Volumetric Properties, Viscosities, and Isobaric Heat Capacities of Imidazolium Octanoate Protic Ionic Liquid in Molecular Solvents

Densities (F), viscosities (?), and isobaric heat molar capacities (Cp) of binary mixtures containing imidazolium octanoate, [Im][C7CO2], a protic ionic liquid (PIL), with four molecular solvents, water, acetonitrile, ethanol, and 1-octanol, are determined as a function of temperature from (298.15 to 323.15) K and within the whole composition range at atmospheric pressure. Excess molar volumes, VE, excess molar heat capacities, Cp E, and the deviation from additivity rules of viscosities, ??, of imidazolium octanoate solutions were then deduced from the experimental results, as well as apparent molar volumes, Vfi, and partial molar volumes, V j m,i. Results are discussed according to the nature of the interaction between the PIL and the molecules and the effect of temperature. The excess Gibbs energies of activation of viscous flow (?G*E) for these systems were then calculated at 298.15 K. The excess isobaric heat capacities, Cp E, of binary ([Im][C7CO2] + solvent) systems, depend also of the nature of the molecular solvent in mixture. The excess properties were then correlated, at each temperature, as a function of composition by a Redlich-Kister-type equation. Finally results have been discussed in terms of molecular interactions and molecular structures in these binary mixtures, and thermodynamic properties of investigated binary mixtures were then compared to literature values together to investigate the impact of the nature of the solvent on these reported properties.

The effectiveness of physical activity interventions in socio-economically disadvantaged communities: A systematic review.

OBJECTIVE: Interventions to increase levels of physical activity (PA) in socio-economically disadvantaged communities are needed but little is known about their effectiveness. This review examines the effectiveness of interventions designed to increase PA in these communities and the theoretical frameworks and components used. METHODS: Five databases were searched for papers published in English between January 2000 and December 2010 that reported outcomes of PA interventions in socio-economically disadvantaged communities. Studies targeting individuals with pre-existing disease and not reporting a measure of free-living PA were excluded. Two reviewers independently extracted data and evaluated quality of evidence against pre-defined criteria. RESULTS: Of 478 publications identified, 27 were included. We found that group-based interventions were effective for adults but not for children; evidence for the effectiveness of interventions targeting individuals was insufficient; limited evidence suggested that community-wide interventions produced small changes in PA. Interventions underpinned by any theoretical framework, compared to none, were more likely to be effective. Several effective interventions included education, PA and social support components. CONCLUSION: Compared to other approaches, multi-component adult group-based interventions with theoretical frameworks are most effective in increasing PA in socio-economically disadvantaged communities. More robust evaluations of interventions targeting individuals in these 'hard-to-reach' communities are required. Copyright © 2012. Published by Elsevier Inc.

The mechanical and rheological characterisation of implantable medical devices formulated from binary mixtures of cellulose derivatives

This study highlights the potential associated with utilising multi-component polymeric gels to formulate materials that possess unique rheological and mechanical properties. The synergistic effect* and interaction between hydroxyethylcellulose (HEC) and sodium carboxymethylcellulose (NaCMC), polymers which are commonly employed as drug delivery platforms for implantable medical devices (1), have been determined using dynamic, continuous shear and texture profile analysis. * The difference between the actual response of a binary mixture and the sum of the two components comprising the mixture Increases in polymer concentration resulted in an increase in G', G? and ?' whereas tan d decreased. Similarly, significant increases were also apparent in continuous shear and texture analysis. All binary mixtures showed positive synergy values which may suggest associative interaction between the two components.

Stochastic and deterministic processes interact in the assembly of desert microbial communities on a global scale

Extreme arid regions in the worlds' major deserts are typified by quartz pavement terrain. Cryptic hypolithic communities colonize the ventral surface of quartz rocks and this habitat is characterized by a relative lack of environmental and trophic complexity. Combined with readily identifiable major environmental stressors this provides a tractable model system for determining the relative role of stochastic and deterministic drivers in community assembly. Through analyzing an original, worldwide data set of 16S rRNA-gene defined bacterial communities from the most extreme deserts on the Earth, we show that functional assemblages within the communities were subject to different assembly influences. Null models applied to the photosynthetic assemblage revealed that stochastic processes exerted most effect on the assemblage, although the level of community dissimilarity varied between continents in a manner not always consistent with neutral models. The heterotrophic assemblages displayed signatures of niche processes across four continents, whereas in other cases they conformed to neutral predictions. Importantly, for continents where neutrality was either rejected or accepted, assembly drivers differed between the two functional groups. This study demonstrates that multi-trophic microbial systems may not be fully described by a single set of niche or neutral assembly rules and that stochasticity is likely a major determinant of such systems, with significant variation in the influence of these determinants on a global scale.

