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

Sci Rep. 2018 Feb 23;8(1):3530. doi: 10.1038/s41598-018-21940-7.

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Adrenergic Agents / chemistry*
  • Chlorides / chemistry
  • Coordination Complexes / chemistry*
  • Electron Spin Resonance Spectroscopy
  • Electrons*
  • Epinephrine / chemistry*
  • Ferric Compounds / chemistry
  • Ferrous Compounds / chemistry
  • Hydrogen Peroxide / chemistry
  • Hydrogen-Ion Concentration
  • Iron / chemistry*
  • Kinetics
  • Oxidation-Reduction
  • Oximetry
  • Oxygen / chemistry*
  • Solutions
  • Spectrum Analysis, Raman

Substances

  • Adrenergic Agents
  • Chlorides
  • Coordination Complexes
  • Ferric Compounds
  • Ferrous Compounds
  • Solutions
  • ferrous sulfate
  • Hydrogen Peroxide
  • Iron
  • Oxygen
  • ferric chloride
  • Epinephrine