Phase relations in the system Ta-Rh-O and thermodynamic properties of TaRhO4

Phase relations in the system Ta-Rh-O were determined by analysis of quenched samples corresponding to thirteen compositions inside the ternary triangle after equilibration at 1273 K. All the Ta-Rh alloys were found to be in equilibrium with Ta2O5. Only one ternary oxide TaRhO4 was detected. Based on phase relations in the ternary system, a solid-state electrochemical cell, incorporating calcia-stabilized zirconia as the electrolyte, was designed to measure the standard Gibbs energy of formation (Delta G degrees, J mol(-1)) of TaRhO4 in the temperature range from 900 to 1300 K. For the reaction, 1/2 beta-Ta2O5 + 1/2 Rh2O3(ortho) -> TaRhO4 Delta G degrees = -42993 + 5.676T (+/- 85) The calculated decomposition temperatures of TaRhO4 are 1644 +/- 5K in pure O-2 and 1543 +/- 5K in air at a total pressure p(o) = 0.1 MPa. Thermodynamic properties of TaRhO4 at 298.15K have been evaluated from the results. The limited experimental thermodynamic data for Rh-rich alloys available in the literature are in fair accord with Miedema's model. The Gibbs energies of formation of the different phases in the binary system Ta-Rh were estimated based on these inputs, consistent with the binary phase diagram. Based on the thermodynamic information on the stability of various phases, an oxygen potential diagram for the system Ta-Rh-O at 1273K was constructed. Also presented are temperature-composition diagrams for the ternary system at constant oxygen partial pressures (po(2)/p(o) = 0.212 and 10(-6)) calculated form the basic data.

Structure and properties of two component hydrogels comprising lithocholic acid and organic amines

We demonstrate the aptitude of supramolecular hydrogel formation using simple bile acid such as lithocholic acid in aqueous solution in the presence of various dimeric or oligomeric amines. By variation of the choice of the amines in such mixtures the gelation properties could be modulated. However, the replacement of lithocholic acid (LCA) by cholic acid or deoxycholic acid resulted in no hydrogel formation. FT-IR studies confirm that the carboxylate and ammonium residues of the two components are involved in the salt (ion-pair) formation. This promotes further assembly of the components reinforced by a continuous hydrogen bonded network leading to gelation. Electron microscopy shows the morphology of the internal organization of gels of two component systems which also depends significantly on the amine part. Variation of the amine component from the simple 1,2-ethanediamine (EDA) to oligomeric amines in such gels of lithocholic acid changes the morphology of the assembly from long one-dimensional nanotubes to three-dimensional complex structures. Single crystal X-ray diffraction analysis with one of the amine-LCA complexes suggested the motif of fiber formation where the amines interact with the carboxylate and hydroxyl moieties through electrostatic forces and hydrogen bonding. From small angle neutron scattering study, it becomes clear that the weak gel from LCA-EDA shows scattering oscillation due to the presence of non-interacting nanotubules while for gels of LCA with oligomeric amines the individual fibers come together to form complex three-dimensional organizations of higher length scale. The rheological properties of this class of two component system provide clear evidence that the flow behavior can be modulated varying the acid-amine ratio.

Effect of substrate temperature on the physical properties of dc magnetron sputtered CuAlO2 films

Copper aluminum oxide films were prepared by direct current (dc) reactive magnetron sputtering under various substrate temperatures in the range of 303–648 K and systematically studied their physical properties. The physical properties of the films were strongly affected by the substrate temperature. The films formed at substrate temperatures <373 K were amorphous while those deposited at higher substrate temperatures (≥373 K) were polycrystalline in nature. The electrical properties of the films enhanced with substrate temperature due to the improved crystallinity. The Hall mobility of 9.4 cm2/V s and carrier concentration of 3.5 × 1017 cm−3 were obtained at the substrate temperature of 573 K. The optical band gap of the films decreased from 3.87 to 3.46 eV with the increase of substrate temperature from 373 to 573 K.

Synthesis, Characterization, and Photocatalytic Properties of ZrMo2O8

ZrMo2O8 was synthesized via two routes, namely, the traditional solid-state method and the solution combustion method. The compounds were characterized by powder X-ray diffraction, UV−visible spectroscopy, scanning electron microscopy, and transmission electron microscopy. The crystals belong to a trigonal crystal system, space group P 1c (No. 163) with a = 10.1391(6) Å, c = 11.7084(8) Å, and Z = 6. The band gap of the compounds was around 2.7 eV, and DFT calculations suggest the indirect nature of the band gap. The irregular MoO4 tetrahedra create a dipole and inhibit the process of electron−hole recombination, thereby making the material photoactive. The photocatalytic activity of the compounds prepared by both routes has been investigated for the degradation of various dyes under UV irradiation, and this showed the specificity of the compounds towards the degradation of non-anthraquinonic dyes.

