Thermal stability of mixed-cation alpha-sialon ceramics

A series of alpha-sialon (alpha') compositions containing mixed stabilising cations were prepared, by introducing additional CaO to a basic Sm alpha-sialon compositions. The thermal stability of these Sm-Ca-containing alpha-sialon phases was investigated using XRD, SEM and EDXS techniques. It was found that the addition of calcium into the Sm alpha-sialon systems greatly improved the stability of the alpha-sialon phases. Calcium was found to be incorporated into the alpha-sialon structure, coexistent with the samarium, and partitioning of the calcium and samarium was observed between the alpha' phase and grain boundary phases. This indicates a technique which may be used to improve the thermal stability of the alpha' phase while maintaining good refractory phases at the gialon grain boundaries. (C) 2003 Elsevier Science B.V. All rights reserved.

Thermal ecology and structural habitat use of two sympatric lizards (Carlia vivax and Lygisaurus foliorum) in subtropical Australia

The thermal ecology and structural habitat use of two closely related sympatric lizards, Carlia vivax (de Vis) and Lygisaurus foliorum de Vis, were examined in an open sclerophyll forest in subtropical Australia. Comparable mean body temperatures (T-b) and habitat temperatures (T-hab) at the point of capture were recorded for both species. However, sex- related differences in the thermal variables for C. vivax, with females displaying higher temperatures than males, resulted in some significant differences in T-b and T-hab between the species. Variation in T-b and T-hab within and between species was unrelated to time of capture. The difference in T-hab within C. vivax suggested that females were selecting warmer thermal environments than males. Both C. vivax and L. foliorum used most structural features of their habitat randomly as indicated by a similarity in canopy, shrub, ground, log and litter cover and litter depth between habitat surveys and random surveys. However, C. vivax displayed a preference for ground vegetation (height

Dormancy release in Lolium rigidum seeds is a function of thermal after-ripening time and seed water content

Dormancy release in seeds of Lolium rigidum Gaud. (annual ryegrass) was investigated in relation to temperature and seed water content. Freshly matured seeds were collected from cropping fields at Wongan Hills and Merredin, Western Australia. Seeds from Wongan Hills were equilibrated to water contents between 6 and 18% dry weight and after-ripened at constant temperatures between 9 and 50degreesC for up to 23 weeks. Wongan Hills and Merredin seeds at water contents between 7 and 17% were also after-ripened in full sun or shade conditions. Dormancy was tested at regular intervals during after-ripening by germinating seeds on agar at 12-h alternating 15degreesC (dark) and 25degreesC (light) periods. Rate of dormancy release for Wongan Hills seeds was a positive linear function of after-ripening temperature above a base temperature (T-b) of 5.4degreesC. A thermal after-ripening time model for dormancy loss accounting for seed moisture in the range 6-18% was developed using germination data for Wongan Hills seeds after-ripened at constant temperatures. The model accurately predicted dormancy release for Wongan Hills seeds after-ripened under naturally fluctuating temperatures. Seeds from Merredin responded similarly but had lower dormancy at collection and a faster rate of dormancy release in seeds below 9% water content.

pH dependence of the progression in NMR T-2 relaxation times in post-mortem muscle

Continuous NMR T-2 relaxation measurements were carried out on seven rabbit longissimus muscle samples in the period from 25 min to 28 h post-mortem at 200 MHz for H-1. To display differences in post-mortern pH progress and extent of changes in water characteristics during conversion of muscle to meat, three of the seven animals were pre-slaughter injected with adrenaline (0.5 mg/kg live weight 4 h before sacrifice) to differentiate muscle glycogen stores at the time of slaughter. Distributed analysis of T-2 data displayed clear differences in the characteristics of the various transverse relaxation components dependent on progress in pH, as did the water-holding capacity of samples 24 h postmortem. This reveals a pronounced effect of the progressive change in pH on the subsequent development in physical/chemical states of water during the conversion of muscle to meat. Finally, the relaxation characteristics are discussed in relation to supposed post-mortem processes of protein denaturation.