Analysis of IL6 Signal Transduction Model using Reduced Rank Regression

This work presents the application of reduced rank regression to the field of systems biology. A computational approach is used to investigate the mechanisms of the janus-associated kinases/signal transducers and transcription factors (JAK/STAT) and mitogen activated protein kinases (MAPK) signal transduction pathways in hepatic cells stimulated by interleukin-6. The results obtained identify the contribution of individual reactions to the dynamics of the model. These findings are compared to previously available results from sensitivity analysis of the model which focused on the parameters involved and their effect. This application of reduced rank regression allows for an understanding of the individual reaction terms involved in the modelled signal transduction pathways and has the benefit of being computationally inexpensive. The obtained results complement existing findings and also confirm the importance of several protein complexes in the MAPK pathway which hints at benefits that can be achieved by further refining the model.

Analysis of voltage source converter-based high-voltage direct current under DC line-to-earth fault

DC line faults on high-voltage direct current (HVDC) systems utilising voltage source converters (VSCs) are a major issue for multi-terminal HVDC systems in which complete isolation of the faulted system is not a viable option. Of these faults, single line-to-earth faults are the most common fault scenario. To better understand the system under such faults, this study analyses the behaviour of HVDC systems based on both conventional two-level converter and multilevel modular converter technology, experiencing a permanent line-to-earth fault. Operation of the proposed system under two different earthing configurations of converter side AC transformer earthed with converter unearthed, and both converter and AC transformer unearthed, was analysed and simulated, with particular attention paid to the converter operation. It was observed that the development of potential earth loops within the system as a result of DC line-to-earth faults leads to substantial overcurrent and results in oscillations depending on the earthing configuration.

Convergence of products from Povarov and von Miller reactions: approaches to helquinoline

Yttrium triflate or triflic acid catalysed Povarov reaction of methyl anthranilate with ethyl vinyl ether, both as aldehyde surrogate and as alkene, gave the desired 2-methyl-4-ethoxytetrahydroquinoline diastereoisomers as the major products along with four component coupling von Miller adducts. A proton NMR-study, using yttrium triflate as catalyst, revealed that the cis-diastereoisomers were the initial major products in both the Povarov and von Miller reactions but that these isomerised to the trans-diastereoisomers under the reaction conditions. Two distinct pathways for forming von Miller adducts were uncovered with the initial Povarov products being converted to von Miller adducts under the reaction conditions. Replacement of the 4-ethoxy with a 4-methoxy group under acidic conditions gave predominantly the trans-diastereoisomer, which was subsequently converted to a cis/trans mixture of the tetrahydroquinoline antibiotic helquinoline. It was also possible to convert the von Miller products to Povarov products under acidic conditions

Interface management for automating finite element analysis workflows

This paper outlines the importance of robust interface management for facilitating finite element analysis workflows. Topological equivalences between analysis model representations are identified and maintained in an editable and accessible manner. The model and its interfaces are automatically represented using an analysis-specific cellular decomposition of the design space. Rework of boundary conditions following changes to the design geometry or the analysis idealization can be minimized by tracking interface dependencies. Utilizing this information with the Simulation Intent specified by an analyst, automated decisions can be made to process the interface information required to rebuild analysis models. Through this work automated boundary condition application is realized within multi-component, multi-resolution and multi-fidelity analysis workflows.

Engineering Simulations

Over recent years, ionic liquids have emerged as a class of novel fluids that have inspired the development of a number of new products and processes. The ability to design these materials with specific functionalities and properties means that they are highly relevant to the growing philosophy of chemical-product design. This is particularly appropriate in the context of a chemical industry that is becoming increasingly focussed on small-volume, high-value added products with relatively short times to market. To support such product and process development, a number of tools can be utilised. A key requirement is that the tool can predict the physical properties and activity coefficients of multi-component mixtures and, if required, model the process in which the materials will be used. Multi-scale simulations that span density functional theory (DFT) to process-engineering computations can address the relevant time and length scales and have increased in usage with the availability of cheap and powerful computers. Herein we will discuss the area of engineering calculations relating to the design of ionic liquid processes, that is, the computational tools that bridge this gap and allow for process simulation tools to utilise and assist in the design of ionic liquids. It will be shown that, at present, it is possible to use available tools to estimate many important properties of ionic liquids and mixtures containing them with a sufficient level of accuracy for preliminary design and selection.

