Fe Complexes (fe + complex)

Distribution by Scientific Domains

Selected Abstracts

Discrete Cyanide-Bridged Mixed-Valence Co/Fe Complexes: Outer-Sphere Redox Behaviour

Paul V. Bernhardt
Abstract The outer-sphere redox behaviour of a series of [LnCoIIINCFeII(CN)5], (Ln = n -membered pentadentate aza-macrocycle) complexes have been studied as a function of pH and oxidising agent. All the dinuclear complexes show a double protonation process at pH , 2 that produces a shift in their UV/Vis spectra. Oxidation of the different non-protonated and diprotonated complexes has been carried out with peroxodisulfate, and of the non-protonated complexes also with trisoxalatocobaltate(III). The results are in agreement with predictions from the Marcus theory. The oxidation of [Fe(phen)3]3+ and [IrCl6]2, is too fast to be measured, although for the latter the transient observation of the process has been achieved at pH = 0. The study of the kinetics of the outer-sphere redox process, with the S2O82, and [Co(ox)3]3, oxidants, has been carried out as a function of pH, temperature, and pressure. As a whole, the values found for the activation volumes, entropies, and enthalpies are in the following margins, for the diprotonated and non-protonated dinuclear complexes, respectively: ,V, from 11 to 13 and 15 to 20 cm3 mol,1; ,S, from 110 to 30 and ,60 to ,90 J K,1 mol,1; ,H, from 115 to 80 and 50 to 65 kJ·mol,1. The thermal activation parameters are clearly dominated by the electrostriction occurring on outer-sphere precursor formation, while the trends found for the values of the volume of activation indicate an important degree of tuning due to the charge distribution during the electron transfer process. The special arrangement on the amine ligands in the isomer trans -[L14CoIIINCFeII(CN)5], accounts for important differences in solvent-assisted hydrogen bonding occurring within the outer-sphere redox process, as has been established in redox reactions of similar compounds. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]

Insertion of Molecular Oxygen in Transition-Metal Hydride Bonds, Oxygen-Bond Activation, and Unimolecular Dissociation of Metal Hydroperoxide Intermediates.

Short Communication
Abstract Thermal activation of molecular oxygen is observed for the late-transition-metal cationic complexes [M(H)(OH)]+ with M=Fe, Co, and Ni. Most of the reactions proceed via insertion in a metalhydride bond followed by the dissociation of the resulting metal hydroperoxide intermediate(s) upon losses of O, OH, and H2O. As indicated by labeling studies, the processes for the Ni complex are very specific such that the O-atoms of the neutrals expelled originate almost exclusively from the substrate O2. In comparison to the [M(H)(OH)]+ cations, the ionmolecule reactions of the metal hydride systems [MH]+ (M=Fe, Co, Ni, Pd, and Pt) with dioxygen are rather inefficient, if they occur at all. However, for the solvated complexes [M(H)(H2O)]+ (M=Fe, Co, Ni), the reaction with O2 involving OO bond activation show higher reactivity depending on the transition metal: 60% for the Ni, 16% for the Co, and only 4% for the Fe complex relative to the [Ni(H)(OH)]+/O2 couple. [source]

Interferon-, and lipopolysaccharide regulate the expression of Nramp2 and increase the uptake of iron from low relative molecular mass complexes by macrophages

FEBS JOURNAL, Issue 22 2000
S. L. Wardrop
The natural resistance associated macrophage protein 2 (Nramp2) is a transporter that is involved in iron (Fe) uptake from transferrin (Tf) and low molecular mass Fe complexes. Here we describe the effect of the inflammatory mediators interferon-, (IFN-,) and lipopolysaccharide (LPS) on the expression of Nramp2 mRNA and Fe uptake by cells of the macrophage lineage. After incubation of the RAW264.7 macrophage cell line with LPS there was a sevenfold increase in the expression of the 2.3 kb Nramp2 mRNA transcript when compared with the control, but little effect on the Nramp2 3.1 kb transcript. These results indicate differential regulation of the two transcripts. Treatment with LPS resulted in an increase in 59Fe uptake from 59Fe,nitrilotriacetic acid, while transferrin receptor (TfR) mRNA levels and 59Fe uptake from 59Fe,Tf were decreased. Paradoxically, at the same time, an increase in iron regulatory protein (IRP)1 RNA-binding activity was observed. Incubation with IFN-, (50 U·mL,1) resulted in a marked decrease in TfR mRNA levels but had no effect on Nramp2 mRNA expression. Exposure of RAW264.7 cells to both IFN-, and LPS resulted in a fourfold increase in the Nramp2 2.3-kb transcript and a four to fivefold decrease in the 3.1-kb transcript when compared with the control. Furthermore, there was a decrease in TfR mRNA levels despite an increase in IRP1 RNA-binding activity and a marked increase in inducible nitric oxide synthase mRNA expression. Hence, TfR and Nramp2 mRNA expression did not appear to be regulated in a concerted manner. Similar responses to those found above for RAW264.7 cells were also observed in the J774 macrophage cell line and also for primary cultures of mouse peritoneal macrophages. These results are of interest as the TfR and Nramp2 are thought to act together during Fe uptake from Tf. This is the first report to demonstrate regulation of the Nramp2 mRNA transcripts by inflammatory mediators. [source]

Comparison of iron chelates and complexes supplied as foliar sprays and in nutrient solution to correct iron chlorosis of soybean

Patricia Rodríguez-Lucena
Abstract The application of synthetic chelates is the most efficient remedy for correcting iron (Fe) chlorosis. However, chelates are usually expensive and nondegradable products. Recently, new degradable chelates have been proposed for their use as Fe fertilizers. Also, Fe complexes cheaper than synthetic chelates and derived from natural products are also used to correct Fe deficiencies. Fifteen products, including five different synthetic chelates (Fe-EDDS, Fe-IDHA, and three Fe-EDTA formulations) and ten natural complexes (humates, lignosulfonates, amino acids, glycoproteins, polyamines, citrate, and gluconate), have been compared when applied at low concentration to soybean (Glycine max L.) chlorotic plants grown in hydroponics under controlled conditions. In the first experiment, Fe compounds were applied to the nutrient solution, while in the second trial, Fe was foliar-supplied. Dry matter, Fe concentration in shoots and roots, and SPAD values were used to evaluate the effectiveness of the Fe in the different products. In the nutrient-solution experiment, synthetic chelates provided better plant growth, Fe concentration, and SPAD values than complexes. Among the Fe complexes, transferrin generally provided good plant responses, similar to those obtained with synthetic chelates. After foliar application, the highest regreening was observed for plants treated with synthetic chelates and amino acid complexes, but the translocation to roots only occurred for Fe lignosulfonate. Fe-EDDS and Fe-EDTA performed in a similar way when applied in nutrient solution or as foliar sprays. [source]