title: Protein control of iron-sulfur cluster redox potentials.
abstract: The relationship between the three-dimensional structures of iron-sulfur proteins and the redox potentials of their iron-sulfur clusters is of fundamental importance. We report calculations of the redox potentials of the [Fe4S4(S-cys)4]-2/-3 couple in four crystallographically characterized proteins: Azotobacter vinelandii ferredoxin I, Peptococcus aerogenes ferredoxin, Bacillus thermoproteolyticus ferredoxin, and Chromatium vinosum high potential iron protein (HiPIP). Our calculations use the "protein dipoles Langevin dipoles" microscopic electrostatic model, which includes both protein and solvent water. The variations in calculated redox potentials are in excellent agreement with experimental data. In particular, our results confirm the important role of amide groups close to the cluster in separating the potential of C. vinosum HiPIP from those of the other three proteins. However, the potentials of these latter exhibit a substantial range despite extremely similar amide group environments of their clusters. Our results show that the potentials in these proteins are tuned in part by varying the access of solvent water to the neighborhood of the cluster. Our calculations provide the first successful quantitative modeling of the protein control of iron-sulfur cluster redox potentials.
authors: Department of Chemistry, University of Southern California, Los Angeles 90089-0482.
authors: R
authors: R
authors: Langen
authors: G M
authors: GM
authors: Jensen
authors: U
authors: U
authors: Jacob
authors: P J
authors: PJ
authors: Stephens
authors: A
authors: A
authors: Warshel
mesh_terms: D016948:Azotobacter vinelandii / Q000378:metabolism; D001407:Bacillus / Q000378:metabolism; D001426:Bacterial Proteins; D002844:Chromatium / Q000378:metabolism; D005288:Ferredoxins / Q000737:chemistry / Q000378:metabolism; D007506:Iron-Sulfur Proteins / Q000737:chemistry* / Q000378:metabolism*; D008958:Models, Molecular; D010084:Oxidation-Reduction; D010460:Peptococcus / Q000378:metabolism; D045322:Photosynthetic Reaction Center Complex Proteins; D011199:Potentiometry; D011487:Protein Conformation
chemical_list: D001426:Bacterial Proteins; D005288:Ferredoxins; D007506:Iron-Sulfur Proteins; D045322:Photosynthetic Reaction Center Complex Proteins; C007943:high potential iron-sulfur protein