81531-990 Curitiba, PR, Brazil – sequence: 4 givenname: Vanderlei G. surname: Machado fullname: Machado, Vanderlei G. organization: Universidade do Sul de Santa Catarina, UNISUL, Tubarão, SC, Brazil – sequence: 5 givenname: Julio C.P. surname: dos Santos fullname: dos Santos, Julio C.P. organization: Departamento de Quı́mica, UFPR, Centro Politécnico, Univ. Federal do Parana, Jardim das Américas, LABEPR, C.P. 19081, CEP 81531-990 Curitiba, PR, Brazil – sequence: 6 givenname: Shirley surname: Nakagaki fullname: Nakagaki, Shirley organization: Departamento de Quı́mica, UFPR, Centro Politécnico, Univ. Federal do Parana, Jardim das Américas, LABEPR, C.P. 19081, CEP 81531-990 Curitiba, PR, Brazil |
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Cites_doi | 10.1016/S0162-0134(01)00405-6 10.1016/0304-4165(94)90006-X 10.1007/BF00336128 10.1016/S0378-4347(01)00486-8 10.1016/S0013-4686(99)00388-6 10.2136/sssaj1965.03615995002900030016x 10.1016/0048-9697(88)90036-8 10.1016/S0925-4439(99)00116-7 10.1016/S0891-5849(98)00234-2 10.1590/S0103-50532001000600008 10.1021/ja00480a044 10.1016/S0162-0134(01)00406-8 10.1016/S0013-4686(98)00096-6 10.1039/f19878303627 10.1021/ja00274a038 10.1021/ic50100a033 10.1021/ic50045a007 10.1016/0020-1693(94)04298-A 10.1016/S1386-1425(01)00519-4 10.1007/BF00335997 10.1016/S0162-0134(00)00207-5 10.1039/dt9790000600 10.1007/s003740050386 |
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Keywords | Melanin cathecolate and indole-2-carboxylic acid coordination sites Synthetic DOPA melanin Copper and vanadium complexes EPR spectroscopy |
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SubjectTerms | Copper and vanadium complexes EPR spectroscopy Melanin cathecolate and indole-2-carboxylic acid coordination sites Synthetic DOPA melanin |
Title | Spectroscopic investigation of hard and soft metal binding sites in synthetic melanin |
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