The synthesis and characterisation of two new iron thioantimonates: [Fe(en)(3)](2)Sb2S5 center dot 0.55H(2)O and [Fe(en)(3)](2)Sb4S8

Two new iron thioantimonates, [Fe(en)(3)](2)Sb2S5 (.) 0.55H(2)O (1) and [Fe(en)(3)](2)Sb4S8 (2). were synthesised under solvothermal conditions from the reactions of Sb2S3, FeCl2 and S in the presence of ethylenediamine at 413 and 438 K, respectively. The products were characterised by single-crystal X-ray diffraction, elemental analysis and SQUID magnetometry. Compound 1 is unusual in containing isolated Sb2S54- anions formed from two corner-sharing SbS33- trigonal pyramids. These units are arranged in rippled layers, 4 A apart, parallel to the bc-plane. Octahedrally coordinated [Fe(en)(3)](2+) cations lie in depressions within these anionic layers. In compound (2), repeated corner linking of SbS33- trigonal pyramids generates SbS2- chains, which may be considered as a polymerised form of the Sb2S54- anions in 1. The SbS2- chains are separated by [Fe(en)(3)](2+) cations. In both compounds, there is an extensive network of hydrogen bonds between the nitrogen atoms of the ethylenediamine ligands and the sulfur atoms of the anions and, in the case of 1, the uncoordinated water molecule. (c) 2005 Elsevier Ltd. All rights reserved.

Synthesis and crystal structure characterization of iron(II), cobalt(II) and nickel(II) complexes with 1,3-bis(2-pyridylmethylthio)propane

Three new mononuclear complexes of nitrogen-sulfur donor sets, formulated as (Fe-II(L)Cl-2] (1), [Co-II(L)Cl-2] (2) and [Ni-II(L)Cl-2] (3) where L = 1,3-bis(2-pyridylmethylthio)propane, were synthesized and isolated in their pure form. All the complexes were characterized by physicochemical and spectroscopic methods. The solid state structures of complexes I and 3 have been established by single crystal X-ray crystallography. The structural analysis evidences isomorphous crystals with the metal ion in a distorted octahedral geometry that comprises NSSN ligand donors with trans located pyridine rings and chlorides in cis positions. In dimethylformamide solution, the complexes were found to exhibit Fe-II/Fe-III, co(II)/co(III) and Ni-II/Ni-III quasi-reversible redox couples in cyclic voltammograms with E-1/2 values (versus Ag/AgCl at 298 K) of +0.295, +0.795 and +0.745 V for 1, 2 and 3, respectively. (C) 2009 Elsevier Ltd. All rights reserved.

A phosphorus analogue of Bis(eta(4)-cyclobutadiene)iron(0)

P makes it possible: The convenient oxidative synthesis of the 16-electron organophosphorus iron sandwich complex [Fe(4-P2C2tBu2)2] suggests that the elusive all-carbon complex [Fe(4-C4H4)2] is a viable synthetic target.

Selenium supplementation of lactating dairy cows: effects on milk production and total selenium content and speciation in blood, milk and cheese

Forty multiparous Holstein cows were used in a 16-week continuous design study to determine the effects of either selenium (Se) source, selenised yeast (SY) (derived from a specific strain of Saccharomyces cerevisiae CNCM 1-3060) or sodium selenite (SS), or Se inclusion rate in the form of SY in the diets of lactating dairy cows on the Se concentration and speciation in blood, milk and cheese. Cows received ad libitum a total mixed ration (TMR) with a 1 : 1 forage: concentrate ratio on a dry matter (DM) basis. There were four diets (T-1 to T-4), which differed only in either source or dose of Se additive. Estimated total dietary Se for T, (no supplement), T-2 (SS), T-3 (SY) and T-4 (SY) was 0.16, 0.30, 0.30 and 0.45 mg/kg DM, respectively. Blood and milk samples were taken at 28-day intervals and at each time point there were positive linear effects of Se in the form of SY on the Se concentration in blood and milk. At day 112 blood and milk Se values for T-1 to T-4 were 177, 208, 248 and 279 +/- 6.6 and 24, 38, 57 and 72 +/- 3.7 ng/g fresh material, respectively, and indicate improved uptake and incorporation of Se from SY. In whole blood, selenocysteine (SeCys) was the main selenised amino acid and the concentration of selenomethionine (SeMet) increased with the increasing inclusion rate of SY In milk, there were no marked treatment effects on the SeCys content, but Se source had a marked effect on the concentration of SeMet. At day 112 replacing SS (T-2) with SY (T-3) increased the SeMet concentration of milk from 36 to 111 ng Se/g and its concentration increased further to 157ng Se/g dried sample as the inclusion rate of SY increased further (T-4) to provide 0.45 mg Se/kg TMR. Neither Se source nor inclusion rate affected the keeping quality of milk. At day 112 milk from T-1, T-2 and T-3 was made into a hard cheese and Se source had a marked effect on total Se and the concentration of total Se comprised as either SeMet or SeCys. Replacing SS (T-2) with SY (T-3) increased total Se, SeMet and SeCys content in cheese from 180 to 340 ng Se/g, 57 to 153 ng Se/g and 52 to 92 ng Se/g dried sample, respectively. The use of SY to produce food products with enhanced Se content as a means of meeting the Se requirements is discussed

