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PubMed2006

Manganoan rockbridgeite Fe4.32Mn0.62Zn0.06(PO4)3(OH)5: structure analysis and 57Fe Mössbauer spectroscopy.

The structure of the basic iron phosphate rockbridgeite [iron manganese zinc tris(phosphate) pentahydroxide] was reinvestigated with special emphasis on the cation distribution deduced from new X-ray and 57Fe Mössbauer data. Rockbridgeite is orthorhombic, space group Cmcm, and shows three different Fe sites, one with 2/m symmetry, another with m symmetry and the third in a general position. One phosphate group has the P atom on a site with m symmetry, while the other has the P atom at a site with mm symmetry. Two Fe sites are fully occupied by ferric iron, while Mn3+ and Fe2+ are situated at a third, principally Fe, site. Structural data, bond-valence sums and polyhedral distortion parameters suggest a new interpretation of the rockbridgeite 57Fe Mössbauer spectrum.

Journal Article↗
PubMed1987

Isotopic hybrids of nitrogenase. Mössbauer study of MoFe protein with selective 57Fe enrichment of the P-cluster.

Previous Mössbauer and EPR studies of the MoFe protein (approximately 30 Fe and 2 Mo) of nitrogenase have revealed the presence of two unique clusters, namely, the P-clusters (presumably of the Fe4S4 type) and the molybdenum- and iron-containing cofactors (or M-clusters). Mössbauer components D (approximately 10-12 Fe) and Fe2+ (approximately 4 Fe) represent subsites of the P-clusters while component S (approximately 2 Fe) appeared to belong to a separate, unidentified cluster. In order to refine the analyses of Mössbauer spectra, we have constructed an isotopic hybrid of the Klebsiella pneumoniae protein which contains 57Fe-enriched P-clusters and 56Fe-enriched M-clusters. The highly resolved 57Fe Mössbauer spectra of this hybrid show that component S behaves spectroscopically like the P-cluster sites D and Fe2+ in oxidized and reduced MoFe protein. This suggests that S is a subset of the P-clusters rather than a different cluster type. The present study shows, for the first time, that the Debye-Waller factors of different P-cluster subsites have a different temperature dependence. Thus, the Fe2+/D absorption ratio is 4.0:10.0 at 4.2 K and 4.0:11.6 at 173 K. We propose that the reduced MoFe protein contains two pairs of P-clusters: one pair containing one Fe2+ and three D-sites and the other one Fe2+, two D, and one S-site. We have argued previously that the oxidized P-clusters occur in pairs as well.

Azotobacter↗
PubMed2004

57Fe NMR spectroscopy of ferrocenes bearing pi-acceptor substituents.

Ferrocene derivatives bearing pi-acceptor substituents in 1- or 1,1'-positions such as carbonyl group(s) (1, 2), a sulfinyl group (4) or boryl group(s) (5, 6, 9) and related [3]ferrocenophanes (3, 7, 10, 12, 13) and a [4]ferrocenophane (8) were studied by 57Fe NMR spectroscopy. The deshielding effect of the respective pi-acceptor substituent can be partially or fully compensated by distortion of the ferrocene geometry. Both aspects become apparent by comparing delta57Fe data of the [n]ferrocenophanes with those of related non-cyclic derivatives.

Ferrous Compounds↗
PubMed1977

Critical appraisal of electronic structure of metmyoglobin. 14N and 57Fe hyperfine interactions.

The electronic structure of metmyoglobin is subjected to a critical examination by comparison of results of recent ENDOR measurements of nitrogen hyperfine interaction constants on the porphyrin ring and on the proximal histidine linking the heme to the protein with theoretical values for these properties from calculated electronic wavefunctions for this molecule. The observed interesting trends of the 14N hyperfine data as well as available 57Fe data are both successfully explained showing that theory has provided a satisfactory description of the electronic distribution in this important molecule.

Ferric Compounds↗
PubMed1993

Binding of the ferric uptake regulation repressor protein (Fur) to Mn(II), Fe(II), Co(II), and Cu(II) ions as co-repressors: electronic absorption, equilibrium, and 57Fe Mössbauer studies.

The binding of the repressor protein (Fur) to Fe(II) as co-repressor was studied. Other transition metal ions such as Mn(II), Co(II), and Cu(II) were also studied as models. From the equilibrium studies Kd values of 55, 85, 36, and 10 microM were obtained for the Fur complex with Fe(II), Mn(II), Co(II), and Cu(II), respectively. The ratio of metal to Fur monomer was 1:1 in both the Fe(II) and Mn(II) complexes. Fur mutants were also studied. Electronic absorption spectra of the Co(II) Fur complex gave evidence of a distorted tetrahedral Co(II) site bound to sulfur. Frozen solution 57Fe Mössbauer spectra of the Fe(II) Fur indicated the presence of Fe(II) in a high spin distorted octahedral environment. The role of the metal ion as co-repressor in the binding of Fur to DNA is discussed in view of the above results.

