Infrared study of CO, CO2, H2 and H2O interactions on potassium-promoted reduced and oxidised silica-supported copper catalysts

FTIR spectra are reported of CO, CO2, H2 and H2O on silica-supported potassium, copper and potassium-copper catalysts. Adsorption of CO on a potassium/silica catalyst resulted in the formation of complexed CO moieties. Whereas exposure of CO2 to the same catalyst produced bands ascribed to CO2 -, bidentate carbonate and complexed CO species. Fully oxidised copper/silica surfaces gave bands due to CO on CuO and isolated Cu2+ cations on silica. Addition of potassium to this catalyst removed a peak attributed to CO adsorption on isolated Cu2+ cations and red-shifted the maximum ascribed to CO adsorbed on CuO. For a reduced copper/silica catalyst bands due to adsorbed CO on both high and low index planes were red-shifted by 10 cm-1 in the presence of potassium, although the strength of the Cu - CO bond did not appear to be increased concomitantly. An explanation in terms of an electrostatic effect between potassium and adsorbed CO is forwarded. A small maximum at ca. 1510 cm-1 for the reduced catalyst increased substantially upon exposing CO to a reoxidised promoted catalyst. Correspondingly, CO2 adsorption allowed the identification of two distinct carboxylate species, one of which was located at an interfacial site between copper and potassium oxide. Carboxylate species reacted with hydrogen at 295 K, on a reduced copper surface, to produce predominantly unidentate formate on potassium. In contrast no interaction was detected on a reoxidised copper catalyst at 295 K until a fraction of the copper surface was in a reduced state. Furthermore the interaction of polar water molecules with carboxylate species resulted in a perturbation of this structure which gave lower C----O stretching frequencies.

Metabolomic analysis characterizes tissue specific indomethacin-induced metabolic perturbations of rats

In this study, the promising metabolomic approach integrating with ingenuity pathway analysis (IPA) was applied to characterize the tissue specific metabolic perturbation of rats that was induced by indomethacin. The selective pattern recognition analyses were applied to analyze global metabolic profiling of urine of rats treated by indomethacin at an acute dosage of reference that has been proven to induce tissue disorders in rats, evaluated throughout the time-course of -24-72 h. The results preliminarily revealed that modifications of amino acid metabolism, fatty acid metabolism and energetically associated metabolic pathways accounted for metabolic perturbation of the rats that was induced by indomethacin. Furthermore, IPA was applied to deeply analyze the biomarkers and their relations with the metabolic perturbations evidenced by pattern recognition analyses. Specific biochemical functions affected by indomethacin suggested that there is an important correlation of its effects in kidney and liver metabolism, based on the determined metabolites and their pathway-based analysis. The IPA correlation of the three major biomarkers, identified as creatinine, prostaglandin E2 and guanosine, suggested that the administration of indomethacin induced certain levels of toxicity in the kidneys and liver. The changes in the levels of biomarker metabolites allowed the phenotypical determination of the metabolic perturbations induced by indomethacin in a time-dependent manner.

Girls and violence : the case for a feminist theory of female violence

Rises recorded for girls’ violence in countries like Australia, Canada, United Kingdom and United States have been hotly contested. One view is these rising rates of violence are an artefact of new forms of policy, policing, criminalisation and social control over young women. Another view is that young women may indeed have become more violent as they have increasingly participated in youth subcultural activities involving gangs and drugs, and cyber‐cultural activities that incite and reward girls’ violence. Any comprehensive explanation will need to address how a complex interplay of cultural, social, behavioural, and policy responses contribute to these rises. This article argues that there is no singular cause, explanation or theory that accounts for the rises in adolescent female violence, and that many of the simple explanations circulating in popular culture are driven by an anti‐feminist ideology. By concentrating on females as victims of violence and very rarely as perpetrators, feminist criminology has for the most part ducked the thorny issue of female violence, leaving a discursive space for anti‐feminist sentiment to reign. The article concludes by arguing the case for developing a feminist theory of female violence.

