Nondeactivating Nanosized Ionic Catalysts for Water-Gas Shift Reaction

The water-gas shift reaction (WGS) is an important reaction to produce hydrogen. In this study, we have synthesized nanosized catalysts where Pt ion is substituted in the +2 state in TiO2, CeO2, and Ce1-xTixO2-delta. These catalysts have been characterized by X-ray diffraction and X-ray photoelectron spectroscopy (XPS), and it has been shown that Pt2+ in these reducible oxides result in solid solutions like Ti0.99Pt0.01O2-delta, Ce0.8Ti0.15Pt0.02O2-delta, and Ce0.98Pt0.02O2-delta. These catalysts were tested for the water gas shift reaction both ill the presence and absence of hydrogen. It was shown that Ti0.99Pt0.01O2-delta exhibited higher catalytic activity than Ce0.83Ti0.15Pt0.02O2-delta and Ce0.98Pt0.02O2-delta. Further, experiments were conducted to determine the deactivation of these catalysts. There was no sintering of Pt and no carbonate formation; therefore, the catalyst did not deactivate even after prolonged reaction. There was no carbonate formation because of the highly acidic nature of Ti4+ ions in the catalysts.

Shift in disease burden from communicable to non-communicable diseases: Aiming to achieve Universal Health Coverage in Nepal

A major barrier to accessing healthcare services is spending, and the extended time that non-communicable diseases require treatment for means that many people around the world do not have proper access to care. Saval Khanal from Sankalpa Foundation, Nepal, Lennert Veerman and Samantha Hollingworth from the University of Queensland and Lisa Nissen from Queensland University of Technology lay out the results of their study and establish a method to forecast medicine use in Nepal.

CSSI-PRO: a method for secondary structure type editing, assignment and estimation in proteins using linear combination of backbone chemical shifts

Estimation of secondary structure in polypeptides is important for studying their structure, folding and dynamics. In NMR spectroscopy, such information is generally obtained after sequence specific resonance assignments are completed. We present here a new methodology for assignment of secondary structure type to spin systems in proteins directly from NMR spectra, without prior knowledge of resonance assignments. The methodology, named Combination of Shifts for Secondary Structure Identification in Proteins (CSSI-PRO), involves detection of specific linear combination of backbone H-1(alpha) and C-13' chemical shifts in a two-dimensional (2D) NMR experiment based on G-matrix Fourier transform (GFT) NMR spectroscopy. Such linear combinations of shifts facilitate editing of residues belonging to alpha-helical/beta-strand regions into distinct spectral regions nearly independent of the amino acid type, thereby allowing the estimation of overall secondary structure content of the protein. Comparison of the predicted secondary structure content with those estimated based on their respective 3D structures and/or the method of Chemical Shift Index for 237 proteins gives a correlation of more than 90% and an overall rmsd of 7.0%, which is comparable to other biophysical techniques used for structural characterization of proteins. Taken together, this methodology has a wide range of applications in NMR spectroscopy such as rapid protein structure determination, monitoring conformational changes in protein-folding/ligand-binding studies and automated resonance assignment.

Sustainable productivity improvements in allium and solanaceous vegetable crops in Indonesia and sub-tropical Australia

The most important vegetable crops grown in Indonesia, and particularly lowland coastal production, are the true shallot and chilli. These crops are usually grown in rotation with rice but are far more valuable crops and are increasingly in high demand. They offer an opportunity for small farmers to generate extra income, increase farm profitability and shift away from subsistence production. However, the yield and profitability of shallot and chilli production is severely limited by a range of agronomic constraints. This project aims towards raising the productivity of allium (shallot and garlic) and chilli/capsicum cropping systems. The methodology will include a benchmarking survey and review of grower practices. This will be supplemented with physical surveys of crops for disease incidence and efficiency of fertiliser use. Once surveys are completed in Indonesia and the important pathogens identified, recommendations can be made for disease management. This will include review of chemical usage in Indonesia and Australia to provide best management guidelines for the application of insecticides, fungicides and other chemicals.

