Anthranilate Hydroxylase from Aspergillus niger: Evidence for the Participation of Iron in the Double Hydroxylation Reaction

Evidence was obtained for the participation of iron in the double hydroxylation reaction catalyzed by anthranilate hydroxylase from Aspergillus niger (UBC 814). Omission of iron from the growth medium gave inactive preparations of anthranilate hydroxylase which could be reactivated by incubating the enzyme preparations with ferric citrate. The enzyme was susceptible to inhibition by metal chelating agents. The Ki for o-phenanthroline, which inhibited the enzyme activity non-competitively with respect to anthranilate, was calculated to be 0.9 mM. The inhibition by o-phenanthroline was counteracted by ferric complexes such as ferric-ethylenediaminetetraacetic acid and ferric citrate. Anthranilate afforded protection against inhibition by o-phenanthroline.

Site of action of iron in the induction of δ-aminolevulinate dehydratase in Neurospora crassa

δ-Aminolevulinate (ALA) dehydratase, the second and rate limiting enzyme of the heme biosynthetic pathway in the mold Neurospora crassa is induced maximally in 30 min by the addition of iron to iron-deficient cultures. The induction of the enzyme is blocked by cycloheximide, protoporphyrin, 8-azaguanine and cordycepin. Iron also brings about an increase in poly(A)-containing RNA synthesis under conditions of induction. The iron dependent increase in poly(A)-containing RNA synthesis is blocked by protoporphyrin. It is suggested that at the time intervals examined, bulk of the messenger RNA synthesized in response to iron addition represents the messenger for ALA dehydratase.

Ternary Iron(III) complex showing photocleavage of DNA in the photodynamic therapy window

A new ternary iron(III) complex [FeL(dpq)] containing dipyridoquinoxaline (dpq) and 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)aminoacetic acid (H3L) is prepared and structurally characterized by X-ray crystallography. The high-spin complex with a FeN3O3 core shows a quasi-reversible iron(III)/iron(II) redox couple at -0.62 V (vs SCE) in DMF/0.1 M TBAP and a broad visible band at 470 nm in DMF/Tris buffer. Laser photoexcitation of this phenolate (L)-to-iron(III) charge-transfer band at visible wavelengths including red light of >= 630 nm leads to cleavage of supercoiled pUC19 DNA to its nicked circular form via a photoredox pathway forming hydroxyl radicals.

Zeta Potential Studies On Some Iron-Ore Minerals In The Presence Of Starches

Authors perform zeta potential studies on hematite, corundum, and quartz samples using starches to understand the adsorption behavior of polymeric starch flocculants at the oxide mineral-solution interface and to correlate this information with their flocculation characteristics and investigate effects of pH and CaCl#72 on zeta potential of Fe ore minerals.

Purification of 3,5-Dichlorocatechol 1,2-Dioxygenase, a Nonheme Iron Dioxygenase and a Key Enzyme in the Biodegradation of a Herbicide, 2,4-Dichlorophenoxyacetic acid (2,4-D), from Pseudomonas cepacia CSV90

An enzyme which cleaves the benzene ring of 3,5-dichiorocatechol has been purified to homogeneity from Pseudomonas cepacia CSV90, grown with 2,4-dichlorophenoxyacetic acid (2,4-D) as the sole carbon source. The enzyme was a nonheme ferric dioxygenase and catalyzed the intradiol cleavage of all the examined catechol derivatives, 3,5-dichlorocatechol having the highest specificity constant of 7.3 μM−1 s−1 in an air-saturated buffer. No extradiol-cleaving activity was observed. Thus, the enzyme was designated as 3,5-dichlorocatechol 1,2-dioxygenase. The molecular weight of the native enzyme was ascertained to be 56,000 by light scattering method, while the Mr value of the enzyme denatured with 6 M guanidine-HCl or sodium dodecyl sulfate was 29,000 or 31,600, respectively, suggesting that the enzyme was a homodimer. The iron content was estimated to be 0.89 mol per mole of enzyme. The enzyme was deep red and exhibited a broad absorption spectrum with a maximum at around 425 nm, which was bleached by sodium dithionite, and shifted to 515 nm upon anaerobic 3,5-dichlorocatechol binding. The catalytic constant and the Km values for 3,5-dichlorocatechol and oxygen were 34.7 s−1 and 4.4 and 652 μM, respectively, at pH 8 and 25°C. Some heavy metal ions, chelating agents and sulfhydryl reagents inhibited the activity. The NH2-terminal sequence was determined up to 44 amino acid residues and compared with those of the other catechol dioxygenases previously reported.

