Modeling the structure of amorphous MoS3: a neutron diffraction and reverse Monte Carlo study

A model for the structure of amorphous molybdenum trisulfide, a-MoS3, has been created using reverse Monte Carlo methods. This model, which consists of chains Of MoS6 units sharing three sulfurs with each of its two neighbors and forming alternate long, nonbonded, and short, bonded, Mo-Mo separations, is a good fit to the neutron diffraction data and is chemically and physically realistic. The paper identifies the limitations of previous models based on Mo-3 triangular clusters in accounting for the available experimental data.

Two new mu-(1,3-azido)-bridged polymers: alternating single and double bridges in a 1D nickel(II) complex and uniform bridge in a 2D copper(II) complex: Syntheses, single-crystal structures and magnetic studies

Two polymeric azido bridged complexes [Ni2L2(N-3)(3)](n)(ClO4). (1) and [Cu(bpdS)(2)(N-3)],(ClO4),(H2O)(2.5n) (2) [L = Schiff base, obtained from the condensation of pyridine-2-aldehyde with N,N,2,2-tetramethyl-1,3-propanediamine; bpds = 4,4'-bipyridyl disulfide] have been synthesized and their crystal structures have been determined. Complex 1, C26H42ClN15Ni2O4, crystallizes in a triclinic system, space group P1 with a 8.089(13), b = 9.392(14), c = 12.267(18) angstrom, a = 107.28(l), b 95.95(1), gamma = 96.92(1)degrees and Z = 2; complex 2, C20H21ClCuN7O6.5S4, crystallizes in an orthorhombic system, space group Pnna with a = 10.839(14), b = 13.208(17), c = 19.75(2) angstrom and Z = 4. The crystal structure of I consists of 1D polymers of nickel(L) units, alternatively connected by single and double bridging mu-(1,3-N-3) ligand with isolated perchlorate anions. Variable temperature magnetic susceptibility data of the complex have been measured and the fitting,of magnetic data was carried out applying the Borris-Almenar formula for such types of alternating one-dimensional S = 1 systems, based on the Hamiltonian H = -J Sigma(S2iS2i-1 + aS(2i)S(2i+1)). The best-fit parameters obtained are J = -106.7 +/- 2 cm(-1); a = 0.82 +/- 0.02; g = 2.21 +/- 0.02. Complex 2 is a 2D network of 4,4 topology with the nodes occupied by the Cu-II ions, and the edges formed by single azide and double bpds connectors. The perchlorate anions are located between pairs of bpds. The magnetic data have been fitted considering the complex as a pseudo-one-dimensional system, with all copper((II)) atoms linked by [mu(1,3-azido) bridging ligands at axial positions (long Cu...N-3 distances) since the coupling through long bpds is almost nil. The best-fit parameters obtained with this model are J = -1.21 +/- 0.2 cm(-1), g 2.14 +/- 0.02. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).

Synthesis and properties of new trinuclear Mo(II) complexes containing imidazole and benzimidazole ferrocene units

The reaction of FcCOC1 (Fc = (C5H5) Fe(C5H4)) with benzimidazole or imidazole in 1: 1 ratio gives the ferrocenyl derivatives FcCO(benzim) (L1) or FcCO(im) (L2), respectively. Two molecules of L1 or L2 can replace two nitrile ligands in [Mo(eta(3)-C3H5)( CO)(2)(CH3CN)(2)Br] or [Mo(eta(3)-C5H5O)(CO)(2)(CH3CN)(2)Br] leading to the new trinuclear complexes [Mo(eta(3)-C3H5)(CO)(2)(L)(2)Br] (C1 for L = L1; C3 for L = L2) and [Mo(eta(3)-C5H5O)(CO)(2)(L)(2)Br] (C-2 for L = L1; C4 for L = L2) with L1 and L2 acting as N-monodentade ligands. L1, L2 and C2 were characterized by X-ray diffraction studies. [Mo(eta(3)-C5H5O)(CO) 2(L1)(2)Br] was shown to be a trinuclear species, with the two L1 molecules occupying one equatorial and one axial position in the coordination sphere of Mo(II). Cyclic voltammetric studies were performed for the two ligands L1 and L2, as well as for their molybdenum complexes, and kinetic and thermodynamic data for the corresponding redox processes obtained. In agreement with the nature of the frontier orbitals obtained from DFT calculations, L1 and L2 exhibit one oxidation process at the Fe(II) center, while C1, C3, and C4 display another oxidation wave at lower potentials, associated with the oxidation of Mo(II). (C) 2007 Elsevier B. V. All rights reserved.