The effect of surface tension and kinetic undercooling on a radially-symmetric melting problem

The addition of surface tension to the classical Stefan problem for melting a sphere causes the solution to blow up at a finite time before complete melting takes place. This singular behaviour is characterised by the speed of the solid-melt interface and the flux of heat at the interface both becoming unbounded in the blow-up limit. In this paper, we use numerical simulation for a particular energy-conserving one-phase version of the problem to show that kinetic undercooling regularises this blow-up, so that the model with both surface tension and kinetic undercooling has solutions that are regular right up to complete melting. By examining the regime in which the dimensionless kinetic undercooling parameter is small, our results demonstrate how physically realistic solutions to this Stefan problem are consistent with observations of abrupt melting of nanoscaled particles.

Teaching sociology within teacher education : revisiting, realigning and re-embedding

This paper uses theoretical resources from the sociology of education to consider the teaching of sociology in teacher education programs in Australia. Once a disciplinary ‘pillar’ of teacher education, sociology’s contribution has become less explicit while more integrated, with consequences for disciplinary identity. Here we explore how sociology is taught in teacher education curricula on two fronts. Firstly we outline how sociology is embedded as one of a number of competing perspectives in foundational studies, and its pedagogic consequences. Then we consider the powerful contribution of sociology in literacy studies, amidst public debate about literacy performance. The analysis draws on Bernstein’s (2000) distinction between singular disciplinary curriculum design and practically-oriented regional curriculum design. We seek to trouble the commonsense binary between theory and practice that structures debates around professional education in higher education more broadly, and to dignify service sociology as a valuable, generative site for the discipline’s future.

Improved sub-cellular resolution via simultaneous analysis of organelle proteomics data across varied experimental conditions

Spatial organisation of proteins according to their function plays an important role in the specificity of their molecular interactions. Emerging proteomics methods seek to assign proteins to sub-cellular locations by partial separation of organelles and computational analysis of protein abundance distributions among partially separated fractions. Such methods permit simultaneous analysis of unpurified organelles and promise proteome-wide localisation in scenarios wherein perturbation may prompt dynamic re-distribution. Resolving organelles that display similar behavior during a protocol designed to provide partial enrichment represents a possible shortcoming. We employ the Localisation of Organelle Proteins by Isotope Tagging (LOPIT) organelle proteomics platform to demonstrate that combining information from distinct separations of the same material can improve organelle resolution and assignment of proteins to sub-cellular locations. Two previously published experiments, whose distinct gradients are alone unable to fully resolve six known protein-organelle groupings, are subjected to a rigorous analysis to assess protein-organelle association via a contemporary pattern recognition algorithm. Upon straightforward combination of single-gradient data, we observe significant improvement in protein-organelle association via both a non-linear support vector machine algorithm and partial least-squares discriminant analysis. The outcome yields suggestions for further improvements to present organelle proteomics platforms, and a robust analytical methodology via which to associate proteins with sub-cellular organelles.

Dynamic effects of electrical pitting in steam-turbine tilting-pad thrust-bearings

This paper merges the analysis of a case history and the simplified theoretical model related to a rather singular phenomenon that may happen in rotating machinery. Starting from the first, a small industrial steam turbine experienced a very strange behavior during megawatt load. When the unit was approaching the maximum allowed power, the temperature of the babbitt metal of the pads of the thrust bearing showed constant increase with an unrecoverable drift. Bearing inspection showed that pad trailing edge had the typical aspect of electrical pitting. This kind of damage was not reparable and bearing pads had to replaced. This problem occurred several times in sequence and was solved only by adding further ground brushes to the shaft-line. Failure analysis indicated electrodischarge machining as the root fault. A specific model, able to take into consideration the effect of electrical pitting and loading capacity decreasing as a consequence of the damage of the babbitt metal, is proposed in the paper and shows that the phenomenon causes the irretrievable failure of the thrust bearing.

Technology : A mobilising force for a radical design pedagogy [Editorial - Special Issue]

This special issue of the Journal of Learning Design, led by Jill Franz and Lindy Osborne, from the School of Design in the Creative Industries Faculty at the Queensland University of Technology, is grounded in Design Education. Its papers are drawn from differing fields of design: digital media, architecture, and environmental design. Each makes use of technologies in differing ways but all share the singular purpose of achieving enhanced learning outcomes from students.