Writing fashion’s future: the gods and monsters of the Anthropocene

This paper identifies two narratives of the Anthropocene and explores how they play out in the realm of future-looking fashion production. Each narrative draws on mythic comparisons to gods and monsters to express humanity’s dilemmas, albeit from different perspectives. The first is a Malthusian narrative of collapse and scarcity, brought about by the monstrous, unstoppable nature of human technology set loose on the natural world. In this vein, philosopher Slavoj Zizek (2010) draws on Biblical analogies, likening ecological crisis to one of the four horsemen of the apocalypse. To find a myth to suit the present times, novelist A.S Byatt (2011) proposes Ragnarök, a Norse myth in which the gods destroy themselves. In contrast, the second narrative is one of technological cornucopia. Stewart Brand (2009, 27), self-described ‘eco-pragmatist’ writes, ‘we are as gods and we have to get good at it’. In his view, human technologies offer the only hope to mitigating the problems caused by human technology – Brand suggests harnessing nuclear power, bioengineering of crops and the geoengineering of the planet as the way forward. Similarly, the French philosopher Bruno Latour (2012, 274), exhorts us to “love our monsters”, likening our technologies to Doctor Frankenstein’s monster – set loose upon the world, and then reviled by his creator. For both Brand and Latour, human technology may be monstrous, but it must also be turned toward solutions. Within this schema, hopeful visions of the future of fashion are similarly divided. In the techno-enabled cornucopian future, the fashion industry embraces wearable technology, speed and efficiency. Technologies such as waterless dyeing, 3D printing and self-cleaning garments shift fashion into a new era of cleaner production. Meanwhile, in the narrative of scarcity, a more cautious approach sees fashion return to a new localism and valuing of the hand-made in a time of shrinking resources. Through discussion of future-looking fashion designers, brands, and activists, this paper explores how they may align along a spectrum to one of these two grand narratives of the future. The paper will discuss how these narratives may unconsciously shape the perspective of both producers and users around the fashion of today and the fashion of tomorrow. This paper poses the question: what stories can be written for fashion’s future in the Anthropocene, and are they fated, or can they be re-written?

1H and 13C NMR spectral studies of C-2 substituted isomeric exo- and endo-5-methyl-bicyclo[3.2.1]octane-6,8-diones

A detailed analysis of the 1H and 13C NMR spectra of C-2 aryl and alkyl/desalkyl substituted isomeric exo- and endo-5-methylbicyclo[3.2.1]octane-6,8-diones is presented. The chemical shift of the C-5 angular methyl, the C-2 alkyl/olefinic (C-10)/C-2 methine protons, the aromatic proton shieldings and the characteristic AMX and ABX spectral pattern of the ketomethylene and bridgehead protons were found to be sensitive to the phenyl ring orientation (anisotropy). These distinctive features could be used for configurational distinction for this class of compounds. With increasing ortho-methoxy substitution on the phenyl ring, considerable deshilelding of the bridgehead proton was observed (ca. 0.6 ppm). Absence of the C-2 alkyl group in the desalkyl isomers resulted in substantial changes in the chemical shifts of different protons. A study of the NMR spectra of the corresponding bicyclic compounds with C-2 methoxy/hydroxy substitution instead of the aryl group revealed that the anisotropy of the phenyl ring and the electronegative oxygen substituents have opposite effects. The 13C NMR spectral assignment of each carbon resonance of C-2 aryl and alkyl/desalkyl substituted isomeric exo- and endo-5-methylbicyclo[3.2.1]octane-6,8-diones and the corresponding C-2 methoxy/hydroxy/chloro and methyl bicyclic compounds are reported. Additional ortho-methoxy substitution on the phenyl ring was found to produce considerable high field shifts of the C-10 and C-1 carbon resonances. A high-field shift was observed for the C-6 and C-8 carbonyl carbons, presumably due to 1,3-dicarbonyl interactions. The chemical shifts of C-1 aromatic, C-10 alkyl and C-2 carbons, which are sensitive to exo/endo isomerism, could be utilized in differentiating a pair of isomers.

Thermodynamic and kinetic studies on saccharide binding to soya-bean agglutinin.