The effects of diet, breed and age of animal at slaughter on the aroma compounds of grilled beef

The aroma volatiles of grilled beef, from animals fed either grass silage or cereal concentrates, were compared. Aberdeen Angus and Holstein-Friesian cross-breed steers, slaughtered at 14 or 24 months, were studied. Compounds formed from linoleic acid, in particular 2-pentylfuran, 1-octen-3-ol, (Z)-2-octen-1-ol, and hexanal were at higher levels in the meat from the animals fed concentrates. Phytenes and compounds formed from α-linolenic acid, in particular 1-penten-3-ol and (Z)-2-penten-1-ol, were at higher levels in the meat of animals fed silage. Differences due to breed were small and not consistent with slaughter age. Dimethyl disulfide, dimethyl disulfide and phenol were at higher levels in the meat of animals slaughtered at 24 months and may contribute to grilled beef aroma.

Alignment of a model amyloid peptide fragment in bulk and at a solid surface

The alignment of model amyloid peptide YYKLVFFC is investigated in bulk and at a solid surface using a range of spectroscopic methods employing polarized radiation. The peptide is based on a core sequence of the amyloid beta (A beta) peptide, KLVFF. The attached tyrosine and cysteine units are exploited to yield information on alignment and possible formation of disulfide or dityrosine links. Polarized Raman spectroscopy on aligned stalks provides information on tyrosine orientation, which complements data from linear dichroism (LD) on aqueous solutions subjected to shear in a Couette cell. LD provides a detailed picture of alignment of peptide strands and aromatic residues and was also used to probe the kinetics of self-assembly. This suggests initial association of phenylalanine residues, followed by subsequent registry of strands and orientation of tyrosine residues. X-ray diffraction (XRD) data from aligned stalks is used to extract orientational order parameters from the 0.48 nm reflection in the cross-beta pattern, from which an orientational distribution function is obtained. X-ray diffraction on solutions subject to capillary flow confirmed orientation in situ at the level of the cross-beta pattern. The information on fibril and tyrosine orientation from polarized Raman spectroscopy is compared with results from NEXAFS experiments on samples prepared as films on silicon. This indicates fibrils are aligned parallel to the surface, with phenyl ring normals perpendicular to the surface. Possible disulfide bridging leading to peptide dimer formation was excluded by Raman spectroscopy, whereas dityrosine formation was probed by fluorescence experiments and was found not to occur except under alkaline conditions. Congo red binding was found not to influence the cross-beta XRD pattern.

Thiolated mucoadhesive and PEGylated nonmucoadhesive organosilica nanoparticles from 3-Mercaptopropyltrimethoxysilane

A novel approach has been developed to synthesize thiolated sub-100 nm organosilica nanoparticles from 3-mercaptopropyltrimethoxysilane (MPTS) through its self-condensation in dimethylsulfoxide in contact with atmospheric oxygen. The formation of MPTS nanoparticles proceeds through the condensation of methoxysilane groups and simultaneous disulfide bridging caused by partial oxidation of thiol groups. These nanoparticles showed excellent colloidal stability in dilute aqueous dispersions but underwent further self-assembly into chains and necklaces at higher concentrations. They exhibited very good ability to adhere to ocular mucosal surfaces, which can find applications in drug delivery. The thiolated nanoparticles could also be easily modified through PEGylation resulting in a loss of their mucoadhesive properties.

Structure of the DNA octanucleotide d(ACGTACGT)2

d(ACGTACGT), C78H84N30O32P7.20H2O, Mr (DNA) = 2170, tetragonal, P43212 (No 96), a = 42.845 (1), b = 42.845(1), c = 24.804 (1) Å, V = 45532.5 (2) Å3, z = 8,(MoK) = 0.71069 Å,µ(MoK) = 0.10 mm-1, T = 295 K, R = 0.18 for 1994 unique reflections between 5.0 and 1.9 Å resolution. The self-complementary octanucleotide d(ACGTACGT)2 has been crystallized and its structure determined to a resolution of 1.9 Å. The asymmetric unit consists of a single strand of octamer with 20 water molecules. It is only the second example of an octanucleotide having terminal A·T base pairs whose structure has been determined by X-ray crystallography. The sequence adopts the modified A-type conformation found for all octanucleotide duplexes studied to date with the helix bent by approximately 15° and an average tilt angle of 0°. Unusually the data collection was carried out using a 3 kW molybdenum sealed-tube source. The conformational details are discussed in comparison with other closely related sequences.