Insights into redox cycling of sulfur and iron in peatlands using high-resolution diffusive equilibrium thin film (DET) gel probe sampling

High spatial resolution vertical profiles of pore-water chemistry have been obtained for a peatland using diffusive equilibrium in thin films (DET) gel probes. Comparison of DET pore-water data with more traditional depth-specific sampling shows good agreement and the DET profiling method is less invasive and less likely to induce mixing of pore-waters. Chloride mass balances as water tables fell in the early summer indicate that evaporative concentration dominates and there is negligible lateral flow in the peat. Lack of lateral flow allows element budgets for the same site at different times to be compared. The high spatial resolution of sampling also enables gradients to be observed that permit calculations of vertical fluxes. Sulfate concentrations fall at two sites with net rates of 1.5 and 5.0nmol cm− 3 day− 1, likely due to a dominance of bacterial sulfate reduction, while a third site showed a net gain in sulfate due to oxidation of sulfur over the study period at an average rate of 3.4nmol cm− 3 day− 1. Behaviour of iron is closely coupled to that of sulfur; there is net removal of iron at the two sites where sulfate reduction dominates and addition of iron where oxidation dominates. The profiles demonstrate that, in addition to strong vertical redox related chemical changes, there is significant spatial heterogeneity. Whilst overall there is evidence for net reduction of sulfate within the peatland pore-waters, this can be reversed, at least temporarily, during periods of drought when sulfide oxidation with resulting acid production predominates.

Ferric and ferrous iron in nitroso-myoglobin: computer simulations of stable and metastable states and their infrared spectra

The binding of NO to iron is involved in the biological function of many heme proteins. Contrary to ligands like CO and O-2, which only bind to ferrous (Fe-II) iron, NO binds to both ferrous and ferric (Fe-II) iron. In a particular protein, the natural oxidation state can therefore be expected to be tailored to the required function. Herein, we present an ob initio potential-energy surface for ferric iron interacting with NO. This potential-energy surface exhibits three minima corresponding to eta'-NO coordination (the global minimum), eta(1)-ON coordination and eta(2) coordination. This contrasts with the potential-energy surface for Fe-II-NO, which ex- hibits only two minima (the eta(2) coordination mode for Fe-II is a transition state, not a minimum). In addition, the binding energies of NO are substantially larger for Fe-III than for Fe-II. We have performed molecular dynamics simulations for NO bound to ferric myoglobin (Mb(III)) and compare these with results obtained for Mb(II). Over the duration of our simulations (1.5 ns), all three binding modes are found to be stable at 200 K and transiently stable at 300 K, with eventual transformation to the eta(1)-NO global-minimum conformation. We discuss the implication of these results related to studies of rebinding processes in myoglobin.