The fluorescence of N-dansylgalactosamine [N-(5-dimethylaminonaphthalene-1-sulphonyl)galactosamine] was enhanced 11-fold with a 25 nm blue-shift in the emission maximum upon binding to soya-bean agglutinin (SBA). This change was used to determine the association constants and thermodynamic parameters for this interaction. The association constant of 1.51 X 10(6) M-1 at 20 degrees C indicated a very strong binding, which is mainly due to a relatively small entropy value, as revealed by the thermodynamic parameters: delta G = -34.7 kJ X mol-1, delta H = -37.9 kJ X mol-1 and delta S = -10.9 J X mol-1 X K-1. The specific binding of this sugar to SBA shows that the lectin can accommodate a large hydrophobic substituent on the C-2 of galactose. Binding of non-fluorescent ligands, studied by monitoring the fluorescence changes when they are added to a mixture of SBA and N-dansylgalactosamine, indicates that a hydrophobic substituent at the anomeric position increases the affinity of the interaction. The C-6 hydroxy group also stabilizes the binding considerably. Kinetics of binding of N-dansylgalactosamine to SBA studied by stopped-flow spectrofluorimetry are consistent with a single-step mechanism and yielded k+1 = 2.4 X 10(5) M-1 X s-1 and k-1 = 0.2 s-1 at 20 degrees C. The activation parameters indicate an enthalpicly controlled association process.

Genomic and functional profiling of gastric cancer

Helicobacter pylori infection is a risk factor for gastric cancer, which is a major health issue worldwide. Gastric cancer has a poor prognosis due to the unnoticeable progression of the disease and surgery is the only available treatment in gastric cancer. Therefore, gastric cancer patients would greatly benefit from identifying biomarker genes that would improve diagnostic and prognostic prediction and provide targets for molecular therapies. DNA copy number amplifications are the hallmarks of cancers in various anatomical locations. Mechanisms of amplification predict that DNA double-strand breaks occur at the margins of the amplified region. The first objective of this thesis was to identify the genes that were differentially expressed in H. pylori infection as well as the transcription factors and signal transduction pathways that were associated with the gene expression changes. The second objective was to identify putative biomarker genes in gastric cancer with correlated expression and copy number, and the last objective was to characterize cancers based on DNA copy number amplifications. DNA microarrays, an in vitro model and real-time polymerase chain reaction were used to measure gene expression changes in H. pylori infected AGS cells. In order to identify the transcription factors and signal transduction pathways that were activated after H. pylori infection, gene expression profiling data from the H. pylori experiments and a bioinformatics approach accompanied by experimental validation were used. Genome-wide expression and copy number microarray analysis of clinical gastric cancer samples and immunohistochemistry on tissue microarray were used to identify putative gastric cancer genes. Data mining and machine learning techniques were applied to study amplifications in a cross-section of cancers. FOS and various stress response genes were regulated by H. pylori infection. H. pylori regulated genes were enriched in the chromosomal regions that are frequently changed in gastric cancer, suggesting that molecular pathways of gastric cancer and premalignant H. pylori infection that induces gastritis are interconnected. 16 transcription factors were identified as being associated with H. pylori infection induced changes in gene expression. NF-κB transcription factor and p50 and p65 subunits were verified using elecrophoretic mobility shift assays. ERBB2 and other genes located in 17q12- q21 were found to be up-regulated in association with copy number amplification in gastric cancer. Cancers with similar cell type and origin clustered together based on the genomic localization of the amplifications. Cancer genes and large genes were co-localized with amplified regions and fragile sites, telomeres, centromeres and light chromosome bands were enriched at the amplification boundaries. H. pylori activated transcription factors and signal transduction pathways function in cellular mechanisms that might be capable of promoting carcinogenesis of the stomach. Intestinal and diffuse type gastric cancers showed distinct molecular genetic profiles. Integration of gene expression and copy number microarray data allowed the identification of genes that might be involved in gastric carcinogenesis and have clinical relevance. Gene amplifications were demonstrated to be non-random genomic instabilities. Cell lineage, properties of precursor stem cells, tissue microenvironment and genomic map localization of specific oncogenes define the site specificity of DNA amplifications, whereas labile genomic features define the structures of amplicons. These conclusions suggest that the definition of genomic changes in cancer is based on the interplay between the cancer cell and the tumor microenvironment.

Impact of partial removal of the invasive macrophyte Lagarosiphon major (hydrocharitaceae) on invertebrates and fish

Invasive macrophyte species are a threat to native biodiversity and often grow to nuisance levels, therefore, making control options necessary. Macrophyte control can have pronounced impacts on littoral fish by reducing habitat heterogeneity and the loss of profitable (high density of invertebrates) foraging areas. Yet, there is little known about the impacts of macrophyte removal on invertebrates themselves. We conducted a macrophyte removal experiment, that is the cutting of channels into dense macrophyte beds, to investigate the impact of mechanical macrophyte control on invertebrate and fish communities in a littoral zone dominated by the invasive macrophyte Lagarosiphon major. The effect of macrophyte removal had only a temporary effect on macrophyte areal cover (4 months). Nevertheless, the treatment increased light penetration significantly. However, we could not detect any difference in epiphyton biomass. Invertebrate biomass increased in macrophyte stands 4 months after treatment and there was a shift in the invertebrate community composition. Mechanical control had no effect on invertebrate biodiversity. The higher invertebrate biomass did not translate into a higher fish density in the treated areas. The results of this study indicated that partial mechanical removal is a suitable option to control unwanted macrophyte stands.

