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.

Optical dating of quartz from young samples and the effects of pre-heat temperature

The optically stimulated luminescence (OSL) signal within quartz may be enhanced by thermal transfer during pre-heating. This may occur via a thermally induced charge transfer from low temperature traps to the OSL traps. Thermal transfer may affect both natural and artificially irradiated samples. The effect, as empirically measured via recuperation tests, is typically observed to be negligible for old samples (<1% of natural signal). However, thermal transfer remains a major concern in the dating of young samples as thermal decay and transfers of geologically unstable traps (typically in the TL range 160–280°C) may be incomplete. Upon pre-heating such a sample might undergo thermal transfer to the dating trap and result in a De overestimate. As a result, there has been a tendency for workers to adopt less rigorous pre-heats for young samples. We have investigated the pre-heat dependence of 23 young quartz samples from various depositional environments using pre-heats between 170°C and 300°C, employing the single aliquot regeneration (SAR) protocol. SAR De's were also calculated for 25 additional young quartz samples of different depositional environments and compared with previous multiple aliquot additive dose (MAAD) data. Results demonstrate no significant De dependence upon pre-heat temperatures. A close correspondence between MAAD data and the current SAR data for the samples tested is also illustrated.

Surface chemistry of alanine on Cu{111}: Adsorption geometry and temperature dependence

Adsorption of l-alanine on the Cu{111} single crystal surface was investigated as a model system for interactions between small chiral modifier molecules and close-packed metal surfaces. Synchrotron-based X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy are used to determine the chemical state, bond coordination and out-of-plane orientation of the molecule on the surface. Alanine adsorbs in its anionic form at room temperature, whilst at low temperature the overlayer consists of anionic and zwitterionic molecules. NEXAFS spectra exhibit a strong angular dependence of the π ⁎ resonance associated with the carboxylate group, which allows determining the tilt angle of this group with respect to the surface plane (48° ± 2°) at room temperature. Low-energy electron diffraction (LEED) shows a p(2√13x2√13)R13° superstructure with only one domain, which breaks the mirror symmetry of the substrate and, thus, induces global chirality to the surface. Temperature-programmed XPS (TP-XPS) and temperature-programmed desorption (TPD) experiments indicate that the zwitterionic form converts into the anionic species (alaninate) at 293 K. The latter desorbs/decomposes between 435 K and 445 K.

Influence of temperature during grain filling on gluten viscoelastic properties and gluten protein composition

BACKGROUND The aim of this study was to investigate the effects of low to moderate temperatures on gluten functionality and gluten protein composition. Four spring wheat cultivars were grown in climate chambers with three temperature regimes (day/night temperatures of 13/10, 18/15 and 23/20 °C) during grain filling. RESULTS The temperature strongly influenced grain weight and protein content. Gluten quality measured by maximum resistance to extension (Rmax) was highest in three cultivars grown at 13 °C. Rmax was positively correlated with the proportion of sodium dodecyl sulfate-unextractable polymeric proteins (%UPP). The proportions of ω-gliadins and D-type low-molecular-weight glutenin subunits (LMW-GS) increased and the proportions of α- and γ-gliadins and B-type LMW-GS decreased with higher temperature, while the proportion of high-molecular-weight glutenin subunits (HMW-GS) was constant between temperatures. The cultivar Berserk had strong and constant Rmax between the different temperatures. CONCLUSION Constant low temperature, even as low as 13 °C, had no negative effects on gluten quality. The observed variation in Rmax related to temperature could be explained more by %UPP than by changes in the proportions of HMW-GS or other gluten proteins. The four cultivars responded differently to temperature, as gluten from Berserk was stronger and more stable over a wide range of temperature

Increases in the longevity of desiccation-phase developing rice seeds: response to high temperature drying depends on harvest moisture content

