Tietze, Daniel ; Sartorius, Jana ; Koley Seth, Banabithi ; Herr, Kevin ; Heimer, Pascal ; Imhof, Diana ; Mollenhauer, Doreen ; Buntkowsky, Gerd (2017)
New insights into the mechanism of nickel superoxide degradation from studies of model peptides.
In: Scientific Reports, 7 (1)
doi: 10.1038/s41598-017-17446-3
Artikel, Bibliographie
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Kurzbeschreibung (Abstract)
A series of small, catalytically active metallopeptides, which were derived from the nickel superoxide dismutase (NiSOD) active site were employed to study the mechanism of superoxide degradation especially focusing on the role of the axial imidazole ligand. In the literature, there are contradicting propositions about the catalytic importance of the N-terminal histidine. Therefore, we studied the stability and activity of a set of eight NiSOD model peptides, which represent the major model systems discussed in the literature to date, yet differing in their length and their Ni-coordination. UV-Vis-coupled stopped-flow kinetic measurements and mass spectrometry analysis unveiled their high oxidation sensitivity in the presence of oxygen and superoxide resulting into a much faster Ni(II)-peptide degradation for the amine/amide Ni(II) coordination than for the catalytically inactive bis-amidate Ni(II) coordination. With respect to these results we determined the catalytic activities for all NiSOD mimics studied herein, which turned out to be in almost the same range of about 2 × 106 M−1 s−1. From these experiments, we concluded that the amine/amide Ni(II) coordination is clearly the key factor for catalytic activity. Finally, we were able to clarify the role of the N-terminal histidine and to resolve the contradictory literature propositions, reported in previous studies.
Typ des Eintrags: | Artikel |
---|---|
Erschienen: | 2017 |
Autor(en): | Tietze, Daniel ; Sartorius, Jana ; Koley Seth, Banabithi ; Herr, Kevin ; Heimer, Pascal ; Imhof, Diana ; Mollenhauer, Doreen ; Buntkowsky, Gerd |
Art des Eintrags: | Bibliographie |
Titel: | New insights into the mechanism of nickel superoxide degradation from studies of model peptides |
Sprache: | Englisch |
Publikationsjahr: | 2017 |
Ort: | Darmstadt |
Verlag: | Springer |
Titel der Zeitschrift, Zeitung oder Schriftenreihe: | Scientific Reports |
Jahrgang/Volume einer Zeitschrift: | 7 |
(Heft-)Nummer: | 1 |
DOI: | 10.1038/s41598-017-17446-3 |
Zugehörige Links: | |
Kurzbeschreibung (Abstract): | A series of small, catalytically active metallopeptides, which were derived from the nickel superoxide dismutase (NiSOD) active site were employed to study the mechanism of superoxide degradation especially focusing on the role of the axial imidazole ligand. In the literature, there are contradicting propositions about the catalytic importance of the N-terminal histidine. Therefore, we studied the stability and activity of a set of eight NiSOD model peptides, which represent the major model systems discussed in the literature to date, yet differing in their length and their Ni-coordination. UV-Vis-coupled stopped-flow kinetic measurements and mass spectrometry analysis unveiled their high oxidation sensitivity in the presence of oxygen and superoxide resulting into a much faster Ni(II)-peptide degradation for the amine/amide Ni(II) coordination than for the catalytically inactive bis-amidate Ni(II) coordination. With respect to these results we determined the catalytic activities for all NiSOD mimics studied herein, which turned out to be in almost the same range of about 2 × 106 M−1 s−1. From these experiments, we concluded that the amine/amide Ni(II) coordination is clearly the key factor for catalytic activity. Finally, we were able to clarify the role of the N-terminal histidine and to resolve the contradictory literature propositions, reported in previous studies. |
Sachgruppe der Dewey Dezimalklassifikatin (DDC): | 500 Naturwissenschaften und Mathematik > 540 Chemie |
Fachbereich(e)/-gebiet(e): | 07 Fachbereich Chemie 07 Fachbereich Chemie > Eduard Zintl-Institut 07 Fachbereich Chemie > Eduard Zintl-Institut > Fachgebiet Physikalische Chemie |
Hinterlegungsdatum: | 01 Dez 2023 10:46 |
Letzte Änderung: | 01 Mär 2024 09:58 |
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Verfügbare Versionen dieses Eintrags
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New insights into the mechanism of nickel superoxide degradation from studies of model peptides. (deposited 17 Dez 2017 20:55)
- New insights into the mechanism of nickel superoxide degradation from studies of model peptides. (deposited 01 Dez 2023 10:46) [Gegenwärtig angezeigt]
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