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The interactions between MnO2+/Mn3+ complexes and ascorbates. A pulse radiolysis study.

D E Cabelli1

  • 1Chemistry Department, Brookhaven National Laboratory, Upton, NY 11973.

Free Radical Biology & Medicine
|January 1, 1989
PubMed
Summary

Manganese complexes react with ascorbic acid, with some forming complexes and others transferring electrons. These reactions are often faster than oxygen, impacting metal-induced oxygen toxicity research.

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Area of Science:

  • Biochemistry
  • Radiochemistry
  • Inorganic Chemistry

Background:

  • Ascorbic acid (vitamin C) is a vital biological reductant.
  • Manganese ions (Mn) play roles in biological systems and can influence oxidative stress.
  • Understanding the reactivity of metal ions with biological molecules is crucial for assessing toxicity.

Purpose of the Study:

  • To investigate the reaction mechanisms between various manganese (Mn) complexes and ascorbic acid/ascorbate.
  • To compare the reactivity of these Mn complexes with free oxygen.
  • To evaluate the implications for metal-induced oxygen toxicity.

Main Methods:

  • Pulse radiolysis was employed to study the kinetics of reactions.
  • Various MnO2+/Mn3+ complexes (sulfate, formate, pyrophosphate) were used.

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  • Reactions with ascorbic acid (AH2) and ascorbate (AH-) were monitored.
  • Main Results:

    • Mn3+-sulfate reacts with ascorbic acid/ascorbate through metal-ascorbate complex formation.
    • MnO2+-formate and Mn3+-pyrophosphate react via electron transfer without complexation.
    • Most Mn complexes reacted with ascorbate faster than free O2-.

    Conclusions:

    • The reaction pathway (complexation vs. electron transfer) depends on the specific Mn complex.
    • The high reactivity of Mn complexes with ascorbate compared to oxygen has implications for oxidative stress.
    • Further discussion is needed on the role of these reactions in metal-induced oxygen toxicity.