• Background and Aims Earlier studies have suggested that the drying conditions routinely used by genebanks may not be optimal for subsequent seed longevity. The aim of this study was to compare the effect of hot-air drying with low temperature drying on subsequent seed longevity for 20 diverse rice accessions and to consider how factors related to seed production history might influence the results. • Methods Seeds were produced according to normal regeneration procedures at IRRI. They were harvested at different times (harvest date and days after anthesis (DAA), once for each accession) and dried either in a drying room (DR; 15% RH, 15°C), or in a flat-bed heated-air batch dryer (BD; 45°C, 8 h d-1) for up to 6 daily cycles followed by drying in the DR. Relative longevity was assessed by storage at 10.9% moisture content (m.c.) and 45°C. • Key Results Initial drying in the BD resulted in significantly greater longevity compared with the DR for 14 accessions (seed lots): the period of time for viability to fall to 50% for seeds dried in the BD as a percentage of that for seeds dried throughout in the DR varied between 1.3 and 372.2% for these 14 accessions. The seed lots that responded the most were harvested earlier in the season and at higher moisture content. Drying in the BD did not reduce subsequent longevity compared with DR drying for any of the remaining accessions. • Conclusions Seeds harvested at a m.c. where, according to the moisture desorption isotherm, they could still be metabolically active (>16.2%), may be in the first stage of the post-mass maturity, desiccation phase of seed development and able to increase longevity in response to hot-air drying. The genebank standards regarding seed drying for rice and, perhaps, for other tropical species should be reconsidered.

Influence of temperature on the composition and polymerization of gluten proteins during grain filling in spring wheat (Triticum aestivum L.)

One Norwegian and one UK spring wheat cultivar, Bjarne and Cadenza, respectively, were grown in climate chambers to investigate the effects of lower to moderate temperatures during grain filling on the gluten quality. Two experiments were carried out with weekly fertilization until anthesis, while post-anthesis fertilization was applied in a third experiment. The proportions of different gluten proteins were affected by temperature in a similar manner for both cultivars when grown without post-anthesis fertilization. However, whereas low temperature strongly decreased %UPP for Cadenza, Bjarne had high %UPP at all temperature regimes. The results indicated that the assembly of glutenin polymers in Bjarne was less sensitive to variation in temperature than in Cadenza. Thus, our results suggested that the temperature influenced the proportion of different gluten proteins in both cultivars, while its effects on the assembly of the glutenin polymers were cultivar dependent. The duration of grain filling was longer at the lower temperatures, and this was associated with increased grain weight. Temperature had little effect on the amount of protein accumulated per grain, thus the proportion of proteins was strongly decreased at lower temperatures. This was to some extent, but not fully counteracted by post-anthesis fertilization.

Ball milling as an effective route for the preparation of doped bornite: synthesis, stability and thermoelectric properties

Bornite, Cu5FeS4, is a naturally-occuring mineral with an ultralow thermal conductivity and potential for thermoelectric power generation. We describe here a new, easy and scalable route to synthesise bornite, together with the thermoelectric behaviour of manganese-substituted derivatives, Cu5Fe1-xMnxS4 (0 ≤ x ≤ 0.10). The electrical and thermal transport properties of Cu5Fe1-xMnxS4 (0 ≤ x ≤ 0.10), which are p-type semiconductors, were measured from room temperature to 573 K. The stability of bornite was investigated by thermogravimetric analysis under inert and oxidising atmospheres. Repeated measurements of the electrical transport properties confirm that bornite is stable up to 580 K under an inert atmosphere, while heating to 890 K results in rapid degradation. Ball milling leads to a substantial improvement in the thermoelectric figure of merit of unsusbtituted bornite (ZT = 0.55 at 543 K), when compared to bornite prepared by conventional high-temperature synthesis (ZT < 0.3 at 543 K). Manganese-substituted samples have a ZT comparable to that of unsubstituted bornite.

The cooler side of mycorrhizas: their occurrence and functioning at low temperatures

Mycorrhizal associations occur in a range of habitats in which soils are subject to low temperature (≤15 °C) for a significant part of the year. Despite this, most of our understanding of mycorrhizal fungi and their interactions with their plant hosts is based on physiological investigations conducted in the range 20–37 °C using fungi of temperate origin. Comparatively little consideration has been given to the cold edaphic conditions in which many mycorrhizas survive and prosper, and the physiological and ecological consequences of their low temperature environments. In this review, we consider the distribution and persistence of arbuscular and ectomycorrhizal mycorrhizal associations in cold environments and highlight progress in understanding adaptations to freezing resistance and nutrient acquisition at low temperature in mycorrhizal fungi.