Investigations Of Iron Adducts Of C-60 - Novel Fec60 In The Solid-State With Fe Inside The C-60 Cage

By carrying out contact-arc vaporization of graphite in a partial atmosphere of Fe(CO)5, an iron-adduct with C60 has been obtained. The adduct has been characterized by various techniques including mass spectrometry, Fe-57 Mossbauer spectroscopy and Fe K-EXAFS. Properties of this adduct are compared with those of an adduct prepared by solution method where Fe is clearly outside the cage. Results suggest that FeC60 obtained from the gas phase reaction has the Fe atom in the cage.

Threshold-like features in the magnetic response of iron-filled multi-walled carbon nanotube and polymer composite

The magnetic properties of iron-filled multi-walled carbon nanotubes dispersed in polystyrene (Fe-MWNT/PS) have been investigated as a function of Fe-MWNT concentration (0.1-15 wt%) from 300 to 10 K. Electron microscopy studies indicate that Fe nanorods (aspect ratio similar to 5) remain trapped at various lengths of MWNT and are thus, prevented from oxidation as well as aggregation. The magnetization versus applied field (M-H loop) data of 0.1 wt% of Fe-MWNTs in PS show an anomalous narrowing at low temperatures which is due to the significant contribution from shape anisotropy of Fe nanorods. The remanence shows a threshold feature at 1 wt%. The enhanced coercivity shows a maximum at 1 wt% due to the dominant dipolar interactions among Fe nanorods. Also the squareness ratio shows a maximum at 1 wt%.

Electrochemical measurement of the oxygen potential of the system iron+alumina+ hercynite in the temperature range 750 to 1600oC

Solid oxide galvanic cells using CaO-ZrO2 and CaO-ZrO2 in combination with YO1.5-ThO2 as electrolyte were used to determine the free energy of formation of hercynite from 750–1600°C. The formation reaction is 2Fe(s,1) + O2(g) + Al2O3(α) = 2FeO.Al2O3(s)for which ΔG° = − 139,790 + 32.83T (±300) cals. (750–1536°C) ΔG° = − 146,390 + 36.48T (±300) cals. (1536–1700°C)These measurements can be used to resolve the discrepancies that exist in published thermochemical data, and provide an accurate oxygen potential standard for calibrating and assessing the performance of oxygen probes under steelmaking conditions.

Selective biodissolution of calcium and iron from bauxite in the presence of Bacillus polymyxa

A bacterium Bacillus polymyxa was found to be capable of selective removal of calcium and iron from bauxite. The bioleached residue was found to be enriched in its alumina content with insignificant amounts of iron and calcium as impurities. The developed bio- process was found to be capable of producing a bauxite product which meets the specifica- tions as a raw material for the manufacture of alumina based ceramics and refractories. The role of bacterial cells and metabolic products in the selective dissolution of calcium (present as calcite) and iron (present as hematite and goethite) from bauxite was assessed and possi- ble mechanisms illustrated. The effect of different parameters such as sucrose concentra- tion, pH, pulp density and time on selective biodissolution was studied. It was observed that periodic decantation and replenishment of the leach medium was beneficial in improving the dissolution kinetics. Calcium removal involves chelation with bacterial exopolysaccha- tides and acidolysis by organic acid generation. Hematite could be solubilized through a reductive dissolution mechanism.

A Histidine Aspartate Ionic Lock Gates the Iron Passage in Miniferritins from Mycobacterium smegmatis