Jacobian-free Newton-Krylov methods with GPU acceleration for computing nonlinear ship wave patterns

The nonlinear problem of steady free-surface flow past a submerged source is considered as a case study for three-dimensional ship wave problems. Of particular interest is the distinctive wedge-shaped wave pattern that forms on the surface of the fluid. By reformulating the governing equations with a standard boundary-integral method, we derive a system of nonlinear algebraic equations that enforce a singular integro-differential equation at each midpoint on a two-dimensional mesh. Our contribution is to solve the system of equations with a Jacobian-free Newton-Krylov method together with a banded preconditioner that is carefully constructed with entries taken from the Jacobian of the linearised problem. Further, we are able to utilise graphics processing unit acceleration to significantly increase the grid refinement and decrease the run-time of our solutions in comparison to schemes that are presently employed in the literature. Our approach provides opportunities to explore the nonlinear features of three-dimensional ship wave patterns, such as the shape of steep waves close to their limiting configuration, in a manner that has been possible in the two-dimensional analogue for some time.

Colonizing while migrating : how do individual enteric neural crest cells behave?

Background Directed cell migration is essential for normal development. In most of the migratory cell populations that have been analysed in detail to date, all of the cells migrate as a collective from one location to another. However, there are also migratory cell populations that must populate the areas through which they migrate, and thus some cells get left behind while others advance. Very little is known about how individual cells behave to achieve concomitant directional migration and population of the migratory route. We examined the behavior of enteric neural crest-derived cells (ENCCs), which must both advance caudally to reach the anal end and populate each gut region. Results The behaviour of individual ENCCs was examined using live imaging and mice in which ENCCs express a photoconvertible protein. We show that individual ENCCs exhibit very variable directionalities and speed; as the migratory wavefront of ENCCs advances caudally, each gut region is populated primarily by some ENCCs migrating non-directionally. After populating each region, ENCCs remain migratory for at least 24 hours. Endothelin receptor type B (EDNRB) signaling is known to be essential for the normal advance of the ENCC population. We now show that perturbation of EDNRB principally affects individual ENCC speed rather than directionality. The trajectories of solitary ENCCs, which occur transiently at the wavefront, were consistent with an unbiased random walk and so cell-cell contact is essential for directional migration. ENCCs migrate in close association with neurites. We showed that although ENCCs often use neurites as substrates, ENCCs lead the way, neurites are not required for chain formation and neurite growth is more directional than the migration of ENCCs as a whole. Conclusions Each gut region is initially populated by sub-populations of ENCCs migrating non-directionally, rather than stopping. This might provide a mechanism for ensuring a uniform density of ENCCs along the growing gut.

The importance of accurate beam data measurement for SRT/SRS treatment planning

Introduction This study investigated the sensitivity of calculated stereotactic radiotherapy and radiosurgery doses to the accuracy of the beam data used by the treatment planning system. Methods Two sets of field output factors were acquired using fields smaller than approximately 1 cm2, for inclusion in beam data used by the iPlan treatment planning system (Brainlab, Feldkirchen, Germany). One set of output factors were measured using an Exradin A16 ion chamber (Standard Imaging, Middleton, USA). Although this chamber has a relatively small collecting volume (0.007 cm3), measurements made in small fields using this chamber are subject to the effects of volume averaging, electronic disequilibrium and chamber perturbations. The second, more accurate, set of measurements were obtained by applying perturbation correction factors, calculated using Monte Carlo simulations according to a method recommended by Cranmer-Sargison et al. [1] to measurements made using a 60017 unshielded electron diode (PTW, Freiburg, Germany). A series of 12 sample patient treatments were used to investigate the effects of beam data accuracy on resulting planned dose. These treatments, which involved 135 fields, were planned for delivery via static conformal arcs and 3DCRT techniques, to targets ranging from prostates (up to 8 cm across) to meningiomas (usually more than 2 cm across) to arterioveinous malformations, acoustic neuromas and brain metastases (often less than 2 cm across). Isocentre doses were calculated for all of these fields using iPlan, and the results of using the two different sets of beam data were evaluated. Results While the isocentre doses for many fields are identical (difference = 0.0 %), there is a general trend for the doses calculated using the data obtained from corrected diode measurements to exceed the doses calculated using the less-accurate Exradin ion chamber measurements (difference\0.0 %). There are several alarming outliers (circled in the Fig. 1) where doses differ by more than 3 %, in beams from sample treatments planned for volumes up to 2 cm across. Discussion and conclusions These results demonstrate that treatment planning dose calculations for SRT/SRS treatments can be substantially affected when beam data for fields smaller than approximately 1 cm2 are measured inaccurately, even when treatment volumes are up to 2 cm across.