Temperature regulation of extracellular proteases in ectomycorrhizal fungi (Hebeloma spp.) grown in axenic culture

Strains of Hebeloma representative of different climatic zones were grown in axenic culture at either 2 °C and 22° or 6° and 22°. Culture filtrates were assayed for proteolytic activity using FITC labelled BSA as a substrate. Assays were run between 0–37°. Growth at low temperature induced greater proteolytic activity (g−1 D.W. mycelium). Many of the strains produced protease(s) which retained significant activity at temperatures as low as 0°, and a thermal optimum between 0–6° with a second optimum at higher temperature. The results are discussed in relation the nutrient acquisition potential of ectomycorrhizal fungi at low temperature and the contribution such cold active proteases might make to the soil enzyme pool.

The effect of temperature and inorganic phosphorus supply on growth and acid phosphatase production in arctic and temperate strains of ectomycorrhizal Hebeloma spp. in axenic culture

Acid phosphatase production by 12 Hebeloma strains was usually derepressed when inorganic phosphorus in the growth medium was limited, but appeared to be constitutive in some strains. At low temperatures (≤ 12°) arctic strains produced more extracellular and wall-bound acid phosphatase, yet grew more slowly than the temperate strains. We suggest that low growth rates in arctic strains may be a physiological response to cold whereby resources are diverted into carbohydrate accumulation for cryoprotection. At near freezing temperatures, increased extracellular phosphatase production may compensate for a loss of enzyme activity at low temperature and serve to hydrolyse organic phosphorus in frozen soil over winter.

Sonogashira coupling on an extended gold surface in vacuo: reaction of phenylacetylene with iodobenzene on Au(111)

Temperature-programmed reaction measurements supported by scanning tunneling microscopy have shown that phenylacetylene and iodobenzene react on smooth Au(111) under vacuum conditions to yield biphenyl and diphenyldiacetylene, the result of homocoupling of the reactant molecules. They also produce diphenylacetylene, the result of Sonogashira cross-coupling, prototypical of a class of reactions that are of paramount importance in synthetic organic chemistry and whose mechanism remains controversial. Roughened Au(111) is completely inert toward all three reactions, indicating that the availability of crystallographically well-defined adsorption sites is crucially important. High-resolution X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy show that the reactants are initially present as intact, essentially flat-lying molecules and that the temperature threshold for Sonogashira coupling coincides with that for C−I bond scission in the iodobenzene reactant. The fractional-order kinetics and low temperature associated with desorption of the Sonogashira product suggest that the reaction occurs at the boundaries of islands of adsorbed reactants and that its appearance in the gas phase is rate-limited by the surface reaction. These findings demonstrate unambiguously and for the first time that this heterogeneous cross-coupling chemistry is an intrinsic property of extended, metallic pure gold surfaces: no other species, including solvent molecules, basic or charged (ionic) species are necessary to mediate the process.

Carcases and mites

Mites are involved in the decomposition of animal carcases and human corpses at every stage. From initial decay at the fresh stage until dry decomposition at the skeletal stage, a huge diversity of Acari, including members of the Mesostigmata, Prostigmata, Astigmata, Endeostigmata, Oribatida and Ixodida, are an integral part of the constantly changing food webs on, in and beneath the carrion. During the desiccation stage in wave 6 of M,gnin's system, mites can become the dominant fauna on the decomposing body. Under conditions unfavourable for the colonisation of insects, such as concealment, low temperature or mummification, mites might become the most important or even the only arthropods on a dead body. Some mite species will be represented by a few specimens, whereas others might build up in numbers to several million individuals. Astigmata are most prominent in numbers and Mesostigmata in diversity. More than 100 mite species and over 60 mite families were collected from animal carcases, and around 75 species and over 20 families from human corpses.