Background: DNA-binding protein from starved cells (Dps) are nano-compartments that can oxidize and store iron rendering protection from free radicals. Results: A histidine-aspartate ionic cluster in mycobaterial Dps2 modulates the rate of iron entry and exit in these proteins. Conclusion: Substitutions that disrupt the cluster interface alter the iron uptake/release properties with localized structural changes. Significance: Identifying important gating residues can help in designing nano-delivery vehicles. Dps (DNA-binding protein from starved cells) are dodecameric assemblies belonging to the ferritin family that can bind DNA, carry out ferroxidation, and store iron in their shells. The ferritin-like trimeric pore harbors the channel for the entry and exit of iron. By representing the structure of Dps as a network we have identified a charge-driven interface formed by a histidine aspartate cluster at the pore interface unique to Mycobacterium smegmatis Dps protein, MsDps2. Site-directed mutagenesis was employed to generate mutants to disrupt the charged interactions. Kinetics of iron uptake/release of the wild type and mutants were compared. Crystal structures were solved at a resolution of 1.8-2.2 for the various mutants to compare structural alterations vis a vis the wild type protein. The substitutions at the pore interface resulted in alterations in the side chain conformations leading to an overall weakening of the interface network, especially in cases of substitutions that alter the charge at the pore interface. Contrary to earlier findings where conserved aspartate residues were found crucial for iron release, we propose here that in the case of MsDps2, it is the interplay of negative-positive potentials at the pore that enables proper functioning of the protein. In similar studies in ferritins, negative and positive patches near the iron exit pore were found to be important in iron uptake/release kinetics. The unique ionic cluster in MsDps2 makes it a suitable candidate to act as nano-delivery vehicle, as these gated pores can be manipulated to exhibit conformations allowing for slow or fast rates of iron release.

Dry sliding wear behaviour of magnesium alloy based hybrid composites in the longitudinal direction

In the present investigation, the wear behaviour of a creep-resistant AE42 magnesium alloy and its composites reinforced with Saffil short fibres and SiC particles in various combinations is examined in the longitudinal direction i.e., the plane containing random fibre orientation is perpendicular to the steel counter-face. Wear tests are conducted on a pin-on-disc set-up under dry sliding condition having a constant sliding velocity of 0.837 m/s for a constant sliding distance of 2.5 km in the load range of 10-40 N. It is observed that the wear rate increases with increase in load for the alloy and the composites, as expected. Wear rate of the composites is lower than the alloy and the hybrid composites exhibit a lower wear rate than the Saffil short fibres reinforced composite at all the loads. Therefore, the partial replacement of Saffil short fibres by an equal volume fraction of SiC particles not only reduces the cost but also improves the wear resistance of the composite. Microstructural investigation of the surface and subsurface of the worn pin and wear debris is carried out to explain the observed results and to understand the wear mechanisms. It is concluded that the presence of SiC particles in the hybrid composites improves the wear resistance because these particles remain intact and retain their load bearing capacity even at the highest load employed, they promote the formation of iron-rich transfer layer and they also delay the fracture of Saffil short fibres to higher loads. Under the experimental conditions used in the present investigation, the dominant wear mechanism is found to be abrasion for the AE42 alloy and its composites. It is accompanied by severe plastic deformation of surface layers in case of alloy and by the fracture of Saffil short fibres as well as the formation of iron-rich transfer layer in case of composites.

Mixed valency in the high-temperature phases of transition metal molybdates,AMoO4 (A=Fe, Co, Ni)

Transition metal molybdates of the formulaAMoO4 whereA=Fe, Co or Ni exhibit a first-order phase transition between 670K–970K. An investigation of the lowtemperature (lt) and high-temperature (ht) phases by x-ray photoelectron spectroscopy, x-ray absorption spectroscopy, magnetic susceptibility and other physical methods shows that the phase transition is associated with a valence change of the typeA 2++Mo6+αA 3++Mo5+ in the cases of iron and cobalt molybdates.

Stresses and Displacements under a Flexible Circular Foundation in the Presence of Friction or Adhesion

Die Vorliegende Arbeit beschäftigt sich mit den Spannungen und Verschiebungen an einem elastischen Halbraum unter einem kreisförmigen biegsamen Fundament, wenn an der Kontaktfläche vollkommenes Haften besteht. Das gemischte Randwertproblem wird mit Hilfe von Hankel-Transformationen auf duale Integralgleichungen von Titchmarsh- Typ zurückgeführt. Für die Berechnung der Spannungen und Verschiebungen werden Gaußsche Quadraturformeln benutzt. Die Ergebnisse werden mit denen verglichen, die man bei glattem Fundament erhält, und der Einfluß der Poisson-Zahl auf die Spannungen und Verschiebungen wird deutlich gemacht. Schließlich werden die Ergebnisse für den praktischen Gebrauch in Diagrammen und Tabellen zusammengefaßt.