Bacterial Proteins↗
PubMed2000

Vibrational and 57Fe-Mössbauer spectra of FeTbGe2O7.

The infrared, Raman and 57Fe-Mössbauer spectra of FeTbGe2O7 were recorded and analyzed on the basis of its crystallographic data. For comparative purposes, similar measurements were also performed with FeYGe2O7 and with other isostructural compounds containing different lanthanide cations.

Ferrous Compounds↗
PubMedDate not supplied

Conformation-controlled trans-effect of the proximal histidine in haemoglobins. An electron spin resonance study of monomeric nitrosyl-57Fe-haemoglobins.

A monomeric allosteric haemoglobin from Chironomus thummi thummi was reconstituted with 57Fe-haem. This reconstituted haemoglobin was found to be identical to the non-reconstituted material with regard to the O2-binding properties and the visible spectra. The 270 MHz proton magnetic resonance of the bis (cyano)-57Fe-haemin shows that the reconstituted haem is identical with the non-reconstituted haem. Furthermore it has been proved by proton magnetic resonance that in Chironomus haemoglobins the prosthetic group is proto-haem IX. The ESR spectrum of the native nitrosyl haemoglobin demonstrates rhombic symmetry of the haem iron (gxx=2.086, gyy=1.981, gzz=2.005) and hyperfine structures at gyy (aNepsilon=1.35 mT) and at gzz (a15NO=3.05 MT, a14NO=2.19 mT, aNepsilon=0.715 mT, a57Fe=0.38 mT). The spectrum is independent of pH and can be classified as a type II spectrum following the classification of ref. 2. NO-binding obviously stabilizes the tertiary structure of this haemoglobin in a "tense" conformation with a relatively strong sigma bond of the 5th ligand (Nepsilon of imidazole) and a relatively weak sigma bond of the 6th ligand (NO). Reaction of this haemoglobin with anionic, cationic and non-ionic detergents, respectively, leads to a transformation of the NO-ligated form into a "relaxed" conformation with a stretched or broken sigma bond of the 5th ligand (Nepsilon of imidazole) and a strong sigma bond of the 6th ligand (NO). The ESR spectrum of this modified NO-haemoglobin shows again a rhombic symmetry of the haem iron (gxx=2.10, gyy=2.06, gzz=2.010), but dramatically changes in the g tensors (low field shift), hyperfine structures and hyperfine splitting constants (a15NO=2.32 MT, a14NO=1.66 mT, a57Fe=0.48 mT). The hyperfine splitting is isotropic. Transition from the "tense" conformation to the "relaxed" conformation corresponds with an increase of the spin density at the iron atom by 26% and a decrease of the spin density at the NO ligand by 25%. The spin density at the Nepsilon of imidazole strongly decreases in the "relaxed" conformation, so that a hyperfine splitting of this ligand is not any more resolved. These results demonstrate the trans-effect of the proximal imidazole which in haemoglobins controls of the binding properties of the external ligand in trans-position.

Animals↗
PubMed1998

A new method to measure iron absorption from the enrichment of 57Fe and 58Fe in young erythroid cells.

Iron absorption can be measured by the incorporation of stable iron isotopes into erythrocytes, 14 days after isotope administration. The disadvantage of this method is the high dose of isotopes needed to obtain a sufficient enrichment. Therefore, in this study cell fractions rich in young erythroid cells were prepared by using a density separation method. From 10 women blood was taken 4, 5, and 7 days after oral and intravenous administration of 57Fe and 58Fe. In these cell fractions and in whole blood taken 14 days after isotope administration, isotope enrichment was measured and absorption calculated. Absorption calculated from the isotope enrichment in the reticulocyte-rich cell fractions (12.2 +/- SEM 3.7%) was not significantly different from absorption based on whole-blood values (13.0 +/- 3.3%). Because a threefold higher isotope enrichment was found in the cell fractions, the required dose of stable isotopes can be reduced to one-third of the dose used in the traditional method without loss of sensitivity.

Absorption↗
PubMed2006

DFT calculations of 57Fe Mössbauer isomer shifts and quadrupole splittings for iron complexes in polar dielectric media: applications to methane monooxygenase and ribonucleotide reductase.

