Structural, magnetic, and electronic properties of VxCr2−xS3(0

A new family of vanadium-substituted chromium sulfides (VxCr2-xS3, 0 < x < 2) has been prepared and characterized by powder X-ray and neutron diffraction, SQUID magnetometry, electrical resistivity, and Seebeck coefficient measurements. Vanadium substitution leads to a single-phase region with a rhombohedral Cr2S3 structure over the composition range 0.0 < x e 0.75, while at higher vanadium contents (1.6 e x < 2.0) a second single-phase region, in which materials adopt a cation-deficient Cr3S4 structure, is observed. Materials with the Cr2S3 structure all exhibit semiconducting behavior. However, both transport and magnetic properties indicate an increasing degree of electron delocalization with increasing vanadium content in this compositional region. Materials that adopt a Cr3S4-type structure exhibit metallic behavior. Magnetic susceptibility data reveal that all materials undergo a magnetic ordering transition at temperatures in the range 90–118 K. Low-temperature magnetization data suggest that this involves a transition to a ferrimagnetic state.

Co3(SO4)3(OH)2[enH2]: a newS= 3/2 Kagome-type layered sulfate with a unique connectivity

The Kagome lattice, comprising a two-dimensional array of corner-sharing equilateral triangles, is central to the exploration of magnetic frustration. In such a lattice, antiferromagnetic coupling between ions in triangular plaquettes prevents all of the exchange interactions being simultaneously satisfied and a variety of novel magnetic ground states may result at low temperature. Experimental realization of a Kagome lattice remains difficult. The jarosite family of materials of nominal composition AM3(SO4)2(OH)6 (A = monovalent cation; M= Fe3+, Cr3+), offers perhaps one of the most promising manifestations of the phenomenon of magnetic frustration in two dimensions. The magnetic properties of jarosites are however extremely sensitive to the degree of coverage of magnetic sites. Consequently, there is considerable interest in the use of soft chemical techniques for the design and synthesis of novel materials in which to explore the effects of spin, degree of site coverage and connectivity on magnetic frustration.

Ultralow-frequency modulation of whistler-mode wave growth

Measurements from ground-based magnetometers and riometers at auroral latitudes have demonstrated that energetic (~30-300keV) electron precipitation can be modulated in the presence of magnetic field oscillations at ultra-low frequencies. It has previously been proposed that an ultra-low frequency (ULF) wave would modulate field and plasma properties near the equatorial plane, thus modifying the growth rates of whistler-mode waves. In turn, the resulting whistler-mode waves would mediate the pitch-angle scattering of electrons resulting in ionospheric precipitation. In this paper, we investigate this hypothesis by quantifying the changes to the linear growth rate expected due to a slow change in the local magnetic field strength for parameters typical of the equatorial region around 6.6RE radial distance. To constrain our study, we determine the largest possible ULF wave amplitudes from measurements of the magnetic field at geosynchronous orbit. Using nearly ten years of observations from two satellites, we demonstrate that the variation in magnetic field strength due to oscillations at 2mHz does not exceed ±10% of the background field. Modifications to the plasma density and temperature anisotropy are estimated using idealised models. For low temperature anisotropy, there is little change in the whistler-mode growth rates even for the largest ULF wave amplitude. Only for large temperature anisotropies can whistler-mode growth rates be modulated sufficiently to account for the changes in electron precipitation measured by riometers at auroral latitudes.

Proteolysis of milk heated at high temperatures by native enzymes analysed by trinitrobenzene sulphonic acid (TNBS) method

Native enzymes play a significant role in proteolysis of milk during storage. This is significant for heat resistant native enzymes. Plasmin is one of the most heat resistant enzymes found in milk. It has been reported to survive several heat treatments, causing spoilage during storage. The aim of this study was to assess susceptibility of high temperature heated milk to proteolysis by native enzymes. The trinitrobenzene sulphonic acid (TNBS) method was used for this purpose. Raw milk was heated at 110, 120, 130,142°C for 2 s and 85°C for 15 s and milk processed at low temperature (85°C /15s) was selected to mimic pasteurisation. TNBS method confirmed that raw milk and milk processed at 85°C /15s were the most proteolysed, whereas treatment of milk at high temperatures (110, 120, 130 and 142°C for 2 s) inactivated the native enzymes. It may thus be concluded that high temperature processing positively affects proteolysis by lowering its susceptibility to spoilage during storage.

