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Coordinate and redox interactions of epinephrine with ferric and ferrous iron at physiological pH.


ABSTRACT: Coordinate and redox interactions of epinephrine (Epi) with iron at physiological pH are essential for understanding two very different phenomena - the detrimental effects of chronic stress on the cardiovascular system and the cross-linking of catecholamine-rich biopolymers and frameworks. Here we show that Epi and Fe3+ form stable high-spin complexes in the 1:1 or 3:1 stoichiometry, depending on the Epi/Fe3+ concentration ratio (low or high). Oxygen atoms on the catechol ring represent the sites of coordinate bond formation within physiologically relevant bidentate 1:1 complex. Redox properties of Epi are slightly impacted by Fe3+. On the other hand, Epi and Fe2+ form a complex that acts as a strong reducing agent, which leads to the production of hydrogen peroxide via O2 reduction, and to a facilitated formation of the Epi-Fe3+ complexes. Epi is not oxidized in this process, i.e. Fe2+ is not an electron shuttle, but the electron donor. Epi-catalyzed oxidation of Fe2+ represents a plausible chemical basis of stress-related damage to heart cells. In addition, our results support the previous findings on the interactions of catecholamine moieties in polymers with iron and provide a novel strategy for improving the efficiency of cross-linking.

SUBMITTER: Korac J 

PROVIDER: S-EPMC5824886 | biostudies-other | 2018 Feb

REPOSITORIES: biostudies-other

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Coordinate and redox interactions of epinephrine with ferric and ferrous iron at physiological pH.

Korać Jelena J   Stanković Dalibor M DM   Stanić Marina M   Bajuk-Bogdanović Danica D   Žižić Milan M   Pristov Jelena Bogdanović JB   Grgurić-Šipka Sanja S   Popović-Bijelić Ana A   Spasojević Ivan I  

Scientific reports 20180223 1


Coordinate and redox interactions of epinephrine (Epi) with iron at physiological pH are essential for understanding two very different phenomena - the detrimental effects of chronic stress on the cardiovascular system and the cross-linking of catecholamine-rich biopolymers and frameworks. Here we show that Epi and Fe<sup>3+</sup> form stable high-spin complexes in the 1:1 or 3:1 stoichiometry, depending on the Epi/Fe<sup>3+</sup> concentration ratio (low or high). Oxygen atoms on the catechol r  ...[more]

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