An equivalent algorithm for simulating thermal effects of magma intrusion problems in porous rocks

An equivalent algorithm is proposed to simulate thermal effects of the magma intrusion in geological systems, which are composed of porous rocks. Based on the physical and mathematical equivalence, the original magma solidification problem with a moving boundary between the rock and intruded magma is transformed into a new problem without the moving boundary but with a physically equivalent heat source. From the analysis of an ideal solidification model, the physically equivalent heat source has been determined in this paper. The major advantage in using the proposed equivalent algorithm is that the fixed finite element mesh with a variable integration time step can be employed to simulate the thermal effect of the intruded magma solidification using the conventional finite element method. The related numerical results have demonstrated the correctness and usefulness of the proposed equivalent algorithm for simulating the thermal effect of the intruded magma solidification in geological systems. (C) 2003 Elsevier B.V. All rights reserved.

Field assessment of thermal after-ripening time for dormancy release prediction in Lolium rigidum seeds

Dormancy release was studied in four populations of annual ryegrass (Lolium rigidum) seeds to determine whether loss of dormancy in the field can be predicted from temperature alone or whether seed water content (WC) must also be considered. Freshly matured seeds were after-ripened at the northern and southern extremes of the Western Australian cereal cropping region and at constant 37degreesC. Seed WC was allowed to fluctuate with prevailing humidity, but full hydration was avoided by excluding rainfall. Dormancy was measured regularly during after-ripening by germinating seeds with 12-hourly light or in darkness. Germination was lower in darkness than in light/dark and dormancy release was slower when germination was tested in darkness. Seeds were consistently drier, and dormancy release was slower, during after-ripening at 37degreesC than under field conditions. However, within each population, the rate of dormancy release in the field (north and south) in terms of thermal time was unaffected by after-ripening site. While low seed WC slowed dormancy release in seeds held at 37degreesC, dormancy release in seeds after-ripened under Western Australian field conditions was adequately described by thermal after-ripening time, without the need to account for changes in WC elicited by fluctuating environmental humidity.

Thermal Characteristics of Polybia scutellaris Nests (Hymenoptera: Vespidae) Using Computational Fluid Dynamics: A Possible Adaptation to Tropical Climates

Polybia scutellaris constructs huge nests characterized by numerous spinal projections on the surface. We investigated the thermal characteristics of P scutellaris nests in order to determine whether their nest temperature is homeothermically maintained and whether the spines play a role in the thermoregulation of the nests. In order to examine these hypotheses, we measured the nest temperature in a active nest and in an abandoned nest. The temperature in the active nest was almost stable at 27 degrees C, whereas that of the abandoned nest varied with changes in the ambient temperature, suggesting that nest temperature was maintained by the thermogenesis of colony individuals. In order to predict the thermal properties of the spines, a numerical simulation was employed. To construct a 3D-model of a P scutellaris nest, the nest architecture was simplified into an outer envelope and the surface spines, for both of which the initial temperature was set at 27 degrees C. The physical properties of the simulated nest were regarded to be those of wood since the nest of this species is constructed from plant materials. When the model was exposed to cool air (12 degrees C), the temperature was lower in the models with more spines. On the other hand, when the nest was heated (42 degrees C), the temperature increase was smaller in models with more spines. It is suggested that the spines act as a heat radiator, not as an insulator, against the changes in ambient temperature.