Side Chain Structure Determines Unique Physiologic and Therapeutic Properties of norUrsodeoxycholic Acid in Mdr2(-/-) Mice

24-norursodeoxycholic acid (norUDCA), a side chain-modified ursodeoxycholic acid derivative, has dramatic therapeutic effects in experimental cholestasis and may be a promising agent for the treatment of cholestatic liver diseases. We aimed to better understand the physiologic and therapeutic properties of norUDCA and to test if they are related to its side chain length and/or relative resistance to amidation. For this purpose, Mdr2-/- mice, a model for sclerosing cholangitis, received either a standard diet or a norUDCA-, tauro norursodeoxycholic acid (tauro- norUDCA)-, or di norursodeoxycholic acid (di norUDCA)-enriched diet. Bile composition, serum biochemistry, liver histology, fibrosis, and expression of key detoxification and transport systems were investigated. Direct choleretic effects were addressed in isolated bile duct units. The role of Cftr for norUDCA-induced choleresis was explored in Cftr-/- mice. norUDCA had pharmacologic features that were not shared by its derivatives, including the increase in hepatic and serum bile acid levels and a strong stimulation of biliary HCO3- -output. norUDCA directly stimulated fluid secretion in isolated bile duct units in a HCO3- -dependent fashion to a higher extent than the other bile acids. Notably, the norUDCA significantly stimulated HCO 3- -output also in Cftr-/- mice. In Mdr2-/- mice, cholangitis and fibrosis strongly improved with norUDCA, remained unchanged with tauro- norUDCA, and worsened with di norUDCA. Expression of Mrp4, Cyp2b10, and Sult2a1 was increased by norUDCA and di norUDCA, but was unaffected by tauro- norUDCA. Conclusion:The relative resistance of norUDCA to amidation may explain its unique physiologic and pharmacologic properties. These include the ability to undergo cholehepatic shunting and to directly stimulate cholangiocyte secretion, both resulting in a HCO3- -rich hypercholeresis that protects the liver from cholestatic injury.

Fluorite and Mixed-Metal Kagome-Related Topologies in Metal-Organic Framework Compounds: Synthesis, Structure, and Properties

Two new three-dimensional metal-organic frameworks (MOFs) [Mn-2(mu(3)-OH)(H2O)(2)(BTC)]-2 H2O, I, and [NaMn(BTC)], II (BTC=1,2,4-benzenetricarboxylate = trimellitate) were synthesized and their structures determined by single-crystal X-ray diffraction (XRD). In I, the Mn-4 cluster, [Mn-4(mu(5)-OH)(2)(H2O)(4)O-12], is connected with eight trimellitate anions and each trimellitate anion connects to four different Mn-4 clusters, resulting in a fluorite-like structure. In II, the Mn2O8 dimer is connected with two Na+ ions through carboxylate oxygen to form mixed-metal distorted Kagome-related two-dimensional -M-O-M- layers, which are pillared by the trimellitate anions forming the three-dimensional structure. The extra-framework water molecules in I are reversibly adsorbed and are also corroborated by powder XRD studies. The formation of octameric water clusters involving free and coordinated water molecules appears to be new. Interesting magnetic behavior has been observed for both compounds. Electron spin resonance (ESR) studies indicate a broadening of the signal below the ordering temperature and appear to support the findings of the magnetic studies.

Optical properties of reduced LiNbO,

Optical characteristics of H2-reduced LiNbO3 have been studied. The optical transmission in the spectral range 0.3 to 5 mu m is progressively narrowed as the sample is reduced. An absorption band centred at about 2.48 eV is assigned to small polarons. This interpretation is consistent with the published defect structure, transport and spectroscopic reports on reduced LiNbO3. A semi-quantitative analysis of the 2.48 eV absorption band is carried out by employing the Reik and Heese theory (1967) for optical properties of small polarons.

