Sublattice magnetism in sigma-phase Fe(100-x)Vx (x=34.4, 39.9, and 47.9) studied via zero-field (51)V NMR

The successful measurements of a sublattice magnetism with (51)V NMR techniques in the sigma-phase Fe(100-x)V(x) alloys with x=34.4, 39.9, and 47.9 are reported. Vanadium atoms, which were revealed to be present on all five crystallographic sites, are found to be under the action of the hyperfine magnetic fields produced by the neighboring Fe atoms, which allow the observation of (51)V NMR signals. Their nuclear magnetic properties are characteristic of a given site, which strongly depend on the composition. Site A exhibits the strongest magnetism while site D is the weakest. The estimated average magnetic moment per V atom decreases from 0.36 mu(B) for x=34.4 to 0.20 mu(B) for x=47.9. The magnetism revealed at V atoms is linearly correlated with the magnetic moment of Fe atoms, which implies that the former is induced by the latter.

Removal of a cysteine ligand from rubredoxin: assembly of Fe2S2 and Fe(S-Cys)(3)(OH) centres

The electron transfer protein rubredoxin from Clostridium pasteurianum contains an Fe(S-Cys)(4) active site. Mutant proteins C9G, C9A, C42G and C42A, in which cysteine ligands are replaced by non-ligating Gly or Ala residues, have been expressed in Escherichia coli. The C42A protein expresses with a (Fe2S2)-S-III cluster in place. In contrast, the other proteins are isolated in colourless forms, although a (Fe2S2)-S-III cluster may be assembled in the C42G protein via incubation with Fe-III and sulfide. The four mutant proteins were isolated as stable mononuclear Hg-II forms which were converted to unstable mononuclear Fe-III preparations that contain both holo and apo protein. The Fe-III systems were characterized by metal analysis and mass spectrometry and by electronic, electron paramagnetic resonance, X-ray absorption and resonance Raman spectroscopies. The dominant Fe-III form in the C9A preparation is a Fe(S-Cys)(3)(OH) centre, similar to that observed previously in the C6S mutant protein. Related centres are present in the proteins NifU and IscU responsible for assembly and repair of iron-sulfur clusters in both prokaryotic and eukaryotic cells. In addition to Fe(S-Cys)(3)(OH) centres, the C9G, C42G and C42A preparations contain a second four-coordinate Fe-III form in which a ligand appears to be supplied by the protein chain. Electronic supplementary material to this paper can be obtained by using the Springer Link server located at http://dx.doi.org/10.1007/s00775-0020355-1.

A purple acid phosphatase from sweet potato contains an antiferromagnetically coupled binuclear Fe-Mn center

A purple acid phosphatase from sweet potato is the first reported example of a protein containing an enzymatically active binuclear Fe-Mn center. Multifield saturation magnetization data over a temperature range of 2 to 200 K indicates that this center is strongly antiferromagnetically coupled. Metal ion analysis shows an excess of iron over manganese. Low temperature EPR spectra reveal only resonances characteristic of high spin Fe(III) centers (Fe(III)-apo and Fe(III)-Zn(II)) and adventitious Cu(II) centers. There were no resonances from either Mn(II) or binuclear Fe-Mn centers. Together with a comparison of spectral properties and sequence homologies between known purple acid phosphatases, the enzymatic and spectroscopic data strongly indicate the presence of catalytic Fe(III)-Mn(II) centers in the active site of the sweet potato enzyme. Because of the strong antiferromagnetism it is likely that the metal ions in the sweet potato enzyme are linked via a mu -oxo bridge, in contrast to other known purple acid phosphatases in which a mu -hydroxo bridge is present. Differences in metal ion composition and bridging may affect substrate specificities leading to the biological function of different purple acid phosphatases.

Novel optical PVC probes for on-site detection/determination of fluoroquinolones in a solid/liquid interface: Application to the determination of Norfloxacin in aquaculture water

A novel optical disposable probe for screening fluoroquinolones in fish farming waters is presented, having Norfloxacin (NFX) as target compound. The colorimetric reaction takes place in the solid/liquid interface consisting of a plasticized PVC layer carrying the colorimetric reagent and the sample solution. NFX solutions dropped on top of this solid-sensory surface provided a colour change from light yellow to dark orange. Several metals were tested as colorimetric reagents and Fe(III) was selected. The main parameters affecting the obtained colour were assessed and optimised in both liquid and solid phases. The corresponding studies were conducted by visible spectrophotometry and digital image acquisition. The three coordinates of the HSL model system of the collected image (Hue, Saturation and Lightness) were obtained by simple image management (enabled in any computer). The analytical response of the optimised solid-state optical probe against concentration was tested for several mathematical transformations of the colour coordinates. Linear behaviour was observed for logarithm NFX concentration against Hue+Lightness. Under this condition, the sensor exhibited a limit of detection below 50 μM (corresponding to about 16 mg/mL). Visual inspection also enabled semi-quantitative information. The selectivity was ensured against drugs from other chemical groups than fluoroquinolones. Finally, similar procedure was used to prepare an array of sensors for NFX, consisting on different metal species. Cu(II), Mn(II) and aluminon were selected for this purpose. The sensor array was used to detect NFX in aquaculture water, without any prior sample manipulation.

