Application of static charge transfer within an ionic-liquid force field and its effect on structure and dynamics

The effects of linear scaling of the atomic charges of a reference potential on the structure, dynamics, and energetics of the ionic liquid 1,3-dimethylimidazolium chloride are investigated. Diffusion coefficients that span over four orders of magnitude are observed between the original model and a scaled model in which the ionic charges are +/- 0.5 e. While the three-dimensional structure of the liquid is less affected, the partial radial distribution functions change markedly-with the positive result that for ionic charges of +/- 0.7 e, an excellent agreement is observed with ab initio molecular dynamics data. Cohesive energy densities calculated from these partial-charge models are also in better agreement with those calculated from the ab initio data. We postulate that ionic-liquid models in which the ionic charges are assumed to be +/- 1 e overestimate the intermolecular attractions between ions, which results in overstructuring, slow dynamics, and increased cohesive energy densities. The use of scaled-charge sets may be of benefit in the simulation of these systems-especially when looking at properties beyond liquid structure-thus providing on alternative to computationally expensive polarisable force fields.

Interaction of directional, neuromuscular and egocentric constraints on the stability of preferred bimanual coordination patterns

We investigated how the relative direction of limb movements in external space (iso- and non-isodirectionality), muscular constraints (the relative timing of homologous muscle activation) and the egocentric frame of reference (moving simultaneously toward/away the longitudinal axis of the body) contribute to the stability of coordinated movements. In the first experiment, we attempted to determine the respective stability of isodirectional and non-isodirectional movements in between-persons coordination. In a second experiment, we determined the effect of the relative direction in external space, and of muscular constraints, on pattern stability during a within-person bimanual coordination task. In the third experiment we dissociated the effects on pattern stability of the muscular constraints, relative direction and egocentric frame of reference. The results showed that (1) simultaneous activation of homologous muscles resulted in more stable performance than simultaneous activation of non-homologous muscles during within-subject coordination, and that (2) isodirectional movements were more stable than non-isodirectional movements during between-persons coordination, confirming the role of the relative direction of the moving limbs in the stability of bimanual coordination. Moreover, the egocentric constraint was to some extent found distinguishable from the effect of the relative direction of the moving limbs in external space, and from the effect of the relative timing of muscle activation. In summary, the present study showed that relative direction of the moving limbs in external space and muscular constraints may interact either to stabilize or destabilize coordination patterns. (C) 2003 Published by Elsevier B.V.

Statistical theory of finite Fermi systems with chaotic excited eigenstates

A theory of strongly interacting Fermi systems of a few particles is developed. At high excit at ion energies (a few times the single-parti cle level spacing) these systems are characterized by an extreme degree of complexity due to strong mixing of the shell-model-based many-part icle basis st at es by the residual two- body interaction. This regime can be described as many-body quantum chaos. Practically, it occurs when the excitation energy of the system is greater than a few single-particle level spacings near the Fermi energy. Physical examples of such systems are compound nuclei, heavy open shell atoms (e.g. rare earths) and multicharged ions, molecules, clusters and quantum dots in solids. The main quantity of the theory is the strength function which describes spreading of the eigenstates over many-part icle basis states (determinants) constructed using the shell-model orbital basis. A nonlinear equation for the strength function is derived, which enables one to describe the eigenstates without diagonalization of the Hamiltonian matrix. We show how to use this approach to calculate mean orbital occupation numbers and matrix elements between chaotic eigenstates and introduce typically statistical variable s such as t emperature in an isolated microscopic Fermi system of a few particles.

Sensory systems and spatial memory in the fruit bat Rousettus aegyptiacus

The megachiropteran fruit bat Rousettus aegyptiacus is able to orient and navigate using both vision and echolocation. These two sensory systems have different environmental constraints however, echolocation being relatively short range when compared with vision. Despite this difference, an experiment testing their memory of a perch location demonstrates that once the location of a perch is learned R. aegyptiacus is not influenced by the movement of local landmark cues in the vicinity of the perch under either light or dark conditions. Thus despite the differing constraints of vision and echolocation, this suggests a place is remembered as a location in space and not by associations with landmarks in the vicinity. A decrease in initial performance when the task was repeated in the dark suggested the possibility that a memory of a location learned using vision does not generalize to echolocation.

R-matrix-Floquet theory of multiphoton processes:VIII. A linear equations method

A new linear equations method for calculating the R-matrix, which arises in the R-matrix-Floquet theory of multiphoton processes, is introduced. This method replaces the diagonalization of the Floquet Hamiltonian matrix by the solution of a set of linear simultaneous equations which are solved, in the present work, by the conjugate gradient method. This approach uses considerably less computer memory and can be readily ported onto parallel computers. It will thus enable much larger problems of current interest to be treated. This new method is tested by applying it to three-photon ionization of helium at frequencies where double resonances with a bound state and autoionizing states are important. Finally, an alternative linear equations method, which avoids the explicit calculation of the R-matrix by incorporating the boundary conditions directly, is described in an appendix.