Purification and properties of synephrinase from Arthrobacter synephrinum

Synephrinase, an enzyme catalyzing the conversion of (−)-synephrine into p-hydroxyphenylacetaldehyde and methylamine, was purified to apparent homogeneity from the cell-free extracts of Arthrobacter synephrinum grown on (±)-synephrine as the sole source of carbon and nitrogen. A 40-fold purification was sufficient to produce synephrinase that is apparently homogeneous as judged by native polyacrylamide gel electrophoresis and has a specific activity of 1.8 μmol product formed /min/mg protein. Thus, the enzyme is a relatively abundant enzyme, perhaps comprising as much as 2.5% of the total protein. The enzyme essentially required a sulfhydryl compound for its activity. Metal ions like Mg2+, Ca2+, and Mn2+ stimulated the enzyme activity. Metal chelating agents, thiol reagents, denaturing agents, and metal ions like Zn2+, Hg2+, Ag1+, and Cu2+ inhibited synephrinase activity. Apart from (−)-synephrine, the enzyme acted upon (±)-octopamine and β-methoxysynephrine. Molecular oxygen was not utilized during the course of the reaction. The molecular mass of the enzyme as determined by Sephadex G-200 chromatography, was around 156,000. The enzyme was made up of four identical subunits with a molecular mass of 42,000.

Properties of iron related quenched-in levels in p-silicon

The electrical and optical properties of the thermally induced quenched-in levels in p-silicon which have heen attributed to iron are studied. The two levels, HI and H2, are located at Ev + 0.42 eV and Ev + 0.52 eV, respectively, as determined by TSCAP, DLTS, and transient photocapacitance methods. The photoionization cross sections are well described by Lucovsky's model. The hole capture by H1 is temperature dependent; a barrier of 40 meV is measured. However, multiphonon emission mechanism cannot be invoked to explain this temperature dependence due to the inferred zero lattice relaxation. The source of iron contamination is found to be the ambient conditions, in particular the quartz tube. The conflicting reports regarding the stability and the variation in the reported capture cross section values suggests that the observed Ev + 0.4 eV level must be a complex centre. The inferred near zero lattice relaxation during the electron transition implies weak coupling to the host lattice.

Partial purification and properties of a transamidinase from Lathyrus sativus seedlings. Involvement in homoarginine metabolism and amine interconversions

A transamidinase was purified 463-fold from Lathyrus sativus seedlings by affinity chromatography on homoarginine--Sepharose. The enzyme exhibited a wide substrate specificity, and catalysed the reversible transfer of the amidino groups from donors such as arginine, homoarginine and canavanine to acceptors such as lysine, putrescine, agmatine, cadaverine and hydroxylamine. The enzyme could not be detected in the seeds, and attained the highest specific activity in the embryo axis on day 10 after seed germination. Its thiol nature was established by strong inhibition by several thiol blockers and thiol compounds in the presence of ferricyanide. In the absence of an exogenous acceptor, it exhibited weak hydrolytic activity towards arginine. It had apparent mol.wt. 210000, and exhibited Michaelis--Menten kinetics with Km 3.0 mM for arginine. Ornithine competitively inhibited the enzyme, with Ki 1.0 mM in the arginine--hydroxylamine amidino-transfer reaction. Conversion experiments with labelled compounds suggest that the enzyme is involved in homoarginine catabolism during the development of plant embryo to give rise to important amino acids and amine metabolites. Presumptive evidence is also provided for its involvement in the biosynthesis of the guanidino amino acid during seed development. The natural occurrence of arcain in L. sativus and mediation of its synthesis in vitro from agmatine by the transamidinase are demonstrated.

Enzyme-catalysed non-oxidative decarboxylation of aromatic acids: I.Purification and spectroscopic properties of 2,3 dihydroxybenzoic acid decarboxylase from Image Image

In order to understand the molecular mechanism of non-oxidative decarboxylation of aromatic acids observed in microbial systems, 2,3 dihydroxybenzoic acid (DHBA) decarboxylase from Image Image was purified to homogeneity by affinity chromatography. The enzyme (Mr 120 kDa) had four identical subunits (28 kDa each) and was specific for DHBA. It had a pH optimum of 5.2 and Km was 0.34mM. The decarboxylation did not require any cofactors, nor did the enzyme had any pyruvoyl group at the active site. The carboxyl group and hydroxyl group in the Image -position were required for activity. The preliminary spectroscopic properties of the enzyme are also reported.

Soil properties and crop yields in a dryland Vertisol sown with cotton-based crop rotations

