Effect of divers anions on the electron-transfer reaction between iron and rusticyanin from Thiobacillus ferrooxidans. 1991

R C Blake, and K J White, and E A Shute
Department of Biochemistry, Meharry Medical College, Nashville, Tennessee 37208.

Rusticyanin is a soluble blue copper protein found in abundance in the periplasmic space of Thiobacillus ferrooxidans, an acidophilic bacterium capable of growing chemolithotrophically on soluble ferrous sulfate. The one-electron-transfer reactions between soluble iron and purified rusticyanin were studied by stopped-flow spectrophotometry in acidic solutions containing each of 14 different anions. The second-order rate constants for both the Fe(II)-dependent reduction and the Fe(III)-dependent oxidation of the rusticyanin varied as a function of the identity of the principal anion in solution. Analogous electron-transfer reactions between soluble iron and bis(dipicolinato)cobaltate(III) or bis(dipicolinato)ferrate(II) were studied by stopped-flow spectrophotometry under solution conditions identical with those of the rusticyanin experiments. Similar anion-dependent reactivity patterns were obtained with soluble iron whether the other reaction partner was rusticyanin or either of the two organometallic complexes. The Marcus theory of outer-sphere electron transfer reactions was applied to this set of kinetic data to demonstrate that the rusticyanin may possess at least two electron-transfer pathways for liganded iron, one where the pattern of electron-transfer reactivity is controlled largely by protein-independent activation parameters and one where the protein exhibits an anion-dependent kinetic specificity. The exact role of rusticyanin in the iron-dependent respiratory electron transport chain of T. ferrooxidans remains unclear.

UI MeSH Term Description Entries
D007501 Iron A metallic element with atomic symbol Fe, atomic number 26, and atomic weight 55.85. It is an essential constituent of HEMOGLOBINS; CYTOCHROMES; and IRON-BINDING PROTEINS. It plays a role in cellular redox reactions and in the transport of OXYGEN. Iron-56,Iron 56
D007700 Kinetics The rate dynamics in chemical or physical systems.
D008024 Ligands A molecule that binds to another molecule, used especially to refer to a small molecule that binds specifically to a larger molecule, e.g., an antigen binding to an antibody, a hormone or neurotransmitter binding to a receptor, or a substrate or allosteric effector binding to an enzyme. Ligands are also molecules that donate or accept a pair of electrons to form a coordinate covalent bond with the central metal atom of a coordination complex. (From Dorland, 27th ed) Ligand
D010084 Oxidation-Reduction A chemical reaction in which an electron is transferred from one molecule to another. The electron-donating molecule is the reducing agent or reductant; the electron-accepting molecule is the oxidizing agent or oxidant. Reducing and oxidizing agents function as conjugate reductant-oxidant pairs or redox pairs (Lehninger, Principles of Biochemistry, 1982, p471). Redox,Oxidation Reduction
D000838 Anions Negatively charged atoms, radicals or groups of atoms which travel to the anode or positive pole during electrolysis. Anion
D001400 Azurin A bacterial protein from Pseudomonas, Bordetella, or Alcaligenes which operates as an electron transfer unit associated with the cytochrome chain. The protein has a molecular weight of approximately 16,000, contains a single copper atom, is intensively blue, and has a fluorescence emission band centered at 308nm.
D001426 Bacterial Proteins Proteins found in any species of bacterium. Bacterial Gene Products,Bacterial Gene Proteins,Gene Products, Bacterial,Bacterial Gene Product,Bacterial Gene Protein,Bacterial Protein,Gene Product, Bacterial,Gene Protein, Bacterial,Gene Proteins, Bacterial,Protein, Bacterial,Proteins, Bacterial
D013816 Thermodynamics A rigorously mathematical analysis of energy relationships (heat, work, temperature, and equilibrium). It describes systems whose states are determined by thermal parameters, such as temperature, in addition to mechanical and electromagnetic parameters. (From Hawley's Condensed Chemical Dictionary, 12th ed) Thermodynamic
D013855 Thiobacillus A genus of gram-negative, rod-shaped bacteria that derives energy from the oxidation of one or more reduced sulfur compounds. Many former species have been reclassified to other classes of PROTEOBACTERIA. Thiobacillus denitrificans,Thiobacillus thioparus

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