Purification and biochemical characterization of a mycelial glucose- and xylose-stimulated beta-glucosidase from the thermophilic fungus Humicola insolens

A mycelial beta-glucosidase from the thermophilic mold Humicola insolens was purified and biochemically characterized. The enzyme showed carbohydrate content of 21% and apparent molecular mass of 94 kDa, as estimated by gel filtration. Sodium dodecyl sulfate polyacrylamide gel electrophoresis analysis showed a single polypeptide band of 55 kDa, suggesting that the native enzyme was a homodimer. Mass spectrometry analysis showed amino acid sequence similarity with a P-glucosidase from Humicola grisea var. thermoidea, with about 22% coverage. Optima of temperature and pH were 60 degrees C and 6.0-6.5, respectively. The enzyme was stable up to I h at 50 degrees C and showed a half-life of approximately 44 min at 55 degrees C. The beta-glucosidase hydrolyzed cellobiose, lactose, p-nitrophenyl-beta-D-glucopyranoside, p-nitrophenyl-beta-D-fucopyranoside, p-nitrophenyl-beta-D-xylopyranoside, p-nitrophenyl-beta-D-galactopyranoside, o-nitrophenyl-beta-D-galactopyranoside, and salicin. Kinetic studies showed that p-nitrophenyl-beta-D-fucopyranoside and cellobiose were the best enzyme substrates. Enzyme activity was stimulated by glucose or xylose at concentrations up to 400 mM, with maximal stimulatory effect (about 2-fold) around 40 mM. The high catalytic efficiency for the natural substrate, good thermal stability, strong stimulation by glucose or xylose, and tolerance to elevated concentrations of these monosaccharides qualify this enzyme for application in the hydrolysis of cellulosic materials. (C) 2009 Elsevier Ltd. All rights reserved.

Thermal Characteristics of the Mud Nests of the Social Wasp Polybia spinifex (Hymenoptera; Vespidae)

The thermal characteristics of mud nests of Polybia spinifex were investigated by measuring internal and surface temperatures of the nests. The nests had a layer of mud envelope and consisted of mud with fine sand particles. The envelope had a vertically long slit-like entrance hole. The mud nests had high thermal conductivities (0.51-0.67 W/(m degrees C)) comparable to brick, rather than insulation materials of wasps` nests such as paper and wood. It was revealed that the long entrance radiated more heat from the thereto-image. The rate of thermal radiation (emissivity) of the nest surface was 0.80, and the value was similar to that of sand. The internal temperatures of the nests were high from top (T(n1), temperature difference between ambient temperature (T(a)) was 10 degrees C) to bottom (T(n3), difference, 5 degrees C) at noon. On the other hand, the temperature distributions were reversed during the night. Temperature T(n1) was lower by 1 degrees C than T(a), possibly from nightly dew on the top surface, whereas, at the middle point (T(n2),) and T(n3), temperatures were higher by 1 degrees C compared to T(a). Temperature fluctuations (ranges between maximum and minimum temperature) at T(n2) and T(n3) were similar to that of T(a), whereas the values at T(n1) and T(s) were higher than that of T(a).

Pt-RuO(2) electrodes prepared by thermal decomposition of polymeric precursors as catalysts for direct methanol fuel cell applications

The electrocatalytic activity of Pt and RuO(2) mixed electrodes of different compositions towards methanol oxidation was investigated. The catalysts were prepared by thermal decomposition of polymeric precursors and characterized by energy dispersive X-ray, scanning electronic microscopy, X-ray diffraction and cyclic voltammetry. This preparation method allowed obtaining uniform films with controlled stoichiometry and high surface area. Cyclic voltammetry experiments in the presence of methanol showed that mixed electrodes decreased the potential peak of methanol oxidation by approximately 100 mV (RHE) when compared to the electrode containing only Pt. In addition, voltammetric experiments indicated that the Pt(0.6)Ru(0.4)O(y) electrode led to higher oxidation current densities at lower potentials. Chronoamperometry experiments confirmed the contribution of RuO(2) to the catalytic activity as well as the better performance of the Pt(0.6)Ru(0.4)O(y) electrode composition. Formic acid and CO(2) were identified as being the reaction products formed in the electrolysis performed at 400 and 600 mV. The relative formation of CO(2) was favored in the electrolysis performed at 400 mV (RHE) with the Pt(0.6)Ru(0.4)O(y) electrode. The presence of RuO(2) in Pt-Ru-based electrodes is important for improving the catalytic activity towards methanol electrooxidation. Moreover, the thermal decomposition of polymeric precursors seems to be a promising route for the production of catalysts applicable to DMFC. (C) 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Quantification of carbamazepine, carbamazepine-10,11-epoxide, phenytoin and phenobarbital in plasma samples by stir bar-sorptive extraction and liquid chromatography