A phosphorus analogue of Bis(eta(4)-cyclobutadiene)iron(0)

Iron is a pivotal element in organometallic chemistry, enabling fundamental insights with high-impact applications.[1] Ferrocene derivatives have countless uses,[2] and the recent advances in iron catalysis are equally impressive.[3]

Assessing the impact of nano- and micro-scale zerovalent iron particles on soil microbial activities: Particle reactivity interferes with assay conditions and interpretation of genuine microbial effects

The effects of nano-scale and micro-scale zerovalent iron (nZVI and mZVI) particles on general (dehydrogenase and hydrolase) and specific (ammonia oxidation potential, AOP) activities mediated by the microbial community in an uncontaminated soil were examined. nZVI (diameter 12.5 nm; 10 mg gÿ1 soil)apparently inhibited AOP and nZVI and mZVI apparently stimulated dehydrogenase activity but had minimal influence on hydrolase activity. Sterile experiments revealed that the apparent inhibition of AOP could not be interpreted as such due to the confounding action of the particles, whereas, the nZVIenhanced dehydrogenase activity could represent the genuine response of a stimulated microbial population or an artifact of ZVI reactivity. Overall, there was no evidence for negative effects of nZVI or mZVI on the processes studied. When examining the impact of redox active particles such as ZVI on microbial oxidation–reduction reactions, potential confounding effects of the test particles on assay conditions should be considered.

Syntheses, structures, some reactions, and electrochemical oxidation of ferrocenylethynyl complexes of iron, ruthenium, and osmium

The syntheses and characterizations of several complexes containing ferrocenylethynyl and ferrocene-1,1'-bis(ethynyl) groups attached to M(PP)Cp'[M = Fe, Ru, PP = dppe, Cp'= Cp*; M = Ru, Os, PP = (PPh3)(2), dppe, Cp' = Cp] are described. Reactions with tetracyanoethene have given either tetracyanobuta-1,3-dienyl or eta(3)-allylic derivatives, while addition of Me+ afforded the corresponding vinylidene derivatives. Some electrochemical measurements are discussed in terms of electronic communication between the redox-active M(PP)Cp' groups through the ferrocene nucleus. The molecular structures of 14 of these complexes have been determined by crystallographic methods.

Isolation and characterisation of EfeM, a periplasmic component of the putative EfeUOBM iron transporter of Pseudomonas syringae pv. syringae

The EfeM protein is a component of the putative EfeUOBM iron-transporter of Pseudomonas syringae pathovar syringae and is thought to act as a periplasmic, ferrous-iron binding protein. It contains a signal peptide of 34 amino acid residues and a C-terminal 'Peptidase_M75' domain of 251 residues. The C-terminal domain contains a highly conserved 'HXXE' motif thought to act as part of a divalent cation-binding site. In this work, the gene (efeM or 'Psyr_3370') encoding EfeM was cloned and over-expressed in Escherichia coli, and the mature protein was purified from the periplasm. Mass spectrometry confirmed the identity of the protein (M(W) 27,772Da). Circular dichroism spectroscopy of EfeM indicated a mainly alpha-helical structure, consistent with bioinformatic predictions. Purified EfeM was crystallised by hanging-drop vapor diffusion to give needle-shaped crystals that diffracted to a resolution of 1.6A. This is the first molecular study of a peptidase M75 domain with a presumed iron transport role.

Phylogenies reveal new interpretation of speciation and the Red Queen

The Red Queen metaphor has species accumulating small changes to keep up with a continually changing environment, with speciation occurring at a constant rate. This constant-rate claim is now tested against four competing models, using 101 phylogenies of animal, plant and fungal taxa. The results provide a new interpretation of the Red Queen; a view linking speciation to rare stochastic events that cause reproductive isolation.

Speciation as an active force in promoting genetic evolution

There is a growing appreciation among evolutionary biologists that the rate and tempo of molecular evolution might often be altered at or near the time of speciation, i.e. that speciation is in some way a special time for genes. Molecular phylogenies frequently reveal increased rates of genetic evolution associated with speciation and other lines of investigation suggest that various types of abrupt genomic disruption can play an important role in promoting speciation via reproductive isolation. These phenomena are in conflict with the gradual view of molecular evolution that is implicit in much of our thinking about speciation and in the tools of modern biology. This raises the prospect of studying the molecular evolutionary consequences of speciation per se and studying the footprint of speciation as an active force in promoting genetic divergence. Here we discuss the reasons to believe that speciation can play such a role and elaborate on possible mechanisms for accelerated rates of evolution following speciation. We provide an example of how it is possible detect whether accelerated bursts of evolution occur in neutral and/or adaptive regions of genes and discuss the implications of rapid episodes of change for conventional models of molecular evolution. Speciation might often owe more to ephemeral and essentially arbitrary events that cause reproductive isolation than to the gradual and regular tug of natural selection that draws a species into a new niche.

