Protein self-modification by heme-generated reactive species.
In the presence of H(2)O(2), heme proteins form active intermediates, which are able to oxidize exogenous molecules. Often these products are not stable compounds but reactive species on their own, such as organic radicals. They can both diffuse to the bulk of the solution or react with the protein that generated them. Here, we describe the self-modification underwent by heme proteins with globin-type fold, that is, myoglobin, hemoglobin, and neuroglobin when treated with NO(2) (-) or catechols in the presence of H(2)O(2). The reactive nitrogen species generated by NO(2) (-) give rise to nitration, oxidation, and/or crosslinking reactions between the proteins or their subunits. The quinones formed upon reaction with catechols easily modify Cys and His residues and eventually cause protein aggregation, which induces precipitation. The pattern of modifications undergone by the protein strongly depends on the nature of the protein and the reaction conditions.
Monzani
Enrico
E
Dipartimento di Chimica Generale, Via Taramelli 12, Pavia, Italy.
Nicolis
Stefania
S
Roncone
Raffaella
R
Barbieri
Marica
M
Granata
Alessandro
A
Casella
Luigi
L
D000595:Amino Acid Sequence; D002396:Catechols / Q000737:chemistry / Q000378:metabolism; D004298:Dopamine / Q000378:metabolism; D005914:Globins / Q000502:physiology; D006420:Hemeproteins / Q000737:chemistry / Q000502:physiology*; D006801:Humans; D008958:Models, Molecular; D009211:Myoglobin / Q000378:metabolism; D009419:Nerve Tissue Proteins / Q000502:physiology; D000078787:Neuroglobin; D009573:Nitrites / Q000378:metabolism; D009585:Nitrogen Dioxide / Q000378:metabolism; D011809:Quinones / Q000378:metabolism; D026361:Reactive Nitrogen Species / Q000378:metabolism*
D002396:Catechols; D006420:Hemeproteins; D009211:Myoglobin; D009419:Nerve Tissue Proteins; D000078787:Neuroglobin; D009573:Nitrites; D011809:Quinones; D026361:Reactive Nitrogen Species; C072305:4-fluorocatechol; D005914:Globins; D009585:Nitrogen Dioxide; D004298:Dopamine