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

2018
Authors
Korać, JelenaStanković, Dalibor

Stanić, Marina

Bajuk-Bogdanović, Danica

Žižić, Milan
Pristov-Bogdanović, Jelena
Grgurić-Šipka, Sanja

Popović-Bijelić, Ana
Spasojević, Ivan
Article (Published version)
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Show full item recordAbstract
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 pl...ausible 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.
Source:
Scientific Reports, 2018, 8Publisher:
- Nature Publishing Group, London
Funding / projects:
- Study of structure-function relationships in the plant cell wall and modifications of the wall structure by enzyme engineering (RS-173017)
- Strengthening of the MagBioVin Research and Innovation Team for Development of Novel Approaches for Tumour Therapy based on Nanostructured Materials (EU-621375)
Note:
- Supplementary material: http://cherry.chem.bg.ac.rs/handle/123456789/3040
DOI: 10.1038/s41598-018-21940-7
ISSN: 2045-2322
PubMed: 29476145
WoS: 000425934200018
Scopus: 2-s2.0-85042549576
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Institution/Community
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Korać, Jelena AU - Stanković, Dalibor AU - Stanić, Marina AU - Bajuk-Bogdanović, Danica AU - Žižić, Milan AU - Pristov-Bogdanović, Jelena AU - Grgurić-Šipka, Sanja AU - Popović-Bijelić, Ana AU - Spasojević, Ivan PY - 2018 UR - https://cherry.chem.bg.ac.rs/handle/123456789/2097 AB - 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. PB - Nature Publishing Group, London T2 - Scientific Reports T1 - Coordinate and redox interactions of epinephrine with ferric and ferrous iron at physiological pH VL - 8 DO - 10.1038/s41598-018-21940-7 ER -
@article{ author = "Korać, Jelena and Stanković, Dalibor and Stanić, Marina and Bajuk-Bogdanović, Danica and Žižić, Milan and Pristov-Bogdanović, Jelena and Grgurić-Šipka, Sanja and Popović-Bijelić, Ana and Spasojević, Ivan", year = "2018", 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 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.", publisher = "Nature Publishing Group, London", journal = "Scientific Reports", title = "Coordinate and redox interactions of epinephrine with ferric and ferrous iron at physiological pH", volume = "8", doi = "10.1038/s41598-018-21940-7" }
Korać, J., Stanković, D., Stanić, M., Bajuk-Bogdanović, D., Žižić, M., Pristov-Bogdanović, J., Grgurić-Šipka, S., Popović-Bijelić, A.,& Spasojević, I.. (2018). Coordinate and redox interactions of epinephrine with ferric and ferrous iron at physiological pH. in Scientific Reports Nature Publishing Group, London., 8. https://doi.org/10.1038/s41598-018-21940-7
Korać J, Stanković D, Stanić M, Bajuk-Bogdanović D, Žižić M, Pristov-Bogdanović J, Grgurić-Šipka S, Popović-Bijelić A, Spasojević I. Coordinate and redox interactions of epinephrine with ferric and ferrous iron at physiological pH. in Scientific Reports. 2018;8. doi:10.1038/s41598-018-21940-7 .
Korać, Jelena, Stanković, Dalibor, Stanić, Marina, Bajuk-Bogdanović, Danica, Žižić, Milan, Pristov-Bogdanović, Jelena, Grgurić-Šipka, Sanja, Popović-Bijelić, Ana, Spasojević, Ivan, "Coordinate and redox interactions of epinephrine with ferric and ferrous iron at physiological pH" in Scientific Reports, 8 (2018), https://doi.org/10.1038/s41598-018-21940-7 . .