The role of Na surface species on oxygen charge transfer in the Pt/YSZ system

The role of sodium surface species in the modification of a platinum (Pt) catalyst film supported on 8 mol% yttria-stabilised-zirconia (YSZ) was investigated under a flow of 20 kPa oxygen at 400 °C. Cyclic and linear sweep voltammetry were used to investigate the kinetics of the oxygen charge transfer reaction. The Pt/YSZ systems of both ‘clean’ and variable-coverage sodium-modified catalyst surfaces were also characterised using SEM, XPS and work function measurements using the Kelvin probe technique.

Samples with sodium coverage from 0.5 to 100% were used. It was found that sodium addition modifies the binding energy of oxygen onto the catalyst surface. Cyclic voltammetry experiments showed that higher overpotentials were required for oxygen reduction with increasing sodium coverage. In addition, sodium was found to modify oxygen storage and/or adsorption and diffusion increasing current densities at higher cathodic overpotential. Ex situ XPS measurements showed the presence of sodium hydroxide, carbonate and/or oxide species on the catalyst surface, while the Kelvin probe technique showed a decrease of approximately 250 meV in the work function of samples with more than 50% sodium coverage (compared to a nominally ‘clean’ sample).

Analysis of Dependence Tracking Algorithms for Task Dataflow Execution

Processor architectures has taken a turn towards many-core processors, which integrate multiple processing cores on a single chip to increase overall performance, and there are no signs that this trend will stop in the near future. Many-core processors are harder to program than multi-core and single-core processors due to the need of writing parallel or concurrent programs with high degrees of parallelism. Moreover, many-cores have to operate in a mode of strong scaling because of memory bandwidth constraints. In strong scaling increasingly finer-grain parallelism must be extracted in order to keep all processing cores busy.

Task dataflow programming models have a high potential to simplify parallel program- ming because they alleviate the programmer from identifying precisely all inter-task de- pendences when writing programs. Instead, the task dataflow runtime system detects and enforces inter-task dependences during execution based on the description of memory each task accesses. The runtime constructs a task dataflow graph that captures all tasks and their dependences. Tasks are scheduled to execute in parallel taking into account dependences specified in the task graph.

Several papers report important overheads for task dataflow systems, which severely limits the scalability and usability of such systems. In this paper we study efficient schemes to manage task graphs and analyze their scalability. We assume a programming model that supports input, output and in/out annotations on task arguments, as well as commutative in/out and reductions. We analyze the structure of task graphs and identify versions and generations as key concepts for efficient management of task graphs. Then, we present three schemes to manage task graphs building on graph representations, hypergraphs and lists. We also consider a fourth edge-less scheme that synchronizes tasks using integers. Analysis using micro-benchmarks shows that the graph representation is not always scalable and that the edge-less scheme introduces least overhead in nearly all situations.

Dynamic identification of building structures: new strategies:Meccanica dei materiali e delle strutture

In this paper the evolution of a time domain dynamic identification technique based on a statistical moment approach is presented. This technique can be used in the case of structures under base random excitations in the linear state and in the non linear one. By applying Itoˆ stochastic calculus, special algebraic equations can be obtained depending on the statistical moments of the response of the system to be identified. Such equations can be used for the dynamic identification of the mechanical parameters and of the input. The above equations, differently from many techniques in the literature, show the possibility of obtaining the identification of the dissipation characteristics independently from the input. Through the paper the first formulation of this technique, applicable to non linear systems, based on the use of a restricted class of the potential models, is presented. Further a second formulation of the technique in object, applicable to each kind of linear systems and based on the use of a class of linear models, characterized by a mass proportional damping matrix, is described.

A-level Mathematics Options – Views of Secondary-level Teachers

The A-level Mathematics qualification is based on a compulsory set of pure maths modules and a selection of applied maths modules with the pure maths representing two thirds of the assessment. The applied maths section includes mechanics, statistics and (sometimes) decision maths. A combination of mechanics and statistics tends to be the most popular choice by far. The current study aims to understand how maths teachers in secondary education make decisions regarding the curriculum options and offers useful insight to those currently designing the new A-level specifications.

Semi-structured interviews were conducted with A-level maths teachers representing 27 grammar schools across Northern Ireland. Teachers were generally in agreement regarding the importance of pure maths and the balance between pure and applied within the A-level maths curriculum. A wide variety of opinions existed concerning the applied options. While many believe that the basic mechanics-statistics (M1-S1) combination is most accessible, it was also noted that the M1-M2 combination fits neatly alongside A-level physics. Lack of resources, timetabling constraints and competition with other subjects in the curriculum hinder uptake of A-level Further Maths.

Teachers are very conscious of the need to obtain high grades to benefit both their pupils and the school’s reputation. The move to a linear assessment system in England while Northern Ireland retains the modular system is likely to cause some schools to review their choice of exam board although there is disagreement as to whether a modular or linear system is more advantageous for pupils. The upcoming change in the specification offers an opportunity to refresh the assessment also and reduce the number of leading questions. However, teachers note that there are serious issues with GCSE maths and these have implications for A-level.

