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

Autor: Korać, Jelena, Stanković, Dalibor M., Stanić, Marina, Bajuk-Bogdanović, Danica, Žižić, Milan, Pristov, Jelena Bogdanović, Grgurić-Šipka, Sanja, Popović-Bijelić, Ana, Spasojević, Ivan
Rok vydání: 2018
Předmět:
Zdroj: Scientific Reports
Scientific Reports, Vol 8, Iss 1, Pp 1-11 (2018)
Popis: 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 O-2 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. Supplementary material: [http://cherry.chem.bg.ac.rs/handle/123456789/3040]
Databáze: OpenAIRE