Synthesis and reactions of [Et3NH]4[Mo8O6]: X-ray crystal structure of [Et3NH]3[NaMo8O26]

[Et3NH]4[Mo8O26] (1) was prepared by reacting triethylamine with either molybdenum trioxide dihydrate or with a solution of ammonium molybdate in aqueous HCl. An aqueous solution of complex 1 reacted with an excess of sodium chloride to give a mixture of [Et3NH]3[NaMo8O26] (2) and [Et3NH]2[Mo6O19] (3). Complex 2 was also formed on reacting sodium molybdate with triethylamine in aqueous HCl. In the reaction of 1 with potassium chloride the nature of the product obtained was critically dependent upon reaction time. After a 5.5 h reflux period a mixture of [Et3NH]3[KMo8O26] (4) and 3 was obtained, whereas upon prolonged reflux (24 h) only K4Mo8O26 · H2O (5) was precipitated. The X-ray crystal structure of 2 shows it to be polymeric, with each Na+ ion sandwiched between two β[Mo8O26]4− ions. Four oxygen atoms on one face of each β[Mo8O26]4− ion are coordinated to a Na+ ion, and four oxygens from the opposite face are bonded to the next Na+ ion in the polymer chain. This produces a zig-zag arrangement of Na+ ions throughout the molecular structure. Spectral, conductivity and voltammetry data are given.

Molybdate and tungstate transfer by rat ileum competitive inhibition by sulphate

For both MoO42− and WO42− the maximum rate of uptake by the small intestine of the rat (studied in vitro using the everted sac technique) occurs in the lower ileum. Kinetic constants, derived by a least squares procedure, are compared with those previously obtained for SO42− transport. For both and , , with only small differences between sacs IV and V. Mutual inhibition of MoO42− and WO42− transport and inhibition of both by SO42− are competitive processes. This is shown by the generally good agreement between values and derived values and by V values in the presence and absence of the inhibiting species. The three ions SO42−, MoO42− and WO42− are probably transferred across the intestine by a common carrier system. Implications for the sulphate-molybdenum interaction in molybdosis are discussed.

Sulphate transport by rat ileum. Effect of molybdate and other anions

Kinetic constants for SO42− transport by upper and lower rat ileum in vitro have been determined by computer fitting of rate vs concentration data obtained using the everted sac technique. MoO42− inhibition of this transport is competitive, and kinetic constants for the inhibition were similarly determined. Transport is also inhibited by the anions WO42−, S2O32− and SeO42−, in the order . These anions have no effect on the transport of l-valine. Low SO42− transport rates were observed in sacs from animals fed a high-molybdenum diet. The significance of the results with respect to the problem of molybdate toxicity in animals is discussed, and related to the known protective effect of SO42−.

Staphylococcal extracellular adherence protein induces platelet activation by stimulation of thiol isomerases

OBJECTIVE: Staphylococcus aureus can induce platelet aggregation. The rapidity and degree of this correlates with the severity of disseminated intravascular coagulation, and depends on platelet peptidoglycans. Surface-located thiol isomerases play an important role in platelet activation. The staphylococcal extracellular adherence protein (Eap) functions as an adhesin for host plasma proteins. Therefore we tested the effect of Eap on platelets. METHODS AND RESULTS: We found a strong stimulation of the platelet-surface thiol isomerases protein disulfide isomerase, endoplasmic reticulum stress proteins 57 and 72 by Eap. Eap induced thiol isomerase-dependent glycoprotein IIb/IIIa activation, granule secretion, and platelet aggregation. Treatment of platelets with thiol blockers, bacitracin, and anti-protein disulfide isomerase antibody inhibited Eap-induced platelet activation. The effect of Eap on platelets and protein disulfide isomerase activity was completely blocked by glycosaminoglycans. Inhibition by the hydrophobic probe bis(1-anilinonaphthalene 8-sulfonate) suggested the involvement of hydrophobic sites in protein disulfide isomerase and platelet activation by Eap. CONCLUSIONS: In the present study, we found an additional and yet unknown mechanism of platelet activation by a bacterial adhesin, involving stimulation of thiol isomerases. The thiol isomerase stimulatory and prothrombotic features of a microbial secreted protein are probably not restricted to S aureus and Eap. Because many microorganisms are coated with amyloidogenic proteins, it is likely that the observed mechanism is a more general one.