Infant education and care: Why is education often overlooked?

The term Early Childhood Education and Care, intended to refer from birth until 8 years, is often erroneously reduced to Early Childhood Care when discussing infant child care settings. With prior to school settings catering for several age groups, why, then, when thoughts turn to infant child care, do stakeholders shift thinking to care over education? Is it because infants’ learning is often subtle, requiring key observational skills to identify learning moments? When we see infants as active learners the possibilities and power of our role as educators is heightened. The more we appreciate infants’ learning the more we can act in intentional ways to support learning...

Thermodynamic and kinetic analysis of carbohydrate binding to the basic lectin from winged bean (Psophocarpus tetragonolobus)

A basic lectin (pI approximately 10.0) was purified to homogeneity from the seeds of winged bean (Psophocarpus tetragonolobus) by affinity chromatography on Sepharose 6-aminocaproyl-D-galactosamine. The lectin agglutinated trypsinized rabbit erythrocytes and had a relative molecular mass of 58,000 consisting of two subunits of Mr 29,000. The lectin binds to N-dansylgalactosamine, leading to a 15-fold increase in dansyl fluorescence with a concomitant 25-nm blue shift in the emission maximum. The lectin has two binding sites/dimer for this sugar and an association constant of 4.17 X 10(5) M-1 at 25 degrees C. The strong binding to N-dansylgalactosamine is due to a relatively positive entropic contribution as revealed by the thermodynamic parameters: delta H = -33.62 kJ mol-1 and delta S0 = -5.24 J mol-1 K-1. Binding of this sugar to the lectin shows that it can accommodate a large hydrophobic substituent on the C-2 carbon of D-galactose. Studies with other sugars indicate that a hydrophobic substituent in alpha- conformation at the anomeric position increases the affinity of binding. The C-4 and C-6 hydroxyl groups are critical for sugar binding to this lectin. Lectin difference absorption spectra in the presence of N-acetylgalactosamine indicate perturbation of tryptophan residues on sugar binding. The results of stopped flow kinetics with N- dansylgalactosamine and the lectin are consistent with a simple one- step mechanism for which k+1 = 1.33 X 10(4) M-1 s-1 and k-1 = 3.2 X 10(- 2) s-1 at 25 degrees C. This k-1 is slower than any reported for a lectin-monosaccharide complex so far. The activation parameters indicate an enthalpically controlled association process.

Infrared and Mössbauer spectroscopic study of the metal-insulator transition in some oxides of perovskite structure

The IR spectra of some LaNi1−xBxO3 (B = Cr, Fe, and Co) compounds having perovskite structure have been studied in the range 1000−300 cm−1. An investigation of the changes in the metal-oxygen stretching frequency as x → xc from the insulating side has been carried out. An important feature is that as x → xc the vibrational features in the infrared spectra disappear when the resistivity is not, vert, similar10−1 Ω cm which is of two orders of magnitude more than the value of varrho0 at which the temperature coefficient of resistance changes sign. Mössbauer studies on Fe-containing samples with various conductivities show that the isomer shift decreases as conductivity increases which is indicative of larger Fe---O overlap.

Trends in therapeutic and prevention strategies for management of Bovine Mastitis: An overview