A cross-calibration of GMS-5 thermal channels against ATSR-2

Motivated by the importance to weather and climate of the Indo-Pacific seas, we present a new calibration of the Visible Infrared Spin-Scan Radiometer (VISSR) on the geostationary meteorological satellite, GMS-5. VISSR imagery has significant potential for exploring the dynamics of the ocean and air–sea interactions in this poorly characterized region, by virtue of the VISSR's surface temperature retrieval capability and hourly sampling. However, the calibration of the thermal imagery supplied by the Japanese Meteorological Agency (JMA) is inconsistent with the spectral characteristics of the channels, and published details of the JMA calibration procedure are scant. We use the well-characterized Along-Track Scanning Radiometer 2 (ATSR-2) as a reference, and determine calibration corrections for GMS-5 VISSR. We obtain more credible VISSR brightness temperatures and demonstrate sea surface temperature (SST) retrieval that validates well against in situ measurements (bias ∼0.3 and scatter ∼0.4 K). Comparison with a widely used sea surface temperature analysis shows that the GMS-5 VISSR SST fields capture important spatial structure, absent in the analysis.

RuII(α-diimine) or RuIII(α-diimine·–)? Structural, spectroscopic, and theoretical evidence for the stabilization of a prominent metal-to-Ligand charge- transfer excited-state configuration in the ground state

The new compounds [Ru(R-DAB)(acac)2] (R-DAB = 1,4-diorganyl- 1,4-diazabuta-1,3-diene; R = tert-butyl, 4-methoxyphenyl, 2,6-dimethylphenyl; acac– = 2,4-pentanedionate) exhibit intrachelate ring bond lengths 1.297low temperature. The results are discussed with respect to metal-to-ligand chargetransfer (MLCT) excited states of conventional (α-diimine)- ruthenium(II) complexes and in view of other (α-diimine)- metal complexes with ambiguous oxidation-state assignments.

Following the creation of active gold nanocatalysts from phosphine-stabilized molecular clusters

The phosphine-stabilised gold cluster [Au6(Ph2P-o-tolyl)6](NO3)2 is converted into an active nanocatalyst for the oxidation of benzyl alcohol through low-temperature peroxide-assisted removal of the phosphines, avoiding the high-temperature calcination process. The process was monitored using in-situ X-ray absorption spectroscopy, which revealed that after a certain period of the reaction with tertiary butyl hydrogen peroxide, the phosphine ligands are removed to form nanoparticles of gold which matches with the induction period seen in the catalytic reaction. Density functional theory calculations show that the energies required to remove the ligands from the [Au6Ln]2+ increase significantly with successive removal steps, suggesting that the process does not occur at once but sequentially. The calculations also reveal that ligand removal is accompanied by dramatic re-arrangements in the topology of the cluster core.

Why the Heyd-Scuseria-Ernzerhof hybrid functional description of VO2 phases is not correct

In contrast with recent claims that the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid functional can provide a good description of the electronic and magnetic structures of VO2 phases [Eyert, Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.107.016401 107, 016401 (2011)], we show here that the HSE lowest-energy solutions for both the low-temperature monoclinic (M1) phase and the high-temperature rutile (R) phase, which are obtained upon inclusion of spin polarization, are at odds with experimental observations. For the M1 phase the ground state is (but should not be) magnetic, while the ground state of the R phase, which is also spin polarized, is not (but should be) metallic. The energy difference between the low-temperature and high-temperature phases has strong discrepancies with the experimental latent heat.

Spin polarization, orbital occupation and band gap opening in vanadium dioxide: the effect of screened Hartree–Fock exchange

The metal–insulator transition of VO2 so far has evaded an accurate description by density functional theory. The screened hybrid functional of Heyd, Scuseria and Ernzerhof leads to reasonable solutions for both the low-temperature monoclinic and high-temperature rutile phases only if spin polarization is excluded from the calculations. We explore whether a satisfactory agreement with experiment can be achieved by tuning the fraction of Hartree Fock exchange (a) in the density functional. It is found that two branches of locally stable solutions exist for the rutile phase for 12:5% 6 a 6 20%. One is metallic and has the correct stability as compared to the monoclinic phase, the other is insulating with lower energy than the metallic branch. We discuss these observations based on the V 3d orbital occupations and conclude that a ¼ 10% is the best possible choice for spin-polarized VO2 calculations.

Spin-polarized electronic-structure of MnBiAl

The self-consistent spin-polarized band-structure calculation of ferromagnetic compound MnBiAl in its low-temperature phase has been performed. In this paper the calculation results are given. Comparison with the results of MnBi is performed in order to find the effect on electronic structure by doping with Al.

Coverage-dependent structural evolution in the interaction of NO2 with Au{111}

We have used low-temperature STM, together with DFT calculations incorporating the effects of dispersion forces, to study from a structural point of view the interaction of NO2 with Au{111} surfaces. NO2 adsorbs molecularly on Au{111} at 80 K, initially as small, disordered clusters at the elbows of the type-x reconstruction lines of the clean-surface herringbone reconstruction, and then as larger, ordered islands on the fcc regions. Within the islands, the NO2 molecules define a (√3 × 2)rect. superlattice, for which we evaluate structural models. By around 0.25 ML coverage, the herringbone reconstruction has been lifted, accompanied by the formation of Au nanoclusters, and the islands have coalesced. At this stage, essentially the whole surface is covered with an overlayer consisting predominantly of domains of the (√3 × 2)rect. structure, but also containing less wellordered regions. With further exposure, the degree of disorder in the overlayer increases; saturation occurs close to 0.43 ML.

