The surface oxidation potential of human neuromelanin reveals a spherical architecture with a pheomelanin core and a eumelanin surface

William D. Bush, Jacob Garguilo, Fabio A. Zucca, Alberto Albertini, Luigi Zecca, Glenn S. Edwards, Robert Nemanich, John D. Simon

Research output: Contribution to journalArticle

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Abstract

Neuromelanin (NM) isolated from the substantia nigra region of the human brain was studied by scanning probe and photoelectron emission microscopies. Atomic force microscopy reveals that NM granules are comprised of spherical structures with a diameter of ≈30 nm, similar to that observed for Sepia cuttlefish, bovine eye, and human eye and hair melanosomes. Photoelectron microscopy images were collected at specific wavelengths of UV light between 248 and 413 nm, using the spontaneous-emission output from the Duke OK-4 free electron laser. Analysis of the data establishes a threshold photoionization potential for NM of 4.5 ± 0.2 eV, which corresponds to an oxidation potential of -0.1 ± 0.2 V vs. the normal hydrogen electrode (NHE). The oxidation potential of NM is within experimental error of the oxidation potential measured for human eumelanosomes (-0.2 ± 0.2 V vs. NHE), despite the presence of a significant fraction of the red pigment, pheomelanin, which is characterized by a higher oxidation potential (+0.5 ± 0.2 V vs. NHE). Published kinetic studies on the early chemical steps of melanogenesis show that in the case of pigments containing a mixture of pheomelanin and eumelanin, of which NM is an example, pheomelanin formation occurs first with eumelanin formation predominantly occurring only after cysteine levels are depleted. Such a kinetic model would predict a structural motif with pheomelanin at the core and eumelanin at the surface, which is consistent with the measured surface oxidation potential of the ≈30-nm constituents of NM granules.

Original languageEnglish (US)
Pages (from-to)14785-14789
Number of pages5
JournalProceedings of the National Academy of Sciences of the United States of America
Volume103
Issue number40
DOIs
StatePublished - Oct 3 2006
Externally publishedYes

Fingerprint

Hydrogen
Electrodes
Microscopy
Sepia
Melanosomes
Decapodiformes
Atomic Force Microscopy
Substantia Nigra
Ultraviolet Rays
Hair
Cysteine
eumelanin
pheomelanin
neuromelanin
Lasers
Electrons
Brain

Keywords

  • Free electron laser
  • Oxidative stress
  • Parkinson's disease
  • Photoelectron imaging
  • Substantia nigra

ASJC Scopus subject areas

  • Genetics
  • General

Cite this

The surface oxidation potential of human neuromelanin reveals a spherical architecture with a pheomelanin core and a eumelanin surface. / Bush, William D.; Garguilo, Jacob; Zucca, Fabio A.; Albertini, Alberto; Zecca, Luigi; Edwards, Glenn S.; Nemanich, Robert; Simon, John D.

In: Proceedings of the National Academy of Sciences of the United States of America, Vol. 103, No. 40, 03.10.2006, p. 14785-14789.

Research output: Contribution to journalArticle

Bush, William D. ; Garguilo, Jacob ; Zucca, Fabio A. ; Albertini, Alberto ; Zecca, Luigi ; Edwards, Glenn S. ; Nemanich, Robert ; Simon, John D. / The surface oxidation potential of human neuromelanin reveals a spherical architecture with a pheomelanin core and a eumelanin surface. In: Proceedings of the National Academy of Sciences of the United States of America. 2006 ; Vol. 103, No. 40. pp. 14785-14789.
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AU - Bush, William D.

AU - Garguilo, Jacob

AU - Zucca, Fabio A.

AU - Albertini, Alberto

AU - Zecca, Luigi

AU - Edwards, Glenn S.

AU - Nemanich, Robert

AU - Simon, John D.

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N2 - Neuromelanin (NM) isolated from the substantia nigra region of the human brain was studied by scanning probe and photoelectron emission microscopies. Atomic force microscopy reveals that NM granules are comprised of spherical structures with a diameter of ≈30 nm, similar to that observed for Sepia cuttlefish, bovine eye, and human eye and hair melanosomes. Photoelectron microscopy images were collected at specific wavelengths of UV light between 248 and 413 nm, using the spontaneous-emission output from the Duke OK-4 free electron laser. Analysis of the data establishes a threshold photoionization potential for NM of 4.5 ± 0.2 eV, which corresponds to an oxidation potential of -0.1 ± 0.2 V vs. the normal hydrogen electrode (NHE). The oxidation potential of NM is within experimental error of the oxidation potential measured for human eumelanosomes (-0.2 ± 0.2 V vs. NHE), despite the presence of a significant fraction of the red pigment, pheomelanin, which is characterized by a higher oxidation potential (+0.5 ± 0.2 V vs. NHE). Published kinetic studies on the early chemical steps of melanogenesis show that in the case of pigments containing a mixture of pheomelanin and eumelanin, of which NM is an example, pheomelanin formation occurs first with eumelanin formation predominantly occurring only after cysteine levels are depleted. Such a kinetic model would predict a structural motif with pheomelanin at the core and eumelanin at the surface, which is consistent with the measured surface oxidation potential of the ≈30-nm constituents of NM granules.

AB - Neuromelanin (NM) isolated from the substantia nigra region of the human brain was studied by scanning probe and photoelectron emission microscopies. Atomic force microscopy reveals that NM granules are comprised of spherical structures with a diameter of ≈30 nm, similar to that observed for Sepia cuttlefish, bovine eye, and human eye and hair melanosomes. Photoelectron microscopy images were collected at specific wavelengths of UV light between 248 and 413 nm, using the spontaneous-emission output from the Duke OK-4 free electron laser. Analysis of the data establishes a threshold photoionization potential for NM of 4.5 ± 0.2 eV, which corresponds to an oxidation potential of -0.1 ± 0.2 V vs. the normal hydrogen electrode (NHE). The oxidation potential of NM is within experimental error of the oxidation potential measured for human eumelanosomes (-0.2 ± 0.2 V vs. NHE), despite the presence of a significant fraction of the red pigment, pheomelanin, which is characterized by a higher oxidation potential (+0.5 ± 0.2 V vs. NHE). Published kinetic studies on the early chemical steps of melanogenesis show that in the case of pigments containing a mixture of pheomelanin and eumelanin, of which NM is an example, pheomelanin formation occurs first with eumelanin formation predominantly occurring only after cysteine levels are depleted. Such a kinetic model would predict a structural motif with pheomelanin at the core and eumelanin at the surface, which is consistent with the measured surface oxidation potential of the ≈30-nm constituents of NM granules.

KW - Free electron laser

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