Analysis of the sulfate-reducing bacterial and methanogenic archaeal populations in contrasting Antarctic sediments

The distribution and activity of communities of sulfate-reducing bacteria (SRB) and methanogenic archaea in two contrasting Antarctic sediments were investigated. Methanogenesis dominated in freshwater Lake Heywood, while sulfate reduction dominated in marine Shallow Bay. Slurry experiments indicated that 90% of the methanogenesis in Lake Heywood was acetoclastic. This finding was supported by the limited diversity of clones detected in a Lake Heywood archaeal clone library, in which most clones were closely related to the obligate acetate-utilizing Methanosaeta concilii. The Shallow Bay archaeal clone library contained clones related to the C-1-utilizing Methanolobus and Methanococcoides and the H-2-utilizing Methanogenium. Oligonucleotide probing of RNA extracted directly from sediment indicated that archaea represented 34% of the total prokaryotic signal in Lake Heywood and that Methanosaeta was a major component (13.2%) of this signal. Archaea represented only 0.2% of the total prokaryotic signal in RNA extracted from Shallow Bay sediments. In the Shallow Bay bacterial clone library, 10.3% of the clones were SRB-like, related to Desulfotalea/Desulforhopalus, Desulfofaba, Desulfosarcina, and Desulfobacter as well as to the sulfur and metal oxidizers comprising the Desulfuromonas cluster. Oligonucleotide probes for specific SRB clusters indicated that SRB represented 14.7% of the total prokaryotic signal, with Desulfotalea/Desulforhopalus being the dominant SRB group (10.7% of the total prokaryotic signal) in the Shallow Bay sediments; these results support previous results obtained for Arctic sediments. Methanosaeta and Desulfotalea/Desulforhopalus appear to be important in Lake Heywood and Shallow Bay, respectively, and may be globally important in permanently low-temperature sediments.

Growth, yield and development of strawberry cv. 'Elsanta' under novel photoselective film clad greenhouses

Film greenhouse claddings are typically used to protect horticultural crops from low temperature and high rainfall conditions. However, a range of novel plastic films have been developed which filter specific radiation wavelengths with the aim of providing the grower with greater control of crop growth and development. A replicated experiment was conducted in 8 small experimental greenhouses, covered with different photoselective films characterised by a range of red/far-red ratios and PAR transmissions to study their effects on the growth, yield and quality of the strawberry cv. 'Elsanta'. Marketable yield per plant was 51% greater under the film with the highest light transmission (control) compared with the lower light transmission films. Similarly, unmarketable fruit number and average non-marketable individual fruit weight per plant was lowest under films with higher light transmissions and higher under lower light transmission films. Cropping duration was longer under films with high R/FR. Also plants under high R/FR were more compact (due to shorter petiole lengths) compared to plants grown under low R/FR. The results are discussed in relation to the increased use of photoselective films in protected horticulture and the need for higher quality fruit and vegetables.

Immobilisation of eta(3)-allyidicarbonyl complexes of Mo-II with bidentate nitrogen ligands within aluminium-pillared clays

Molybdenum(II) complexes [MOX(CO)(2)(eta(3)-allyl)(CH3CN)(2)] (X = Cl or Br) were encapsulated in an aluminium-pillared natural clay or a porous clay heterostructure and allowed to react with bidentate diimine ligands. All the materials obtained were characterised by several solid-state techniques. Powder XRD, and Al-27 and Si-29 MAS NMR were used to investigate the integrity of the pillared clay during the modification treatments. C-13 CP MAS NMR, FTIR, elemental analyses and low-temperature nitrogen adsorption showed that the immobilisation of the precursor complexes was successful as well as the in situ ligand-substitution reaction. The new complex [MoBr(CO)(2)(eta(3)-allyl)(2-aminodipyridyl)] was characterised by single-crystal X-ray diffraction and spectroscopic techniques, and NMR studies were used to investigate its fluxional behaviour in solution. The prepared materials are active for the oxidation of cis-cyclooctene using tert-butyl hydroperoxide as oxidant, though the activity of the isolated complexes is higher. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).