Characterization and modelling of software defined radio front-ends

O presente trabalho tem por objectivo estudar a caracterização e modelação de arquitecturas de rádio frequência para aplicações em rádios definidos por software e rádios cognitivos. O constante aparecimento no mercado de novos padrões e tecnologias para comunicações sem fios têm levantado algumas limitações à implementação de transceptores rádio de banda larga. Para além disso, o uso de sistemas reconfiguráveis e adaptáveis baseados no conceito de rádio definido por software e rádio cognitivo assegurará a evolução para a próxima geração de comunicações sem fios. A ideia base desta tese passa por resolver alguns problemas em aberto e propor avanços relevantes, tirando para isso partido das capacidades providenciadas pelos processadores digitais de sinal de forma a melhorar o desempenho global dos sistemas propostos. Inicialmente, serão abordadas várias estratégias para a implementação e projecto de transceptores rádio, concentrando-se sempre na aplicabilidade específica a sistemas de rádio definido por software e rádio cognitivo. Serão também discutidas soluções actuais de instrumentação capaz de caracterizar um dispositivo que opere simultaneamente nos domínios analógico e digital, bem como, os próximos passos nesta área de caracterização e modelação. Além disso, iremos apresentar novos formatos de modelos comportamentais construídos especificamente para a descrição e caracterização não-linear de receptores de amostragem passa-banda, bem como, para sistemas nãolineares que utilizem sinais multi-portadora. Será apresentada uma nova arquitectura suportada na avaliação estatística dos sinais rádio que permite aumentar a gama dinâmica do receptor em situações de multi-portadora. Da mesma forma, será apresentada uma técnica de maximização da largura de banda de recepção baseada na utilização do receptor de amostragem passa-banda no formato complexo. Finalmente, importa referir que todas as arquitecturas propostas serão acompanhadas por uma introdução teórica e simulações, sempre que possível, sendo após isto validadas experimentalmente por protótipos laboratoriais.

Modelling the airline costs of delay propagation

Reactionary delays constitute nearly half of all delay minutes in Europe. A capped, multi-component model is presented for estimating reactionary delay costs, as a non-linear function of primary delay duration. Maximum Take-Off Weights, historically established as a charging mechanism, may be used to model delay costs. Current industry reporting on delay is flight-centric. Passenger-centric metrics are needed to better understand delay propagation. In ATM, it is important to take account of contrasting flight- and passenger-centric effects, caused by cancellations, for example. Costs to airlines and passenger disutility will both continue to be driven by delay relative to the original schedule.

Strength prediction of single- and double-lap joints by standard and extended finite element modelling

The structural integrity of multi-component structures is usually determined by the strength and durability of their unions. Adhesive bonding is often chosen over welding, riveting and bolting, due to the reduction of stress concentrations, reduced weight penalty and easy manufacturing, amongst other issues. In the past decades, the Finite Element Method (FEM) has been used for the simulation and strength prediction of bonded structures, by strength of materials or fracture mechanics-based criteria. Cohesive-zone models (CZMs) have already proved to be an effective tool in modelling damage growth, surpassing a few limitations of the aforementioned techniques. Despite this fact, they still suffer from the restriction of damage growth only at predefined growth paths. The eXtended Finite Element Method (XFEM) is a recent improvement of the FEM, developed to allow the growth of discontinuities within bulk solids along an arbitrary path, by enriching degrees of freedom with special displacement functions, thus overcoming the main restriction of CZMs. These two techniques were tested to simulate adhesively bonded single- and double-lap joints. The comparative evaluation of the two methods showed their capabilities and/or limitations for this specific purpose.

Effect of school based physical activity programme (KISS) on fitness and adiposity in primary schoolchildren: cluster randomised controlled trial.

To assess the effectiveness of a school based physical activity programme during one school year on physical and psychological health in young schoolchildren. Cluster randomised controlled trial. 28 classes from 15 elementary schools in Switzerland randomly selected and assigned in a 4:3 ratio to an intervention (n=16) or control arm (n=12) after stratification for grade (first and fifth grade), from August 2005 to June 2006. 540 children, of whom 502 consented and presented at baseline. Children in the intervention arm (n=297) received a multi-component physical activity programme that included structuring the three existing physical education lessons each week and adding two additional lessons a week, daily short activity breaks, and physical activity homework. Children (n=205) and parents in the control group were not informed of an intervention group. For most outcome measures, the assessors were blinded. Primary outcome measures included body fat (sum of four skinfolds), aerobic fitness (shuttle run test), physical activity (accelerometry), and quality of life (questionnaires). Secondary outcome measures included body mass index and cardiovascular risk score (average z score of waist circumference, mean blood pressure, blood glucose, inverted high density lipoprotein cholesterol, and triglycerides). 498 children completed the baseline and follow-up assessments (mean age 6.9 (SD 0.3) years for first grade, 11.1 (0.5) years for fifth grade). After adjustment for grade, sex, baseline values, and clustering within classes, children in the intervention arm compared with controls showed more negative changes in the z score of the sum of four skinfolds (-0.12, 95 % confidence interval -0.21 to -0.03; P=0.009). Likewise, their z scores for aerobic fitness increased more favourably (0.17, 0.01 to 0.32; P=0.04), as did those for moderate-vigorous physical activity in school (1.19, 0.78 to 1.60; P<0.001), all day moderate-vigorous physical activity (0.44, 0.05 to 0.82; P=0.03), and total physical activity in school (0.92, 0.35 to 1.50; P=0.003). Z scores for overall daily physical activity (0.21, -0.21 to 0.63) and physical quality of life (0.42, -1.23 to 2.06) as well as psychological quality of life (0.59, -0.85 to 2.03) did not change significantly. A school based multi-component physical activity intervention including compulsory elements improved physical activity and fitness and reduced adiposity in children. Trial registration Current Controlled Trials ISRCTN15360785.