Adaptive divergence and speciation among sexual and pseudoviviparous populations of Festuca

Pseudovivipary is an environmentally induced flowering abnormality in which vegetative shoots replace seminiferous (sexual) inflorescences. Pseudovivipary is usually retained in transplantation experiments, indicating that the trait is not solely induced by the growing environment. Pseudovivipary is the defining characteristic of Festuca vivipara, and arguably the only feature separating this species from its closest seminiferous relative, Festuca ovina. We performed phylogenetic and population genetic analysis on sympatric F. ovina and F. vivipara samples to establish whether pseudovivipary is an adaptive trait that accurately defines the separation of genetically distinct Festuca species. Chloroplast and nuclear marker-based analyses revealed that variation at a geographical level can exceed that between F. vivipara and F. ovina. We deduced that F. vivipara is a recent species that frequently arises independently within F. ovina populations and has not accumulated significant genetic differentiation from its progenitor. We inferred local gene flow between the species. We identified one amplified fragment length polymorphism marker that may be linked to a pseudovivipary-related region of the genome, and several other markers provide evidence of regional local adaptation in Festuca populations. We conclude that F. vivipara can only be appropriately recognized as a morphologically and ecologically distinct species; it lacks genetic differentiation from its relatives. This is the first report of a ‘failure in normal flowering development’ that repeatedly appears to be adaptive, such that the trait responsible for species recognition constantly reappears on a local basis.

Analysis of aluminium content and iron homeostasis in nipple aspirate fluids from healthy women and breast cancer-affected patients

Aluminium is not a physiological component of the breast but has been measured recently in human breast tissues and breast cyst fluids at levels above those found in blood serum or milk. Since the presence of aluminium can lead to iron dyshomeostasis, levels of aluminium and iron-binding proteins (ferritin, transferrin) were measured in nipple aspirate fluid (NAF), a fluid present in the breast duct tree and mirroring the breast microenvironment. NAFs were collected noninvasively from healthy women (NoCancer; n = 16) and breast cancer-affected women (Cancer; n = 19), and compared with levels in serum (n = 15) and milk (n = 45) from healthy subjects. The mean level of aluminium, measured by ICP-mass spectrometry, was significantly higher in Cancer NAF (268.4 ± 28.1 μg l−1; n = 19) than in NoCancer NAF (131.3 ± 9.6 μg l−1; n = 16; P < 0.0001). The mean level of ferritin, measured through immunoassay, was also found to be higher in Cancer NAF (280.0 ± 32.3 μg l−1) than in NoCancer NAF (55.5 ± 7.2 μg l−1), and furthermore, a positive correlation was found between levels of aluminium and ferritin in the Cancer NAF (correlation coefficient R = 0.94, P < 0.001). These results may suggest a role for raised levels of aluminium and modulation of proteins that regulate iron homeostasis as biomarkers for identification of women at higher risk of developing breast cancer. The reasons for the high levels of aluminium in NAF remain unknown but possibilities include either exposure to aluminium-based antiperspirant salts in the adjacent underarm area and/or preferential accumulation of aluminium by breast tissues.

Speciation and variation in the occurrence of haloacetic acids in three water supply systems in England

An investigation into the speciation and occurrence of nine haloacetic acids (HAAs) was conducted during the period of April 2007 to March 2008 and involved three drinking water supply systems in England, which were chosen to represent a range of source water conditions; these were an upland surface water, a lowland surface water and a groundwater. Samples were collected seasonally from the water treatment plants and at different locations in the distribution systems. The highest HAA concentrations occurred in the upland surface water system, with an average total HAA concentration of 21.3 μg/L. The lowest HAA levels were observed in the groundwater source, with a mean concentration of 0.6 μg/L. Seasonal variations were significant in the HAA concentrations; the highest total HAA concentrations were found during the autumn, when the concentrations were approximately two times higher than in winter and spring. HAA speciation varied among the water sources, with dichloroacetic acid and trichloroacetic acid dominant in the lowland surface water system and brominated species dominant in the upland surface water system. There was a strong correlation between trihalomethanes and HAAs when considering all samples from the three systems in the same data set (r2=0.88); however, the correlation was poor/moderate when considering each system independently.