To predict the isomer shifts of Fe complexes in different oxidation and spin states more accurately, we have performed linear regression between the measured isomer shifts (delta(exp)) and DFT (PW91 potential with all-electron triple-zeta plus polarization basis sets) calculated electron densities at Fe nuclei [rho(0)] for the Fe(2+,2.5+) and Fe(2.5+,3+,3.5+,4+) complexes separately. The geometries and electronic structures of all complexes in the training sets are optimized within the conductor like screening (COSMO) solvation model. Based on the linear correlation equation delta(exp) = alpha[rho(0) - 11884.0] + C, the best fitting for 17 Fe(2+,2.5+) complexes (totally 31 Fe sites) yields alpha = -0.405 +/- 0.042 and C = 0.735 +/- 0.047 mm s(-1). The correlation coefficient is r = -0.876 with a standard deviation of SD = 0.075 mm s(-1). In contrast, the linear fitting for 19 Fe(2.5+,3+,3.5+,4+) complexes (totally 30 Fe sites) yields alpha = -0.393 +/- 0.030 and C = 0.435 +/- 0.014 mm s(-1), with the correlation coefficient r = -0.929 and a standard deviation SD = 0.077 mm s(-1). We provide a physical rationale for separating the Fe(2+,2.5+) fit from the Fe(2.5+,3+,3.5+,4+) fit, which also is clearly justified on a statistical empirical basis. Quadrupole splittings have also been calculated for these systems. The correlation between the calculated (DeltaE(Q(cal))) and experimental (DeltaE(Q(exp))) quadrupole splittings based on |DeltaE(Q(exp))| = A |DeltaE(Q(cal))| + B yields slope A, which is almost the ideal value 1.0 (A = 1.002 +/- 0.030) and intercept B almost zero (B = 0.033 +/- 0.068 mm s(-1)). Further calculations on the reduced diferrous and oxidized diferric active sites of class-I ribonucleotide reductase (RNR) and the hydroxylase component of methane monooxygenase (MMOH), and on a mixed-valent [(tpb)Fe3+(mu-O)(mu-CH3CO2)Fe4+(Me3[9]aneN3)]2+ (S = 3/2) complex and its corresponding diferric state have been performed. Calculated results are in very good agreement with the experimental data.

Electrochemistry↗
PubMed2002

The dynamics of 57Fe nuclei in Fe(II)-DNA and [Fe(II)(1-methyl-2-mercaptoimidazole)2]-DNA condensates.

Alcoholic solutions of FeCl(2) and Fe(II)(Hmmi)(2)Cl(2) (Hmmi=1-methyl-2-mercaptoimidazole) induce calf thymus DNA condensation from aqueous solutions buffered at pH 7.4. A 1:1 Fe(II)-(DNA monomer) stoichiometry is assumed. The (57)Fe Mössbauer hyperfine parameters suggest an octahedral coordination environment, severely distorted, in both Fe(II)-(DNA monomer) and [Fe(II)(Hmmi)(2)]-(DNA monomer) condensates. The dynamic properties of iron nuclei in freeze-dried samples were investigated by means of variable temperature (57)Fe Mössbauer spectroscopy. Mean square displacements, (T), were calculated, such as the effective vibrating mass and the Mössbauer lattice temperature of the solids. increases linearly with the temperature in the whole temperature range explored; the absolute values are typical for lattice or solid-state vibrations. Very similar values for the effective vibrating masses were extracted, suggesting comparable covalency of the bonding interaction between the metal atom and its ligands, while the Mössbauer lattice temperatures show a softening of the lattice for [Fe(II)(Hmmi)(2)]-(DNA monomer) with respect to Fe(II)-(DNA monomer) condensate.

Animals↗
PubMed1992

14,15N, 13C, 57Fe, and 1,2H Q-band ENDOR study of Fe-S proteins with clusters that have endogenous sulfur ligands.

The benefits of performing ENDOR experiments at higher microwave frequency are demonstrated in a Q-band (35 GHz) ENDOR investigation of a number of proteins with [nFe-mS] clusters, n = 2, 3, 4. Each protein displays several resonances in the frequency range of 0-20 MHz. In all instances, features are seen near v approximately 13 and 8 MHz that can be assigned, respectively, to "distant ENDOR" from 13C in natural-abundance (1.1%) and from 14N (the delta m1 = +/- 2 transitions); the nuclei involved in this phenomenon are remote from and have negligible hyperfine couplings to the cluster. In addition, a number of proteins show local 13C ENDOR signals with resolved hyperfine interactions; these are assigned to the beta carbons of cysteines bound to the cluster [A(13C) approximately 1.0 MHz]. Five proteins show resolved, local delta m1 = +/- 2 ENDOR signals from 14N with an isotropic hyperfine coupling, 0.4 less than or equal to A(14N) less than or equal to 1.0, similar to those seen in ESEEM studies; these most likely are associated with N-H...S hydrogen bonds to the cluster. Anabaena ferredoxin further shows a signal corresponding to A(14N) approximately 4 MHz. Quadrupole coupling constants are derived for both local and distant 14N signals. The interpretation of the data is supported by studies on 15N- and 13C-enriched ferredoxin (Fd) from Anabaena 7120, where the 15N signals can be clearly correlated with the corresponding 14N signals and where the 13C signals are strongly enhanced. Thus, the observation of 14N delta m1 = +/- 2 signals at Q-band provides a new technique for examining weak interactions with a cluster.(ABSTRACT TRUNCATED AT 250 WORDS)