A sensitive and reproducible stir bar-sorptive extraction and high-performance liquid chromatography-UV detection (SBSE/HPLC-UV) method for therapeutic drug monitoring of carbamazepine, carbamazepine-10,11-epoxide, phenytoin and phenobarbital in plasma samples is described and compared with a liquid:liquid extraction (LLE/HPLC-UV) method. Important factors in the optimization of SBSE efficiency such as pH, extraction time and desorption conditions (solvents, mode magnetic stir, mode ultrasonic stir, time and number of steps) assured recoveries ranging from 72 to 86%, except for phenytoin (62%). Separation was obtained using a reverse phase C-18 column with UV detection (210 nm). The mobile phase consisted of water: acetonitrile (78:22, v/v). The SBSE/HPLC-UV method was linear over a working range of 0.08-40.0 mu g mL(-1) for carbamazepine, carbamazepine-10,11-epoxide and phenobarbital and 0.125-40.0 mu g mL(-1) for phenytoin, The intra-assay and inter-assay precision and accuracy were studied at three concentrations (1.0, 4.0 and 20.0 mu g mL(-1)). The intra-assay coefficients of variation (CVs) for all compounds were less than 8.8% and all inter-CVs were less than 10%. Limits of quantification were 0.08 mu g mL(-1) for carbamazepine, carbamazepine-10,11-epoxide and phenobarbital and 0.125 mu g mL(-1) for phenytoin. No interference of the drugs normally associated with antiepileptic drugs was observed. Based on figures of merit results, the SBSE/HPLC-UV proved adequate for antiepileptic drugs analyses from therapeutic levels. This method was successfully applied to the analysis of real samples and was as effective as the LLE/HPLC-UV method. (c) 2008 Elsevier B.V. All rights reserved.

The use of electrospray ionization tandem mass spectrometry on the structural characterization of novel asymmetric metallo-organic supermolecules, based on pentafluorophenylporphyrins and ruthenium complexes

The novel asymmetric metallo-organic triads cis- and trans-[B(4-py)BPFPH(2){Ru(3)O(Ac)(6)(py)(2)}(Ru(bpy)(2)Cl}](PF(6))(2) (5a,b) for which cis- and trans-B(4-py)BPFPH(2)=5,10-bis(pentafluorophenyl)-15,20-bis(4-pyridyl)porphyrin and 5,15-bis(pentafluorophenyl)-10,20-bis(4-pyridyl)porphyrin, respectively; Ac = acetate; py = pyridine and bpy = 2,2`-bipyridine, as well as their corresponding monosubstituted dyads cis- and trans-[B(4-py)BPFPH(2){Ru(3)O(Ac)(6)(py)(2)}]PF(6) (4a,b) have been structurally characterized via electrospray ionization mass spectrometry (ESI-MS and ESI-MS/MS). The ESI-MS of dyads 4a,b display two characteristic Ru-multicomponent clusters of isotopologue ions corresponding to singly charged ions 4a,b(+) of m/z 1629 and doubly charged ions [4a,b+H](2+) of m/z 815 and the triads 5a,b are detected by ESI-MS as the intact doubly charged cluster of isotopologue ions of m/z 1039 [5a,b](2+). The ESI-MS/MS of 4a,b(+), [4a,b+H](2+) and [5a,b](2+) reveal characteristic dissociation pathways, which confirm the structural assignments providing additional information on the intrinsic binding strengths of the gaseous ions. Although the gas-phase behavior of each pair of isomers was rather similar, the less symmetric dyads 4a,b are distinguished via the (1)H NMR spectral profile of the pyrrolic signals. Exploratory photophysical assays have shown that both modifying motifs alter the porphyrinic core emission profile, opening the possibility to use these asymmetric systems as photophysical devices. (C) 2008 Elsevier Ltd. All rights reserved.

