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54 Publications

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    10/01/03 | Crystal structure of the nickel-responsive transcription factor NikR.
    Schreiter ER, Sintchak MD, Guo Y, Chivers PT, Sauer RT, Drennan CL
    Nature Structural Biology. 2003 Oct;10(10):794-9. doi: 10.1038/nsb985

    NikR is a metal-responsive transcription factor that controls nickel uptake in Escherichia coli by regulating expression of a nickel-specific ATP-binding cassette (ABC) transporter. We have determined the first two structures of NikR: the full-length apo repressor at a resolution of 2.3 A and the nickel-bound C-terminal regulatory domain at a resolution of 1.4 A. NikR is the only known metal-responsive member of the ribbon-helix-helix family of transcription factors, and its structure has a quaternary arrangement consisting of two dimeric DNA-binding domains separated by a tetrameric regulatory domain that binds nickel. The position of the C-terminal regulatory domain enforces a large spacing between the contacts that each NikR DNA-binding domain can make with the nik operator. The regulatory domain of NikR contains four nickel-binding sites at the tetramer interface, each exhibiting a novel square-planar coordination by three histidines and one cysteine side chain.

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    10/09/01 | Life on carbon monoxide: X-ray structure of Rhodospirillum rubrum Ni-Fe-S carbon monoxide dehydrogenase.
    Drennan CL, Heo J, Sintchak MD, Schreiter ER, Ludden PW
    Proceedings of the National Academy of Sciences of the United States of America. 2001-10-09;98(21):11973-8. doi: 10.1073/pnas.211429998

    A crystal structure of the anaerobic Ni-Fe-S carbon monoxide dehydrogenase (CODH) from Rhodospirillum rubrum has been determined to 2.8-Å resolution. The CODH family, for which the R. rubrum enzyme is the prototype, catalyzes the biological oxidation of CO at an unusual Ni-Fe-S cluster called the C-cluster. The Ni-Fe-S C-cluster contains a mononuclear site and a four-metal cubane. Surprisingly, anomalous dispersion data suggest that the mononuclear site contains Fe and not Ni, and the four-metal cubane has the form [NiFe3S4] and not [Fe4S4]. The mononuclear site and the four-metal cluster are bridged by means of Cys531 and one of the sulfides of the cube. CODH is organized as a dimer with a previously unidentified [Fe4S4] cluster bridging the two subunits. Each monomer is comprised of three domains: a helical domain at the N terminus, an α/β (Rossmann-like) domain in the middle, and an α/β (Rossmann-like) domain at the C terminus. The helical domain contributes ligands to the bridging [Fe4S4] cluster and another [Fe4S4] cluster, the B-cluster, which is involved in electron transfer. The two Rossmann domains contribute ligands to the active site C-cluster. This x-ray structure provides insight into the mechanism of biological CO oxidation and has broader significance for the roles of Ni and Fe in biological systems.

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    05/07/01 | Ionic liquids based on FeCl(3) and FeCl(2). Raman scattering and ab initio calculations.
    Sitze MS, Schreiter ER, Patterson EV, Freeman RG
    Inorganic Chemistry. 2001 May 7;40(10):2298-304

    We have prepared ionic liquids by mixing either iron(II) chloride or iron(III) chloride with 1-butyl-3-methylimidazolium chloride (BMIC). Iron(II) chloride forms ionic liquids from a mole ratio of 1 FeCl(2)/3 BMIC to almost 1 FeCl(2)/1 BMIC. Both Raman scattering and ab initio calculations indicate that FeCl(4)(2-) is the predominant iron-containing species in these liquids. Iron(III) chloride forms ionic liquids from a mole ratio of 1 FeCl(3)/1.9 BMIC to 1.7 FeCl(3)/1 BMIC. When BMIC is in excess, Raman scattering indicates the presence of FeCl(4-). When FeCl(3) is in excess, Fe(2)Cl(7-) begins to appear and the amount of Fe(2)Cl(7-) increases with increasing amounts of FeCl(3). Ionic liquids were also prepared from a mixture of FeCl(2) and FeCl(3) and are discussed. Finally, we have used both Hartree-Fock and density functional theory methods to compute the optimized structures and vibrational spectra for these species. An analysis of the results using an all-electron basis set, 6-31G, as well as two different effective core potential basis sets, LANL2DZ and CEP-31G is presented.

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    08/23/99 | A room-temperature molten salt prepared from AuCl3 and 1-Ethyl-3-methylimidazolium chloride.
    Schreiter ER, Stevens JE, Ortwerth MF, Freeman RG
    Inorganic Chemistry. 1999 Aug 23;38(17):3935-7. doi: 10.1021/ic990062u

    A room-temperature molten salt has been prepared from AuCl3 and 1-ethyl-3-methylimidazolium chloride (EMIC). At a ratio of 1 mol of AuCl3 to 2 mol of EMIC, the salt is a bright yellow-orange and shows Raman spectral features at 170, 328, and 352 cm-1, indicating the presence of AuCl4-. Ab initio calculations indicate that a dinuclear Au2Cl7- species containing a bridging chlorine should be stable, but no such species has been observed.

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