title: Tetrathiolate coordination of germanium(IV) in a protein active site.
abstract: The tetracysteine metal coordination site of the rubredoxins from Clostridium pasteurianum (Cp) and Pyrococcus furiosus (Pf) are shown to stably bind the inorganic Ge(IV) ion. This is the first characterized coordination complex of tetravalent germanium with a biological macromolecule. Zn(II), Ga(III) and Ge(IV) substitution yields differential NMR chemical shifts for the 1H and 15N amide resonances throughout much of the protein structure. The differential shifts for the six backbone amides that hydrogen bond to the metal-coordinated sulfurs indicate that the pseudo 2-fold symmetry of the active site is more closely maintained in the hyperthermophile Pf rubredoxin than in its mesophile Cp homolog. These three metal substitutions form an isoelectronic series of small diamagnetic proteins for which reference structures are known to 1A resolution. These series provide a promising system to analyze theoretical predictions of the effects of differential charge distribution on chemical shifts from both proximal and long range interactions.
authors.affiliation: Wadsworth Center, New York State Department of Health, Empire State Plaza, Albany, NY 12201-0509, USA.
authors.forename: David M
authors.initials: DM
authors.lastname: LeMaster
authors.forename: Michael
authors.initials: M
authors.lastname: Minnich
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Parsons
authors.forename: Janet S
authors.initials: JS
authors.lastname: Anderson
authors.forename: Griselda
authors.initials: G
authors.lastname: Hernández
mesh_terms: D001419:Bacteria / Q000201:enzymology; D001665:Binding Sites; D003545:Cysteine / Q000737:chemistry / Q000378:metabolism; D005857:Germanium / Q000737:chemistry* / Q000378:metabolism; D008958:Models, Molecular; D011485:Protein Binding; D011506:Proteins / Q000737:chemistry* / Q000378:metabolism; D012416:Rubredoxins / Q000737:chemistry / Q000378:metabolism; D013438:Sulfhydryl Compounds / Q000737:chemistry* / Q000378:metabolism
chemical_list: D011506:Proteins; D012416:Rubredoxins; D013438:Sulfhydryl Compounds; D005857:Germanium; D003545:Cysteine