Using stimulus equivalence to teach monetary skills to school-age children with autism

The present study evaluated the use of stimulus equivalence in teaching monetary skills to school aged children with autism. An AB within-subject design with periodic probes was used. At pretest, three participants demonstrated relation DA, an auditory-visual relation (matching dictated coin values to printed coin prices). Using a three-choice match-to-sample procedure, with a multi-component intervention package, these participants were taught two trained relations, BA (matching coins to printed prices) and CA (matching coin combinations to printed prices). Two participants achieved positive tests of equivalence, and the third participant demonstrated emergent performances with a symmetric and transitive relation. In addition, two participants were able to show generalization of learned skills with a parent, in a second naturalistic setting. The present research replicates and extends the results of previous studies by demonstrating that stimulus equivalence can be used to teach an adaptive skill to children with autism.

ESI-MS[n] of anticancer pt[iv] organoamido complexes and their interactions with DNA-model compounds /

The general solution behaviour and" the major fragmentation pathways of the anticanceractive PtIV coordination complexes, trans, trans, cis, cis-[PtCIOH{N(pFC6F4) CH2h(pY)2] (1), trans, cis, cis-[Pt(OH)2{N(p-FC6F4)CH2h(Py)2] (2), trans, cis, cis-[Pt(OH)2{N(p-HC6F4)CH2h(Py)2] (3), trans, trans, cis, cis-[PtCIOH{N(pHC6F4) CH2h(Py)2] (4), and trans, trans, cis, cis-[PtOH(OCH3){N(p-HC6F4)CH2h(PY)2] (5) (Py = pyridine) have been deduced by positive-ion tandem-in-time ESI-MS. Overall, the acquired full-scan, positive-ion ESI-MS spectra of 2, 3, and 5 were characterized by the presence of relatively low-intensity [M+Nar and [M+Kt mass spectral peaks, whereas those of 1 and 4 were dominated by extremely intense [M+Hr peaks. Complexes 2 and 3 were also noted to form [2M+Ht and [2M+Nat dilneric cations. The source of Na + and K+ ions is believed to be the sample, the solvent systems used or the transport line carrying the sample solutions into the ES ion source. Further, the fragmentation pathway of all complexes studied was found to be almost identical with concurrent loss of py and H20 molecules, loss of a {N(p-YC6F4)CH2} (Y = F, H) group and/or concomitant release of the latter group and a py ligand being the most conunon. The photochemical degradation behaviour of 1 and 2 was also investigated using either fluorescent or ultraviolet light and some products of that degradation were positively identified. Altogether, light irradiation of solutions of both complexes resulted in cation cationisation, reductive-elimination, ligand-release, ligand-exchange and ligand-addition reactions. Finally, positive- and negative-ion ESI-MSn spectra of 5' -GMP, guanosine, inosine and products of their reactions with 1, 2,3, and 4 were also recorded. On the whole, full-scan ESI-MS spectra of the pure nucleobases revealed the presence of cationic and anionic species that are highly reflective of both their solution ionic composition and their propensity t9 form polymeric clusters. Analyses of mass spectra acquired from their reaction solutions with the aforementioned platinum complexes indicated very slow kinetics. However, all complexes investigated formed, to various degrees, Pt-nucleobase adducts with guanosine and inosine, but not with 5'-GMP. The products included species having coordination numbers of III, IV, V, and VI, among which the first-time· observed, coordinatively saturated, jive-coordinate PtlI-nucleobase complexes were of most interest. The latter complexes are presumably stabilized by 7tback- donation involving the filled d orbitals of the PtII centre and the empty pz· orbital of MeCN. All products, whose peaks appeared inlull-scan ESI-MS spectra, are believed to represent solution species rather than artifacts of gas-phase processes. Finally, negativeion ESI-MSn spectra recorded in reaction solutions of 1 and 4 with guanosine and of the latter complex with inosine revealed the negative-ion-ESI-MS first-time observed, noncovalent, nucleoside-chloride adducts, with the source of chloride anion being complexes 1 and 4 theillselves. In contrast, no such adducts were observed to form with Na25'-GMP or its protonated fonn. Few suggestions are offered for the possible cause(s) behind the absence of such adduct ions.