The Valanginian δ13C excursion may not be an expression of a global oceanic anoxic event

Marine and terrestrial sediments of the Valanginian age display a distinct positive δ13C excursion, which has recently been interpreted as the expression of an oceanic anoxic episode (OAE) of global importance. Here we evaluate the extent of anaerobic conditions in marine bottom waters and explore the mechanisms involved in changing carbon storage on a global scale during this time interval. We asses redox-sensitive trace-element distributions (RSTE; uranium, vanadium, cobalt, arsenic and molybdenum) and the quality and quantity of preserved organic matter (OM) in representative sections along a shelf-basin transect in the western Tethys, in the Polish Basin and on Shatsky Rise. OM-rich layers corresponding in time to the δ13C shift are generally rare in the Tethyan sections and if present, the layers are not thicker than several centimetres and total organic carbon (TOC) contents do not surpass 1.68 wt..%. Palynological observations and geochemical properties of the preserved OM suggest a mixed marine and terrestrial origin and deposition in an oxic environment. In the Polish Basin, OM-rich layers show evidence for an important continental component. RSTE exhibit no major enrichments during the δ13C excursion in all studied Tethyan sections. RSTE enrichments are, however, observed in the pre-δ13C excursion OM-rich “Barrande” levels of the Vocontian Trough. In addition, all Tethyan sections record higher Mn contents during the δ13C shift, indicating rather well-oxygenated bottom waters in the western Tethys and the presence of anoxic basins elsewhere, such as the restricted basins of the North Atlantic and Weddell Sea. We propose that the Valanginian δ13C shift is the consequence of a combination of increased OM storage in marginal seas and on continents (as a sink of 12C-enriched organic carbon), coupled with the demise of shallow-water carbonate platforms (diminishing the storage capacity of 13C-enriched carbonate carbon). As such the Valanginian provides a more faithful natural analogue to present-day environmental change than most other Mesozoic OAEs, which are characterized by the development of ocean-wide dysaerobic to anaerobic conditions.

Contribution of non-volatile and volatile compounds to the umami taste and overall flavour of shiitake mushroom extracts and their application as flavour enhancers in cooked minced meat

Aqueous extracts of dried shiitake mushrooms (Lentinus edodes) were prepared as taste and flavour enhancers for meat formulations. Effects of time and temperature on the chemical and sensory properties of the extracts were examined. Extracts prepared at 70 °C had significantly higher concentrations (p<0.001) of the savoury tasting 5’-ribonucleotides than those prepared at 22 °C but increasing the extraction time from 30 to 360 mins only increased their recovery slightly (p=0.053). In contrast, higher temperature extracts had considerably smaller concentrations of the major volatile compounds, such as lenthionine, 1-octen-3-ol, 1,3-dithiethane and dimethyl disulfide, because of loss through volatilisation. A sensory discrimination test showed that the lower temperature extract was perceived to have less umami taste than the higher temperature extract (p=0.048). Incorporating the 70 °C shiitake extract into minced meat formulations led to significantly higher levels of savoury tasting 5’-ribonucleotides in the cooked meat but no significant difference in umami perception.

Speleothems as sensitive recorders of volcanic eruptions - the Bronze Age Minoan eruption recorded in a stalagmite from Turkey

Mounting evidence exists that variations in sulphur content in stalagmites are closely linked to changes in volcanic or anthropogenic atmospheric sulphur. The strong dependency of sulphur on soil pH and ecosystem storage, however, can result in a delay of several years to decades in the registration of volcanic eruptions and anthropogenic emissions by stalagmites. Here we present synchrotron-radiation based trace element analysis performed on a precisely-dated section of a stalagmite from Sofular Cave in Northern Turkey. As this section covers the time interval of the intensively studied Minoan volcanic eruption between 1600 and 1650 BC, we can test whether this vigorous eruption can be traced in a stalagmite. Of all measured trace elements, only bromine shows a clear short-lived peak at 1621±251621±25 BC, whereas sulphur and molybdenum show peaks later at 1617±251617±25 and 1589±251589±25 respectively. We suggest that all trace element peaks are related to the Minoan eruption, whereas the observed phasing of bromine, molybdenum and sulphur is related to differences in their retention rates in the soil above Sofular Cave. For the first time, we can show that bromine appears to be an ideal volcanic tracer in stalagmites, as it is a prominent volatile component in volcanic eruptions, can be easily leached in soils and rapidly transferred from the atmosphere through the soil and bedrock into the cave and stalagmite respectively. Highly resolved oxygen and carbon isotope profiles indicate that the Minoan eruption had no detectable climatic and environmental impact in Northern Turkey.

Redox- and glucose-responsive hydrogels from poly(vinyl alcohol) and 4-mercaptophenylboronic acid

Novel redox- and glucose-responsive hydrogels have been synthesized by simple mixing of poly(vinyl alcohol) (PVA) and 4-mercaptophenylboronic acid (MPBA) in aqueous solutions (pH > 9) in an oxidative aqueous media. These hydrogels are produced through the formation of disulfide linkages between MPBA molecules in an oxidative environment (oxygen dissolved in solution or hydrogen peroxide added to the reaction mixture) and complexation via dynamic covalent bonds between PVA and MPBA dimer. These hydrogels show degradation in solutions of l-glutathione and d-glucose.