A copper protein and a cytochrome bind at the same site on bacterial cytochrome c peroxidase

Biochemistry, 2004, 43 (46), pp 14566–14576 DOI: 10.1021/bi0485833

Formation of a stable cyano-bridged dinuclear iron cluster following oxidation of the superoxide reductases from Treponema pallidum and Desulfovibrio vulgaris with K(3)Fe(CN)(6)

Inorg. Chem., 2003, 42 (4), pp 938–940 DOI: 10.1021/ic0262886

Proteomic and Metabolomic Analyses of Mitochondrial Complex I-deficient Mouse Model Generated by Spontaneous B2 Short Interspersed Nuclear Element (SINE) Insertion into NADH Dehydrogenase (Ubiquinone) Fe-S Protein 4 (Ndufs4) Gene.

Eukaryotic cells generate energy in the form of ATP, through a network of mitochondrial complexes and electron carriers known as the oxidative phosphorylation system. In mammals, mitochondrial complex I (CI) is the largest component of this system, comprising 45 different subunits encoded by mitochondrial and nuclear DNA. Humans diagnosed with mutations in the gene NDUFS4, encoding a nuclear DNA-encoded subunit of CI (NADH dehydrogenase ubiquinone Fe-S protein 4), typically suffer from Leigh syndrome, a neurodegenerative disease with onset in infancy or early childhood. Mitochondria from NDUFS4 patients usually lack detectable NDUFS4 protein and show a CI stability/assembly defect. Here, we describe a recessive mouse phenotype caused by the insertion of a transposable element into Ndufs4, identified by a novel combined linkage and expression analysis. Designated Ndufs4(fky), the mutation leads to aberrant transcript splicing and absence of NDUFS4 protein in all tissues tested of homozygous mice. Physical and behavioral symptoms displayed by Ndufs4(fky/fky) mice include temporary fur loss, growth retardation, unsteady gait, and abnormal body posture when suspended by the tail. Analysis of CI in Ndufs4(fky/fky) mice using blue native PAGE revealed the presence of a faster migrating crippled complex. This crippled CI was shown to lack subunits of the "N assembly module", which contains the NADH binding site, but contained two assembly factors not present in intact CI. Metabolomic analysis of the blood by tandem mass spectrometry showed increased hydroxyacylcarnitine species, implying that the CI defect leads to an imbalanced NADH/NAD(+) ratio that inhibits mitochondrial fatty acid β-oxidation.

Geological setting of the Guelb Moghrein Fe oxide-Cu-Au-Co mineralization, Akjoujt area, Mauritania

The Guelb Moghrein Fe oxide-Cu-Au-Co deposit is located at the western boundary of the West African craton in NW Mauritania. The wall rocks to the mineralization represent a meta-volcanosedimentary succession typical of Archaean greenstone belts. Two types of meta-volcanic rocks are distinguished: (1) volcanoclastic rocks of rhyodacite-dacite composition (Sainte Barbe volcanic unit), which form the stratigraphic base; (2) tholeiitic andesites-basalts (Akjoujt meta-basalt unit). The trace element signature of both types is characteristic of a volcanic arc setting. A small meta-pelitic division belongs to the Sainte Barbe volcanic unit. A meta-carbonate body, which contains the mineralization, forms a tectonic lens in the Akjoujt meta-basalt unit. It can be defined by the high X(mg) (=36) of Fe-Mg carbonate, the REE pattern and the delta(13)C values of -18 to -17 parts per thousand as a marine precipitate similar to Archaean banded iron formation (BIF). Additionally, small slices of Fe-Mg clinoamphibole-chlorite schist in the meta-carbonate show characteristics of marine shale. This assemblage, therefore, does not represent an alteration product, but represents an iron formation unit deposited on a continental shelf, which probably belongs to the Lembeitih Formation. The hydrothermal mineralization at 2492 Ma was contemporaneous with regional D(2) thrusting of the Sainte Barbe volcanic unit and imbrications of the meta-carbonate in the upper greenschist facies. This resulted in the formation of an ore breccia in the meta-carbonate, which is enriched in Fe, Ni, Co, Cu, Bi, Mo, As and Au. Massive sulphide ore breccia contains up to 20 wt% Cu. The ore fluid was aqueous-carbonic in nature and either changed its composition from a Mg-rich oxidizing to an Fe-rich reducing fluid or the two fluid types mixed at the trap site. All lithologies at Guelb Moghrein were deformed by D(3) thrusting to the east in the lower greenschist facies. The mobility of REE in the retrogressed rocks explains the formation of a second generation of hydrothermal monazite, which was dated at c. 1742 Ma. Archaean rocks of the West African craton extend to the west to Guelb Moghrein. The active continental margin was deformed and mineralized in the Late Archaean-Early Proterozoic and again reactivated in the Mid-Proterozoic and Westphalian, showing that the western boundary of the craton was reactivated several times.