Mastitis is one of the most economically significant diseases for the dairy industry for backyard farmers in developing countries and high producing herds worldwide. Two of the major factors impeding reduction in the incidence of this disease is [a] the lack of availability of an effective vaccine capable of protecting against multiple etiological agents and [b] propensity of some of the etiological agents to develop persistent antibiotic resistance in biofilms. This is further complicated by the continuing revolving shift in the predominant etiological agents of mastitis, depending upon a multitude of factors such as variability in hygienic practices on farms, easy access leading to overuse of appropriate or inappropriate antibiotics at suboptimal concentrations, particularly in developing countries, and lack of compliance with the recommended treatment schedules. Regardless, Staphylococcus aureus and Streptococcus uberis followed by Escherichia coli, Streptococcus agalactiae has become the predominant etiological agents of bovine mastitis followed Streptococcus agalactiae, Streptococcus dysagalactiae, Klebsiella pneumonia and the newly emerging Mycoplasma bovis. Current approaches being pursued to reduce the negative economic impact of this disease are through early diagnosis of infection, immediate treatment with an antibiotic found to either inhibit or kill the pathogen(s) in vitro using planktonic cultures and the use of the currently marketed vaccines regardless of their demonstrated effectiveness. Given the limitations of breeding programs, including genetic selection to improve resistance against infectious diseases including mastitis, it is imperative to have the availability of an effective broad-spectrum, preferably cross-protective, vaccine capable of protecting against bovine mastitis for reduction in the incidence of bovine mastitis, as well as interrupting the potential cross-species transmission to humans. This overview highlights the major etiological agents, factors affecting susceptibility to mastitis, and the current status of antibiotic-based therapies and prototype vaccine candidates or commercially available vaccines against bovine mastitis as potential preventative strategies. © 2013 Tiwari JG, et al.

A review of the application of molecular genetics for fisheries management and conservation of sharks and rays

Since the first investigation 25 years ago, the application of genetic tools to address ecological and evolutionary questions in elasmobranch studies has greatly expanded. Major developments in genetic theory as well as in the availability, cost effectiveness and resolution of genetic markers were instrumental for particularly rapid progress over the last 10 years. Genetic studies of elasmobranchs are of direct importance and have application to fisheries management and conservation issues such as the definition of management units and identification of species from fins. In the future, increased application of the most recent and emerging technologies will enable accelerated genetic data production and the development of new markers at reduced costs, paving the way for a paradigm shift from gene to genome-scale research, and more focus on adaptive rather than just neutral variation. Current literature is reviewed in six fields of elasmobranch molecular genetics relevant to fisheries and conservation management (species identification, phylogeography, philopatry, genetic effective population size, molecular evolutionary rate and emerging methods). Where possible, examples from the Indo-Pacific region, which has been underrepresented in previous reviews, are emphasized within a global perspective. (C) 2012 The Authors Journal of Fish Biology (C) 2012 The Fisheries Society of the British Isles

Soil phosphorus–crop response calibration relationships and criteria for winter cereal crops grown in Australia

Soil testing is the most widely used tool to predict the need for fertiliser phosphorus (P) application to crops. This study examined factors affecting critical soil P concentrations and confidence intervals for wheat and barley grown in Australian soils by interrogating validated data from 1777 wheat and 150 barley field treatment series now held in the BFDC National Database. To narrow confidence intervals associated with estimated critical P concentrations, filters for yield, crop stress, or low pH were applied. Once treatment series with low yield (<1 t/ha), severe crop stress, or pHCaCl2 <4.3 were screened out, critical concentrations were relatively insensitive to wheat yield (>1 t/ha). There was a clear increase in critical P concentration from early trials when full tillage was common compared with those conducted in 1995–2011, which corresponds to a period of rapid shift towards adoption of minimum tillage. For wheat, critical Colwell-P concentrations associated with 90 or 95% of maximum yield varied among Australian Soil Classification (ASC) Orders and Sub-orders: Calcarosol, Chromosol, Kandosol, Sodosol, Tenosol and Vertosol. Soil type, based on ASC Orders and Sub-orders, produced critical Colwell-P concentrations at 90% of maximum relative yield from 15 mg/kg (Grey Vertosol) to 47 mg/kg (Supracalcic Calcarosols), with other soils having values in the range 19–27 mg/kg. Distinctive differences in critical P concentrations were evident among Sub-orders of Calcarosols, Chromosols, Sodosols, Tenosols, and Vertosols, possibly due to differences in soil properties related to P sorption. However, insufficient data were available to develop a relationship between P buffering index (PBI) and critical P concentration. In general, there was no evidence that critical concentrations for barley would be different from those for wheat on the same soils. Significant knowledge gaps to fill to improve the relevance and reliability of soil P testing for winter cereals were: lack of data for oats; the paucity of treatment series reflecting current cropping practices, especially minimum tillage; and inadequate metadata on soil texture, pH, growing season rainfall, gravel content, and PBI. The critical concentrations determined illustrate the importance of recent experimental data and of soil type, but also provide examples of interrogation pathways into the BFDC National Database to extract locally relevant critical P concentrations for guiding P fertiliser decision-making in wheat and barley.