Dendrimer intercalation in layered double hydroxides

New organic/inorganic (O/I) hybrid assemblies based on Layered Double Hydroxide (LDH) with polyamide amine dendrimer (PAMAM, generation -0.5 and generation +0.5) were prepared by two different routes using either the direct coprecipitation at constant pH or the anion exchange procedure in double surfactant S(+)S(-) phases. The obtained materials were characterized by means of powder X-ray diffraction, thermal gravimetric analysis associated with mass spectrometry, and Fourier-transform infrared spectroscopy. X-ray powder diffraction pattern of the O/I LDH assembly exhibit characteristic profiles of LDH-based materials with basal spacing depending on the nature of the dendrimer. Indeed, for both synthetic procedures, interleaved PAMAM -0.5 gives rise to an interlayer space in agreement with a perpendicular molecular arrangement against the layer of the host structure. For PAMAM+0.5, considering its spherical dimension, a much smaller basal spacing was observed. This observation was interpreted as shrinkage of the molecule to accommodate the interlayer LDH gap, which was rendered possible by the bond angle twisting within PAMAM-0.5. FTIR spectra confirm the presence of both moieties inside both Zn(2)Al/PAMAM G-0.5 and Zn(2)Al/PAMAM G+0.5 assemblies. Finally, thermal analysis associated with mass spectrometry confirm this composition, and in situ temperature XRD data reveal that the highly constrained arrangement for the generation +0.5 is not accompanied by a gain in thermal structural stability; in fact, the assembly prepared from PAMAM -0.5 is more stable. Both O/I PAMAM LDH assemblies constitute well-defined materials which are candidate for catalytic applications.

Characterization and voltammetric behavior of Pt(y)Mo(z)O(x)/C electrodes prepared by the thermal decomposition of polymeric precursors

Carbon-supported catalysts containing platinum and molybdenum oxide are prepared by thermal decomposition of polymeric precursors. The Pt(y)Mo(z)O(x)/C materials are characterized by energy dispersive X-ray spectroscopy, transmission electron microscopy, and X-ray diffraction. The catalysts present a well-controlled stoichiometry and nanometric particles. Molybdenum is present mainly as the MoO(3) orthorhombic structure, and no Pt alloys are detected. The voltammetric behavior of the electrodes is investigated; a correlation with literature results for PtMo/C catalysts prepared by other methods is established. The formation of soluble species and the aging effect are discussed. (C) 2009 Elsevier B.V. All rights reserved.

Potential of Amaranthus cruentus BRS Alegria in the production of flour, starch and protein concentrate: chemical, thermal and rheological characterization

BACKGROUND: Amaranth is a little-known culture in Brazilian agriculture. Amaranthus cruentus BRS Alegria was the first cultivar recommended by Embrapa for the soil of the Brazilian scrubland. In order to evaluate the potential of this species in the production of flour, starch and protein concentrates, the latter products were obtained from A. cruentus BRS Alegria seeds, characterized and compared with the products obtained from the A. caudatus species cultivated in its soil of origin. RESULTS: The seeds of A. cruentus BRS Alegria furnished high-purity starch and flour with significant content of starch, proteins, and lipids. The starch and flour of this species presented higher gelatinization temperatures and formed stronger gels upon cooling compared with those obtained from the A. caudatus species. This is due to their greater amylose content and a difference in the composition of the more important fatty acids, such as stearic, oleic and linoleic acids, which indicates that they have greater heat stability. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis and differential scanning calorimetry revealed the presence of albumins, globulins, glutelins and prolamins in the protein concentrate, which was obtained as a byproduct of starch production. CONCLUSION: Amaranthus cruentus BRS Alegria has potential application in the production of flour, starch and protein concentrates, with interesting characteristics for use as food ingredients. (C) 2010 Society of Chemical Industry