Zeolite Encapsulated Complexes Of Fe,Co,Ni,Cu And Pd:Synthesis , Characterization And Catalysis-2003

This thesis deals with the synthesis, characterization and catalysis activity studies of some zeolite encapsulated complexes. Encapsulation inside the zeolite cages makes the catalysts more stable. Further, the framework prevents the complexes from dimerising. Catalysis by metal complexes encapsulated in the cavities of zeolites and other molecular sieves has many features of homogeneous, heterogenous and enzymatic catalysis. Serious attempts has been made to gain product selectivity in catalysis .The catalytic activity shown by the encapsulated complexes can be correlated to the structure of the active site inside the zeolite pore. It deals with the studies on the partial oxidation of benzyl alcohol to benzaldehyde. The oxidatio was carried out using hydrogen peroxide as oxidant in presence of PdYDMG and CuYSPP as catalysts. The product (benzaldehyde) was detected using TLC and confirmed using GC.The catalytic activity of the complexes was tested for oxidation under various conditions. The operating conditions like the amount of the catalyst, reaction time, oxidant to substrate ratio, reaction temprature, and solvents have been optimized. No further oxidation products were obtained on continuing the reaction for four hours beyond the optimum time. Maximum conversion was obtained at room temperature and the percentage conversion decreased with increase in temperature. Activity was found to be dependent on the solvent used. With increasing awareness about the dangers of environmental degradation, research in chemistry is getting increasing geared to the development of “green chemistry,” by designing environmentally friendly products and processes that bring down the generation and use of hazardous substances.

Surface acidity and catalytic activity of mixed Fe-Al and Cr-Al pillared montmorillonites

The incorporation of transition metal oxide pillars such as those of iron and chromium along with Al2O3, pillars within the interlayers of a montmorillonite clay is investigated. The surface acidity of these catalysts has been evaluated for the first time employing the equilibrium adsorption of an electron donor, perylene, and the results are compared with those obtained by temperature programmed desorption of ammonia. The principle is based on the ability of a catalyst surface site to accept a single electron from an electron donor like perylene to form charge transfer complexes and the amount of adsorbed species is measured quantitatively by UV-vis spectroscopy. Fina1ly, an attempt has been made to correlate the acidity determined by the two independcnt methods and the catalytic activity of present systems in the benzoylation of toluene with benzoyl chloride. Incorporation of Fe and Cr has changed the properties of AI pitlared montmorillonite. Fe pillared systems have been found to be vcry good catalysts for benzoylation reaction

Electronic Structure and Spectro-Structural Correlations of Fe(III)Zn(II) Biomimetics for Purple Acid Phosphatases: Relevance to DNA Cleavage and Cytotoxic Activity

Purple acid phosphatases (PAPs) are a group of metallohydrolases that contain a dinuclear Fe(II)M(II) center (M(II) = Fe, Mn, Zn) in the active site and are able to catalyze the hydrolysis of a variety of phosphoric acid esters. The dinuclear complex [(H(2)O)Fe(III)(mu-OH)Zn(II)(L-H)](CIO(4))(2) (2) with the ligand 2-[N-bis(2-pyridylmethyl)aminomethyl]-4-methyl-6-[N-(2-pyridylmethyl)(2-hydroxybenzyl) aminomethyl]phenol (H(2)L-H) has recently been prepared and is found to closely mimic the coordination environment of the Fe(III)Zn(II) active site found in red kidney bean PAP (Neves et al. J. Am. Chem. Soc. 2007, 129, 7486). The biomimetic shows significant catalytic activity in hydrolytic reactions. By using a variety of structural, spectroscopic, and computational techniques the electronic structure of the Fe(III) center of this biomimetic complex was determined. In the solid state the electronic ground state reflects the rhombically distorted Fe(III)N(2)O(4) octahedron with a dominant tetragonal compression align ad along the mu-OH-Fe-O(phenolate) direction. To probe the role of the Fe-O(phenolate) bond, the phenolate moiety was modified to contain electron-donating or -withdrawing groups (-CH(3), -H, -Br, -NO(2)) in the 5-position. Tie effects of the substituents on the electronic properties of the biomimetic complexes were studied with a range of experimental and computational techniques. This study establishes benchmarks against accurate crystallographic struck ral information using spectroscopic techniques that are not restricted to single crystals. Kinetic studies on the hydrolysis reaction revealed that the phosphodiesterase activity increases in the order -NO(2)<- Br <- H <- CH(3) when 2,4-bis(dinitrophenyl)phosphate (2,4-bdnpp) was used as substrate, and a linear free energy relationship is found when log(k(cat)/k(0)) is plotted against the Hammett parameter a. However, nuclease activity measurements in the cleavage of double stranded DNA showed that the complexes containing the electron-withdrawing -NO(2) and electron-donating CH3 groups are the most active while the cytotoxic activity of the biomimetics on leukemia and lung tumoral cells is highest for complexes with electron-donating groups.

