Solvent-induced EPR anisotropy change of the non-heme chromophore of spinach ferredoxin

Coffman, Robert E.; Stavens, Bruce W.

doi:10.1016/0006-291x(70)90483-3

Cited by 15 publications

(5 citation statements)

References 13 publications

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“…We will also mention in our analysis the xanthine oxidase type enzymes. 13 For these [2Fe-2S*] proteins, there exists a phenomenological model rationalizing the correlation observed 14 between the three {g i } principal values (g max > g mid > g min , with an average value around 1.96) when plotting each g i as a function of g midg min (Bertrand and Gayda's model 7,8 ). Because an increasing number of 3D crystal structures for the [2Fe-2S*] systems are becoming available, we can now try to ground this model on a firm experimental (i.e., structural) basis, because there is a growing need to establish a clear correlation between spectroscopic values (readily obtained in frozen solutions: g tensors, Mo ¨ssbauer parameters, etc.)…”

Section: Introductionmentioning

confidence: 86%

Correlation between the Magnetic g Tensors and the Local Cysteine Geometries for a Series of Reduced [2Fe−2S*] Protein Clusters. A Quantum Chemical Density Functional Theory and Structural Analysis

Gambarelli

Mouesca

2004

Inorg. Chem.

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We relied on the density functional theory (DFT) to study the electronic structure of the [2Fe-2S*](SH)4 model of the active site of 2Fe ferredoxins and other proteins containing reduced [2Fe-2S*] clusters. The two (Fe(3+)-Fe(2+)-S-H) dihedral angles Omega1 and Omega2 defined for the two ligands on the ferrous side were allowed to vary, while the two other (Fe(2+)-Fe(3+)-S-H) angles Omega3 and Omega4 on the ferric side were kept constant. The Landé (g), magnetic hyperfine, and quadrupole tensors for two geometries, C2 (Omega1 = Omega2) and Cs (Omega1 = -Omega2), were calculated. To apply our model to the actual proteins, we listed all of the crystallographic structures available for the [2Fe-2S*] systems. A classification of these proteins, based on the four dihedral angles [Omega(i)](i=1-4), separates them into three main classes. The main structural feature of the first class (Omega1 approximately Omega2), with an average dihedral angle Omega(av) = (Omega1 + Omega2)/2 comprised between 115 degrees and 150 degrees, corresponds to a local ferrous C2 geometry (rather than C2nu, as previously assumed by Bertrand and Gayda: Biochim. Biophys. Acta 1979, 579, 107). We then established a direct correlation between the three principal g values and Omega(av). It is the first time that such a link has been made between the spectroscopic and structural parameters, a link, moreover, fully rationalized by our DFT calculations. We finally point out the basic differences between our C2 results with those of the C2nu phenomenological model proposed in the late 1970s by Bertrand and Gayda.

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Section: Introductionmentioning

confidence: 86%

Correlation between the Magnetic g Tensors and the Local Cysteine Geometries for a Series of Reduced [2Fe−2S*] Protein Clusters. A Quantum Chemical Density Functional Theory and Structural Analysis

Gambarelli

Mouesca

2004

Inorg. Chem.

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“…Any of six possible permutations of the x, y, z axes accompanied by the corresponding redefinition of the mixing parameter 0 and energy splittings A~p does not change the general form of Eqs. (6). Assuming this uncertainty, we witl further refer (if the other is not indicated) to the original x, y, z coordinate system (as in Fig.…”

Section: Symmetry Of the G-tensormentioning

confidence: 99%

“…The distinguishing feamre between the reduced plant ferredoxin and the Rieske cluster is the average value of the g-tensor components gav, which is about 1.96 for plant ferredoxins and about 1.91 for Rieske proteins [5]. In addition, available experimental data show that the g-tensor components of each class of the [2Fe-2S] cluster are not stable but demonstrate measurable, correlated va¡ [4][5][6][7][8][9][10]. These variations were explained on the basis of a phenomenological theory, which was based on a crystal field analysis of Fe 2 § ion energy levels in the reduced cluster [7,8].…”

Section: Introductionmentioning

confidence: 99%

Variations ofg-tensor principal values in reduced [2Fe−2S] cluster of iron-sulfur proteins

Shubin

Dikanov

2006

Appl. Magn. Reson.

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This article discusses the present status of the theoretical and experimental studies of the electronic structure of the reduced [2Fe-2S] cluster with a special emphasis on the g-tensor variations in the Rieske-type proteins. The necessity of this analysis is dictated by the fact that the changes in the electron paramagnetic resonance line shape of the redueed cluster are broadly exploited as the basis for different mechanistic conclusions in the stmcture-function studies of the bc~/b6f families.

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“…18 Fd [2Fe-2S] cluster is detected by EPR when reduced. 19 Fig. 2B, dark cyan, shows the Fd EPR signal following reduction by sodium dithionite.…”

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confidence: 99%

Aqueous light driven hydrogen production by a Ru–ferredoxin–Co biohybrid

et al. 2015

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Herein we report the creation of a novel solar fuel biohybrid for light-driven H2 production utilizing the native electron transfer protein ferredoxin (Fd) as a scaffold for binding of a ruthenium photosensitizer (PS) and a molecular cobaloxime catalyst (Co). EPR and transient optical experiments provide direct evidence of a long-lived (>1.5 ms) Ru(III)-Fd-Co(I) charge separated state formed via an electron relay through the Fd [2Fe-2S] cluster, initiating the catalytic cycle for 2H(+) + 2e(-) → H2.

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Solvent-induced EPR anisotropy change of the non-heme chromophore of spinach ferredoxin

Cited by 15 publications

References 13 publications

Correlation between the Magnetic g Tensors and the Local Cysteine Geometries for a Series of Reduced [2Fe−2S*] Protein Clusters. A Quantum Chemical Density Functional Theory and Structural Analysis

Correlation between the Magnetic g Tensors and the Local Cysteine Geometries for a Series of Reduced [2Fe−2S*] Protein Clusters. A Quantum Chemical Density Functional Theory and Structural Analysis

Variations ofg-tensor principal values in reduced [2Fe−2S] cluster of iron-sulfur proteins

Aqueous light driven hydrogen production by a Ru–ferredoxin–Co biohybrid

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