Aconitate Hydratase↗
PubMed2005

Crystal structure, magnetic properties, and 57Fe Mössbauer spectroscopy of the two-dimensional coordination polymers [M(1,2-bis(1,2,4-triazol-4-yl)ethane)2(NCS)2] (MII = Fe, Co).

New coordination polymers of the formula [M(btre)(2)(NCS)(2)] (btre = 1,2-bis(1,2,4-triazol-4-yl)ethane; M(II) = Fe, Co) have been synthesized, and their crystal structures have been determined at 293 K by X-ray analysis. The Fe(II) compound (C(7)H(8)FeN(7)S(2)) crystallizes in the monoclinic space group P2(1)/n, a = 12.439(5) A, b = 8.941(2) A, c = 9.321(3) A, beta = 90.88(2) degrees , V = 1036.6(6) A(3), Z = 2, 3791 reflections [I > 3sigma(I)], R(F) = 0.036, wR2 = 0.123. The Co(II) compound is isostructural to the Fe(II) compound. The crystal structure consists of a 2D sheet in which the metal ions are linked by bis monodentate (N1, N1') 1,2,4-triazole ligands. The structure is stabilized by pi-bond interactions between two adjacent sheets and by S...S interactions. Temperature-dependent SQUID, (57)Fe Mössbauer, and X-ray diffraction measurements indicate that [Fe(btre)(2)(NCS)(2)] retains a HS ground state upon cooling from 293 K down to 8 K. The surprising absence of spin-crossover behavior for this Fe(II)-1,2,4-triazole polymeric coordination compound that has been confirmed by pressure experiments up to approximately 12 kbar and by light irradiation experiments at 10 K is discussed on the basis of its structural features. Insight into the origin of the cooperative effects of the spin transition in [Fe(btr)(2)(NCS)(2)].H(2)O (btr = 4,4'-bis-1,2,4-triazole) is also given thanks to a re-evaluation of its distortion parameters in the high- and low-spin states.

Journal Article↗
PubMed2005

57Fe-labeled octamethylferrocenium tetrafluoroborate. X-ray crystal structures of conformational isomers, hyperfine interactions, and spin-lattice relaxation by Moessbauer spectroscopy.

X-ray structure determinations of two different single crystals of octamethylferrocenium tetrafluoroborate (OMFc(+)BF(4)(-)) revealed conformational polymorphism with ligand twist angles of 180 degrees and 108 degrees , respectively. Their concomitant occurrence could be explained by the small lattice energy difference of 3.2 kJ mol(-1). Temperature-dependent Moessbauer spectroscopy of (57)Fe-labeled OMFc(+)BF(4)(-) over the range 90 < T < 370 K did not show the anomalous sudden increase in the motion of the metal atom as observed in neutral OMFc. Broadened absorption curves characteristic of relaxation spectra were obtained with an isomer shift of 0.466(6) mm s(-1) at 90 K. The temperature dependence of the isomer shift corresponded to an effective vibrating mass of 79 +/- 10 Da and, in conjunction with the temperature dependence of the recoil-free fraction, to a Moessbauer lattice temperature of 89 K. The spin relaxation rate could be better described by an Orbach rather than a Raman process. At 400 K, a reversible solid-solid transition to a plastic crystalline mesophase was noted.

Journal Article↗
PubMed2006

57Fe Mössbauer spectroscopy on multiwalled carbon nanotubes with metal filling.

Mössbauer measurements at different temperatures are reported for MWCNTs with metallic encapsulations ("nanowires"). The spectra can reasonably be refined with two subpatterns: one providing clear evidence of an iron carbide Fe(3)C (cementite) phase as the main nanowire component and the other yielding a relaxation doublet most probably belonging to the same phase. Whereas the former one displays a well resolved magnetic hyperfine spectrum with Brillouin type temperature dependence, the latter one gains importance with rising temperature or onset of an inhomogeneous external magnetic field. The comparably large incoherent scattering is attributed to the graphene layers of the tube walls. The experimental results are discussed on the background of an interpretation model trying to explain unusual magnetometric results published elsewhere.

Journal Article↗