Correlation of reactivity with structural factors in a series of Fe(II) substituted cobalt ferrites

A series of powdered cobalt ferrites, CoxFe3-xO4 with 0.66 <= x< 1.00 containing different amounts of Fe-II, were synthesized by a mild procedure, and their Fe and Co site occupancies and structural characteristics were explored using X-ray anomalous scattering and the Rietveld refinement method. The dissolution kinetics, measured in 0.1 M oxalic acid aqueous solution at 70 degrees C, indicate in all cases the operation of a contracting volume rate law. The specific rates increased with the Fell content following approximately a second-order polynomial expression. This result suggests that the transfer of Fe-III controls the dissolution rate, and that the leaching of a first layer of ions Co-II and Fe-II leaves exposed a surface enriched in slower dissolving octahedral Fe-III ions. Within this model, inner vicinal lattice Fe-II accelerates the rate of Fe-III transfer via internal electron hopping. A chain mechanism, involving successive electron transfers, fits the data very well. (C) 2006 Elsevier B.V. All rights reserved.

Theoretical study of MgO(001) surfaces: Pure, doped with Fe, Ca, and Al, and with and without adsorbed water

Ab initio calculations of large cluster models have been performed in order to study water adsorption at the five-fold coordinated adsorption site on pure Mg(001) and MgO(001) surfaces doped with Fe, Ca, and Al. The geometric parameters of the adsorbed water molecule have been optimized preparatory to analysis of binding energies, charge transfer, preferential sites of interaction, and bonding distances. We have used Mulliken population analysis methods in order to analyze charge distributions and the direction of charge transfer. We have also investigated energy gaps, HOMO energies, and SCF orbital energies as well as the acid-base properties of our cluster model. Numerical results are compared, where possible, with experiment and interpreted in the framework of various analytical models. (C) 2001 John Wiley & Sons, Inc.

Characterization of humic-rich hydrocolloids and their metal species by means of competing ligand and metal exchange - an on-site approach

An improved on-site characterization of humic-rich hydrocolloids and their metal species in aquatic environments was the goal of the present approach. Both ligand exchange with extreme chelators ( diethylenetetraaminepentaacetic acid ( DTPA), ethylendiaminetetraacetic acid ( EDTA)) and metal exchange with strongly competitive cations (Cu(II)) were used on-site to characterize the conditional stability and availability of colloidal metal species in a humic-rich German bogwater lake ( Venner Moor, Munsterland). A mobile time-controlled tangential-flow ultrafiltration technique (cut-off: 1 kDa) was applied to differentiate operationally between colloidal metal species and free metal ions, respectively. DOC ( dissolved organic carbon) and metal determinations were carried out off-site using a home-built carbon analyzer and conventional ICP-OES ( inductively-coupled plasma-optical emission spectrometry), respectively. From the metal exchange equilibria obtained on-site the kinetic and thermodynamic stability of the original metal species ( Fe, Mn, Zn) could be characterized. Conditional exchange constants K ex obtained from aquatic metal species and competitive Cu(II) ions follow the order Mn > Zn >> Fe. Obviously, Mn and Zn bound to humic-rich hydrocolloids are very strongly competed by Cu( II) ions, in contrast to Fe which is scarcely exchangeable. The exchange of aquatic metal species (e.g. Fe) by DTPA/EDTA exhibited relatively slow kinetics but rather high metal availabilities, in contrast to their Cu(II) exchange.

Magnetic behavior of interstitial Fe impurities in divalent Ca, Sr, and Yb hosts

We have used a first-principles real-space approach to investigate the electronic structure and the magnetic behavior of interstitial Fe impurities in divalent Ca, Sr, and Yb hosts. The dependence of the local moment as a function of lattice relaxation around the impurity is obtained and contrasted with that of interstitial Fe in trivalent and tetravalent Zr, Y, Ti, and Sc hosts. The trends obtained for local moment formation at the impurity site an in agreement with experimental time-differential perturbed gamma-ray angular distribution technique observations.