Photoelectron spectroscopic study of the oxyallyl diradical

The photoelectron spectrum of the oxyallyl (OXA) radical anion has been measured. The radical anion has been generated in the reaction of the atomic oxygen radical anion (O center dot-) with acetone. Three low-lying electronic states of OXA have been observed in the spectrum. Electronic structure calculations have been performed for the triplet states (B-3(2) and B-3(1)) of OXA and the ground doublet state ((2)A(2)) of the radical anion using density, functional theory (DFT). Spectral simulations have been carried out for the triplet statics based on the results of the DFT calculations. The simulation identifies a vibrational progression of the CCC bending mode of the B-3(2) state of OXA in the lower electron binding energy (eBE) portion of the spectrum. On top of the B-3(2) feature, however, the experimental spectrum exhibits additional photoelectron peaks whose angular distribution is distinct from that for the vibronic peaks of the B-3(2) state. Complete active space self-consistent field (CASSCF) method and second-order perturbation theory based on the CASSCF wave function (CASPT2) have been employed to study the lowest singlet state ((1)A(1)) of OXA. The simulation based on the results of these electronic structure calculations establishes that the overlapping peaks represent the vibrational ground level of the (1)A(1) state and its vibrational progression of the CO stretching mode. The A, state is the lowest electronic state of,OXA, and the electron affinity (EA) of OXA is 1.940 +/- 0.010 eV. The B-3(2) state is the first excited state with an electronic term energy of 55 +/- 2 meV. The widths of the vibronic peaks of the (X) over tilde (1)A(1) state are much broader than those of the (a) over tilde B-3(2) state, implying that the (1)A(1) state is indeed a transition state. The CASSCF and CASPT2 calculations suggest that the (1)A(1) state is at a potential maximum along the nuclear coordinate representing disrotatory motion of the two methylene groups, which leads to three-membered-ring formation, i.e., cydopropanone. The simulation of (b) over tilde B-3(1) OXA reproduces the higher eBE portion of the spectrum very well. The term energy of the B-3(1) state is 0.883 +/- 0.012 eV. Photoelectron spectroscopic measurements have also been conducted for the other ion products of the O center dot- reaction with acetone. The photoelectron imaging spectrum of the acetylcarbene (AC) radical anion exhibits a broad, structureless feature, which is assigned to the (X) over tilde (3)A '' state of AC. The ground ((2)A '') and first excited ((2)A') states of the 1-methylvinoxy (1-MVO) radical have been observed in the photoelectron spectrum of the 1-MVO ion, and their vibronic structure has been analyzed.

Amplitude equations and asymptotic expansions for multi-scale problems

In this paper we introduce a new technique to obtain the slow-motion dynamics in nonequilibrium and singularly perturbed problems characterized by multiple scales. Our method is based on a straightforward asymptotic reduction of the order of the governing differential equation and leads to amplitude equations that describe the slowly-varying envelope variation of a uniformly valid asymptotic expansion. This may constitute a simpler and in certain cases a more general approach toward the derivation of asymptotic expansions, compared to other mainstream methods such as the method of Multiple Scales or Matched Asymptotic expansions because of its relation with the Renormalization Group. We illustrate our method with a number of singularly perturbed problems for ordinary and partial differential equations and recover certain results from the literature as special cases. © 2010 - IOS Press and the authors. All rights reserved.

Examples illustrating the use of renormalization techniques for singularly perturbed differential equations

With nine examples, we seek to illustrate the utility of the Renormalization Group approach as a unification of other asymptotic and perturbation methods.

Reduction of amplitude equations by the renormalization group approach

This article elucidates and analyzes the fundamental underlying structure of the renormalization group (RG) approach as it applies to the solution of any differential equation involving multiple scales. The amplitude equation derived through the elimination of secular terms arising from a naive perturbation expansion of the solution to these equations by the RG approach is reduced to an algebraic equation which is expressed in terms of the Thiele semi-invariants or cumulants of the eliminant sequence { Zi } i=1 . Its use is illustrated through the solution of both linear and nonlinear perturbation problems and certain results from the literature are recovered as special cases. The fundamental structure that emerges from the application of the RG approach is not the amplitude equation but the aforementioned algebraic equation. © 2008 The American Physical Society.