Consumer acceptability and sensory profile of cooked broccoli with mustard seeds added to improve chemoprotective properties

Broccoli, a rich source of glucosinolates, is a commonly consumed vegetable of the Brassica family. Hydrolysis products of glucosinolates, isothiocyanates, have been associated with health benefits and contribute to the flavour of Brassica. However, boiling broccoli causes the myrosinase enzyme needed for hydrolysis to denature. In order to ensure hydrolysis, broccoli must either be mildly cooked or active sources of myrosinase, such as mustard seed powder, can be added post-cooking. In this study, samples of broccoli were prepared in six different ways; standard boiling with and without mustard seeds, sous-vide cooking at low temperature (70 °C) and sous-vide cooking at higher temperature (100 ºC) without mustard and with mustard at two different concentrations. The majority of consumers disliked the mildly cooked broccoli samples (70 ºC, 12 min, sous-vide) which had a hard and stringy texture. The highest mean consumer liking was for standard boiled samples (100 ºC, 7 min). Addition of 1% mustard seed powder developed sensory attributes such as pungency, burning sensation, mustard odour and flavour. One cluster of consumers (32%) found mustard seeds to be a good complement to cooked broccoli, however, the majority disliked the mustard-derived sensory attributes. Where the mustard seeds were partially processed, doubling the addition to 2% led to only the same level of mustard flavour and pungency as 1% unprocessed seeds, and mean consumer liking remained unaltered. This suggests that optimisation of the addition level of partially processed mustard seeds may be a route to enhance bioactivity of cooked broccoli without compromising consumer acceptability.

Influence of inherent structure shear stress of supercooled liquids on their shear moduli

Configurations of supercooled liquids residing in their local potential minimum (i.e. in their inherent structure, IS) were found to support a non-zero shear stress. This IS stress was attributed to the constraint to the energy minimization imposed by boundary conditions, which keep size and shape of the simulation cell fixed. In this paper we further investigate the influence of these boundary conditions on the IS stress. We investigate its importance for the computation of the low frequency shear modulus of a glass obtaining a consistent picture for the low- and high frequency shear moduli over the full temperature range. Hence, we find that the IS stress corresponds to a non-thermal contribution to the fluctuation term in the Born-Green expression. This leads to an unphysical divergence of the moduli in the low temperature limit if no proper correction for this term is applied. Furthermore, we clarify the IS stress dependence on the system size and put its origin on a more formal basis.

The importance of anisotropic Coulomb interaction in LaMnO3

In low-temperature anti-ferromagnetic LaMnO3, strong and localized electronic interactions among Mn 3d electrons prevent a satisfactory description from standard local density and generalized gradient approximations in density functional theory calculations. Here we show that the strong on-site electronic interactions are described well only by using direct and exchange corrections to the intra-orbital Coulomb potential. Only DFT+U calculations with explicit exchange corrections produce a balanced picture of electronic, magnetic and structural observables in agreement with experiment. To understand the reason, a rewriting of the functional form of the +U corrections is presented that leads to a more physical and transparent understanding of the effect of these correction terms. The approach highlights the importance of Hund’s coupling (intra-orbital exchange) in providing anisotropy across the occupation and energy eigenvalues of the Mn d states. This intra-orbital exchange is the key to fully activating the Jahn-Teller distortion, reproducing the experimental band gap and stabilizing the correct magnetic ground state in LaMnO3. The best parameter values for LaMnO3 within the DFT(PBEsol)+U framework are determined to be U = 8 eV and J = 1.9 eV.

Microbial decomposition of skeletal muscle tissue (Ovis aries) in a sandy loam soil at different temperatures

A laboratory experiment was conducted to determine the effect of temperature (2, 12, 22 °C) on the rate of aerobic decomposition of skeletal muscle tissue (Ovis aries) in a sandy loam soil incubated for a period of 42 days. Measurements of decomposition processes included skeletal muscle tissue mass loss, carbon dioxide (CO2) evolution, microbial biomass, soil pH, skeletal muscle tissue carbon (C) and nitrogen (N) content and the calculation of metabolic quotient (qCO2). Incubation temperature and skeletal muscle tissue quality had a significant effect on all of the measured process rates with 2 °C usually much lower than 12 and 22 °C. Cumulative CO2 evolution at 2, 12 and 22 °C equaled 252, 619 and 905 mg CO2, respectively. A significant correlation (P<0.001) was detected between cumulative CO2 evolution and tissue mass loss at all temperatures. Q10s for mass loss and CO2 evolution, which ranged from 1.19 to 3.95, were higher for the lower temperature range (Q10(2– 12 °C)>Q10(12–22 °C)) in the Ovis samples and lower for the low temperature range (Q10(2–12 °C)lower microbial catabolic requirements at lower temperature.