Vibrational mode structure and symmetry in proteins and analogs containing Fe4S4 clusters: resonance Raman evidence that HiPIP is tetrahedral while ferredoxin undergoes a D2d distortion

Czernuszewicz, Roman S.; Macor, Kathleen A.; Johnson, Michael K.; Gewirth, Andrew A.; Spiro, Thomas G.

doi:10.1021/ja00257a045

Cited by 107 publications

(111 citation statements)

References 3 publications

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“…Strong absorptions observed at 353 cm −1 for complexes I, III, and IV are corresponding to the Fe-μ 3 -S stretching transitions. 26,27 The same infrared transition for the [Fe 4 S 4 (SCH 2 Ph) 4 ] 2− cluster was reported to be found at 359 cm −1 at 77 K. 28 However, in the case of complex II, the corresponding peak was observed at 363 cm −1 and 324 cm −1 due to the two different Fe coordination geometries.…”

Section: Methodssupporting

confidence: 65%

Synthesis, Structure, and Reactivity of the [Fe₄S₄(SR)₄]^2-(R = 2-, 3-, and 4-Pyridinemethane) Clusters

Kim¹,

Han²

2012

Bulletin of the Korean Chemical Society

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The [Fe 4 S 4 ]2+ clusters with 2-, 3-, and 4-pyridinemethanethiolate (S2-Pic, S3-Pic, and S4-Pic, respectively) terminal ligands have been synthesized from the ligand substitution reaction of the ( + transition decreased in the order of II, III and IV, and the reduction potential changes by the ligands were explained based on the structural differences among the complexes. The complex III was reacted with sulfonium salt of [PhMeSCH 2 -p-C 6 H 4 CN](BF 4 ) in MeCN to test possible radical-involving reaction as a functional model of the [Fe 4 S 4 ]-SAM (S-adenosylmethionine) cofactor. However, the isolated reaction products of 3-pyridinemethanethiolate-p-cyanobenzylsulfide and thioanisole suggested that the reaction followed an ionic mechanism and the products formed from the terminal ligand attack to the sulfonium.

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Section: Methodssupporting

confidence: 65%

Synthesis, Structure, and Reactivity of the [Fe₄S₄(SR)₄]^2-(R = 2-, 3-, and 4-Pyridinemethane) Clusters

Kim¹,

Han²

2012

Bulletin of the Korean Chemical Society

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“…2, traces A and B). On the basis of extensive assignments by Johnson and co-workers (31,32), two weak bands at 334 cm Ϫ1 and ϳ358 cm Ϫ1 , whose signal relative intensities were enhanced upon 457.9 nm Ar ϩ ion laser excitation (Fig. 2, trace , and at least two bands associated primarily with Fe-S terminal modes at 369 cm Ϫ1 and 387 cm Ϫ1 (31,32).…”

Section: Purification and Characterization Of T Acidophilum Diclustermentioning

confidence: 93%

“…On the basis of extensive assignments by Johnson and co-workers (31,32), two weak bands at 334 cm Ϫ1 and ϳ358 cm Ϫ1 , whose signal relative intensities were enhanced upon 457.9 nm Ar ϩ ion laser excitation (Fig. 2, trace , and at least two bands associated primarily with Fe-S terminal modes at 369 cm Ϫ1 and 387 cm Ϫ1 (31,32). Thus, although 7Fe ferredoxin of T. acidophilum strain HO-62 contains a zinc center, the EPR and resonance Raman spectral properties are very similar to those of conventional 7Fe ferredoxins reported earlier (31), clearly demonstrating the existence of common [3Fe-4S] and [4Fe-4S] core structures.…”

