The oxidation-reduction kinetics of the reaction of cytochrome c1 with non-physiological redox agents

Biochim Biophys Acta. 1982 Jul 22;681(1):54-61. doi: 10.1016/0005-2728(82)90277-8.

Abstract

The kinetics of the oxidation-reduction reactions of cytochrome c1 with ascorbate, ferricyanide, triphenanthrolinecobalt(III) and N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) have been examined using the stopped-flow technique. The reduction of ferricytochrome c1 by ascorbic acid is investigated as a function of pH. It is shown that at neutral and alkaline pH the reduction of the protein is mainly performed by the doubly deprotonated form of ascorbate. From the ionic-strength-dependence studies of the reactions of cytochrome c1 with ascorbate, ferricyanide and triphenanthrolinecobalt(III), it is demonstrated that the reactions rate is governed by electrostatic interactions. The second-order rate constants for the reaction of cytochrome c1 with ascorbate, ferricyanide, TMPD and triphenanthrolinecobalt(III) are 1.4 . 10(4), 3.2 . 10(3), 3.8 . 10(4) and 1.3 . 10(8) M-1 . s-1 (pH 7.9, I = 0, 10 degrees C), respectively. Application of the Debye-Hückel theory to the data of the ionic-strength-dependence studies of these redox reactions of cytochrome c1 yielded for ferrocytochrome c1 and ferricytochrome c1 a net charge of --5 and --4, respectively. The latter value is close to that of --3 for the oxidized enzyme, calculated from the amino acid sequence of the protein. This implies that not a local charge on the surface of the protein, but the overall net charge of cytochrome c1 governs the reaction rate with small redox molecules.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Animals
  • Ascorbic Acid / pharmacology*
  • Cattle
  • Cobalt / pharmacology*
  • Cytochrome c Group / analogs & derivatives*
  • Cytochromes c1 / metabolism*
  • Ferricyanides / pharmacology*
  • Indicators and Reagents
  • Kinetics
  • Organometallic Compounds*
  • Osmolar Concentration
  • Oxidation-Reduction
  • Phenanthrolines / pharmacology*
  • Phenylenediamines / pharmacology*
  • Tetramethylphenylenediamine / pharmacology*

Substances

  • Cytochrome c Group
  • Ferricyanides
  • Indicators and Reagents
  • Organometallic Compounds
  • Phenanthrolines
  • Phenylenediamines
  • triphenanthrolinecobalt(III)
  • Cobalt
  • Cytochromes c1
  • Tetramethylphenylenediamine
  • Ascorbic Acid