Information on the effects of growing cotton (Gossypium hirsutum L.)-based crop rotations on soil quality of dryland Vertisols is sparse. The objective of this study was to quantify the effects of growing cereal and leguminous crops in rotation with dryland cotton on physical and chemical properties of a grey Vertisol near Warra, SE Queensland, Australia. The experimental treatments, selected after consultations with local cotton growers, were continuous cotton (T1), cotton-sorghum (Sorghum bicolor (L.) Moench.) (T2), cotton-wheat (Triticum aestivum L.) double cropped (T3), cotton-chickpea (Cicer arietinum L.) double cropped followed by wheat (T4) and cotton-wheat (T5). From 1993 to 1996 land preparation was by chisel ploughing to about 0.2 m followed by two to four cultivations with a Gyral tyne cultivator. Thereafter all crops were sown with zero tillage except for cultivation with a chisel plough to about 0.07-0.1 m after cotton picking to control heliothis moth pupae. Soil was sampled from 1996 to 2004 and physical (air-filled porosity of oven-dried soil, an indicator of soil compaction; plastic limit; linear shrinkage; dispersion index) and chemical (pH in 0.01 M CaCl2, organic carbon, exchangeable Ca, Mg, K and Na contents) properties measured. Crop rotation affected soil properties only with respect to exchangeable Na content and air-filled porosity. In the surface 0.15 m during 2000 and 2001 lowest air-filled porosity occurred with T1 (average of 34.6 m3/100 m3) and the highest with T3 (average of 38.9 m3/100 m3). Air-filled porosity decreased in the same depth between 1997 and 1998 from 45.0 to 36.1 m3/100 m3, presumably due to smearing and compaction caused by shallow cultivation in wet soil. In the subsoil, T1 and T2 frequently had lower air-filled porosity values in comparison with T3, T4 and T5, particularly during the early stages of the experiment, although values under T1 increased subsequently. In general, compaction was less under rotations which included a wheat crop (T3, T4, T5). For example, average air-filled porosity (in m3/100 m3) in the 0.15-0.30 m depth from 1996 to 1999 was 19.8 with both T1 and T2, and 21.2 with T3, 21.1 with T4 and 21.5 with T5. From 2000 to 2004, average air-filled porosity (in m3/100 m3) in the same depth was 21.3 with T1, 19.0 with T2, 19.8 with T3, 20.0 with T4 and 20.5 with T5. The rotation which included chickpea (T4) resulted in the lowest exchangeable Na content, although differences among rotations were small. Where only a cereal crop with a fibrous root system was sown in rotation with cotton (T2, T3, T5) linear shrinkage in the 0.45-0.60 m depth was lower than in rotations, which included tap-rooted crops such as chickpea (T4) or continuous cotton (T1). Dispersion index and organic carbon decreased, and plastic limit increased with time. Soil organic carbon stocks decreased at a rate of 1.2 Mg/ha/year. Lowest average cotton lint yield occurred with T2 (0.54 Mg/ha) and highest wheat yield with T3 (2.8 Mg/ha). Rotations which include a wheat crop are more likely to result in better soil structure and cotton lint yield than cotton-sorghum or continuous cotton.

New insights into the altered adhesive and mechanical properties of red blood cells parasitized by Babesia bovis

Sequestration of parasite-infected red blood cells (RBCs) in the microvasculature is an important pathological feature of both bovine babesiosis caused by Babesia bovis and human malaria caused by Plasmodium falciparum. Surprisingly, when compared with malaria, the cellular and molecular mechanisms that underlie this abnormal circulatory behaviour for RBCs infected with B. bovis have been relatively ignored. Here, we present some novel insights into the adhesive and mechanical changes that occur in B. bovis-infected bovine RBCs and compare them with the alterations that occur in human RBCs infected with P. falciparum. After infection with B. bovis, bovine RBCs become rigid and adhere to vascular endothelial cells under conditions of physiologically relevant flow. These alterations are accompanied by the appearance of ridge-like structures on the RBC surface that are analogous, but morphologically and biochemically different, to the knob-like structures on the surface of human RBCs infected with P. falciparum. Importantly, albeit for a limited number of parasite lines examined here, the extent of these cellular and rheological changes appear to be related to parasite virulence. Future investigations to identify the precise molecular composition of ridges and the proteins that mediate adhesion will provide important insight into the pathogenesis of both babesiosis and malaria.

Exploring the potential of VIS-NIR spectroscopy to predict sensory properties of foods

Sensory analysis of food involves the measurement, interpretation and understanding of human responses to the properties of food perceived by the senses such as sight, smell, and taste (Cozzolino et al. 2005). It is important to have a quantitative means for assessing sensory properties in a reasonable way, to enable the food industry to rapidly respond to the changing demands of both consumers and the market. Aroma and flavour are among the most important properties for the consumer and numerous studies have been performed in attempts to find correlations between sensory qualities and objective instrumental measurements. Rapid, non-destructive instrumental methods such as near infrared spectroscopy (NIR) might be advantageous to predict quality of food and agricultural products due to the speed of analysis, minimum sample preparation and low cost. The advantages of such technologies are not only to assess chemical structures but also to build a spectrum, characteristic of the sample, which behaves as a “finger print”.