Section: Purification and Characterization Of T Acidophilum Diclustermentioning

confidence: 99%

Novel Zinc-containing Ferredoxin Family in Thermoacidophilic Archaea

Iwasaki

Suzuki

Kon

et al. 1997

Journal of Biological Chemistry

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The dicluster-type ferredoxins from the thermoacidophilic archaea such as Thermoplasma acidophilum and Sulfolobus sp. are known to contain an unusually long extension of unknown function in the N-terminal region. Recent x-ray structural analysis of the Sulfolobus ferredoxin has revealed the presence of a novel zinc center, which is coordinated by three histidine ligand residues in the N-terminal region and one aspartate in the ferredoxin core domain. We report here the quantitative metal analyses together with electron paramagnetic resonance and resonance Raman spectra of T. acidophilum ferredoxin, demonstrating the presence of a novel zinc center in addition to one [3Fe-4S] and one [4Fe-4S] cluster (Fe/Zn ‫؍‬ 6.8 mol/mol). A phylogenetic tree constructed for several archaeal monocluster and dicluster type ferredoxins suggests that the zinc-containing ferredoxins of T. acidophilum and Sulfolobus sp. form an independent subgroup, which is more distantly related to the ferredoxins from the hyperthermophiles than those from the methanogenic archaea, indicating the existence of a novel group of ferredoxins, namely, a "zinc-containing ferredoxin family" in the thermoacidophilic archaea. Inspection of the N-terminal extension regions of the archaeal zinc-containing ferredoxins suggested strict conservation of three histidine and one aspartate residues as possible ligands to the novel zinc center.

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“…By onalogy, the Raman spectrum for oxidized iron protein can be completely assigned under T,r symmetry, see Table I. A Dt(l distortion is generally apparent in the Fe&G cores encountered in bacterial ferredoxins and synthetic analogs in the crystalline state and manifests itself in Raman spectrum by resolvable splittings of degenerate modes [12]. However, it is not possible to rule out a similar distortion for the Fe.& core in iron protein since the Raman bands are broader despite comparable spectral resoluti.on.…”

Section: June 1991mentioning

confidence: 99%

Resonance Raman studies of the [4Fe‐4S] to [2Fe‐2S] cluster conversion in the iron protein of nitrogenase

Morgan

Mortenson

et al. 1991

FEBS Letters

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Resonance Raman spectroscopy has been used to investigate the Fe-S stretching modes of the [4Fe-4SP+ cluster in the oxidized iron protein of Closfri~iron pusrertrianrrm nitrogenase. The results are consistent with a cubane [4Fe_4S] cluster having effective Td symmetry with cysteinyl coordination for each iron. In accord with previous optical and EPR studies [(1984) Biochemistry 23,21 lg-21221. treatment with the iron chelator CI,GL'-dipyyidyl in the presence of MgATP is shown to effect cluster conversion to a [ZFe-2SlZ+ cluster. Resonance Raman data also indicate that partial conversion to a [2Fe-tS]*+ cluster is induced by thionine-oxidation in the presence of MgATP in the absence of an iron chelator. This result suggests new explanations for the dramatic change in the CD spectrum that accompanies MgATP-binding to the oxidized Fe protein and the anomalous resonance Raman spectra of thionine-oxidized Clnsrridiunr pusreuriunum bidirectional hydrogenase.

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Vibrational mode structure and symmetry in proteins and analogs containing Fe4S4 clusters: resonance Raman evidence that HiPIP is tetrahedral while ferredoxin undergoes a D2d distortion

Cited by 107 publications

References 3 publications

Synthesis, Structure, and Reactivity of the [Fe₄S₄(SR)₄]^2-(R = 2-, 3-, and 4-Pyridinemethane) Clusters

Synthesis, Structure, and Reactivity of the [Fe₄S₄(SR)₄]^2-(R = 2-, 3-, and 4-Pyridinemethane) Clusters

Novel Zinc-containing Ferredoxin Family in Thermoacidophilic Archaea

Resonance Raman studies of the [4Fe‐4S] to [2Fe‐2S] cluster conversion in the iron protein of nitrogenase

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Vibrational mode structure and symmetry in proteins and analogs containing Fe4S4 clusters: resonance Raman evidence that HiPIP is tetrahedral while ferredoxin undergoes a D2d distortion

Cited by 107 publications

References 3 publications

Synthesis, Structure, and Reactivity of the [Fe4S4(SR)4]2-(R = 2-, 3-, and 4-Pyridinemethane) Clusters

Synthesis, Structure, and Reactivity of the [Fe4S4(SR)4]2-(R = 2-, 3-, and 4-Pyridinemethane) Clusters

Novel Zinc-containing Ferredoxin Family in Thermoacidophilic Archaea

Resonance Raman studies of the [4Fe‐4S] to [2Fe‐2S] cluster conversion in the iron protein of nitrogenase

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Synthesis, Structure, and Reactivity of the [Fe₄S₄(SR)₄]^2-(R = 2-, 3-, and 4-Pyridinemethane) Clusters

Synthesis, Structure, and Reactivity of the [Fe₄S₄(SR)₄]^2-(R = 2-, 3-, and 4-Pyridinemethane) Clusters