Direct oxidation of amines to nitriles in the presence of ruthenium-terpyridyl complex immobilized on ILs/SILP

The immobilization of a ruthenium complex (Ru2Cl4(az-tpy)2) within a range of supported ionic liquids ([C4C1im]Cl, [C4C1im][NTf2], [C6C1im]Cl, [C4C1pyrr]Br, [C4C1im]Br, [C4C1pyrr]Cl) dispersed silica (SILP) operates as an efficient heterogeneous catalyst in oxidation of long chain linear primary amines to corresponding nitriles. This reaction follows a “green” route using a cheap and easy to handles oxidant (oxygen or air). The conversion was found to be strongly influenced by the alkyl chain length of the amine substrate and the choice of oxidant. No condensation reaction was observed between the starting amines and the selectivity to nitrile is 100%. Moving from a composition of 20 atm N2/5 atm O2 to 5 atm N2/20 atm O2 led to enhancements in the conversion (n-alkylamines) and selectivity (benzonitrile) which have been correlated with an increase of the solubilized oxygen. This was further supported by using different inert gas (nitrogen, helium, argon)/oxygen mixtures indicating that the O2 solubility in the SILP system, has an important effect on conversions and TON in this reaction using SILP catalysts. Experiments performed in the presence of CO2 led to a different behaviour due to the formation of amine-CO2 adducts. The application of the Weisz–Prater criterion confirmed the absence of any diffusional constraints.

Fusion of Static and Temporal Information for Threat Evaluation in Sensor Networks

In many CCTV and sensor network based intelligent surveillance systems, a number of attributes or criteria are used to individually evaluate the degree of potential threat of a suspect. The outcomes for these attributes are in general from analytical algorithms where data are often pervaded with uncertainty and incompleteness. As a result, such individual threat evaluations are often inconsistent, and individual evaluations can change as time elapses. Therefore, integrating heterogeneous threat evaluations with temporal influence to obtain a better overall evaluation is a challenging issue. So far, this issue has rarely be considered by existing event reasoning frameworks under uncertainty in sensor network based surveillance. In this paper, we first propose a weighted aggregation operator based on a set of principles that constraints the fusion of individual threat evaluations. Then, we propose a method to integrate the temporal influence on threat evaluation changes. Finally, we demonstrate the usefulness of our system with a decision support event modeling framework using an airport security surveillance scenario.

An approach to determine the local boundary of small disturbance voltage stability region in a cut-set power space:基于微扰的割集电压稳定域局部边界求解方法

A new approach to determine the local boundary of voltage stability region in a cut-set power space (CVSR) is presented. Power flow tracing is first used to determine the generator-load pair most sensitive to each branch in the interface. The generator-load pairs are then used to realize accurate small disturbances by controlling the branch power flow in increasing and decreasing directions to obtain new equilibrium points around the initial equilibrium point. And, continuous power flow is used starting from such new points to get the corresponding critical points around the initial critical point on the CVSR boundary. Then a hyperplane cross the initial critical point can be calculated by solving a set of linear algebraic equations. Finally, the presented method is validated by some systems, including New England 39-bus system, IEEE 118-bus system, and EPRI-1000 bus system. It can be revealed that the method is computationally more efficient and has less approximation error. It provides a useful approach for power system online voltage stability monitoring and assessment. This work is supported by National Natural Science Foundation of China (No. 50707019), Special Fund of the National Basic Research Program of China (No. 2009CB219701), Foundation for the Author of National Excellent Doctoral Dissertation of PR China (No. 200439), Tianjin Municipal Science and Technology Development Program (No. 09JCZDJC25000), National Major Project of Scientific and Technical Supporting Programs of China During the 11th Five-year Plan Period (No. 2006BAJ03A06). ©2009 State Grid Electric Power Research Institute Press.

Storage of sediment-associated nutrients and contaminants in river channel and floodplain systems

Samples of fine-grained channel bed sediment and overbank floodplain deposits were collected along the main channels of the Rivers Aire (and its main tributary, the River Calder) and Swale, in Yorkshire, UK, in order to investigate downstream changes in the storage and deposition of heavy metals (Cr, Cu, Pb, Zn), total P and the sum of selected PCB congeners, and to estimate the total storage of these contaminants within the main channels and floodplains of these river systems. Downstream trends in the contaminant content of the <63 μm fraction of channel bed and floodplain sediment in the study rivers are controlled mainly by the location of the main sources of the contaminants, which varies between rivers. In the Rivers Aire and Calder, the contaminant content of the <63 μm fraction of channel bed and floodplain sediment generally increases in a downstream direction, reflecting the location of the main urban and industrialized areas in the middle and lower parts of the basin. In the River Swale, the concentrations of most of the contaminants examined are approximately constant along the length of the river, due to the relatively unpolluted nature of this river. However, the Pb and Zn content of fine channel bed sediment decreases downstream, due to the location of historic metal mines in the headwaters of this river, and the effect of downstream dilution with uncontaminated sediment. The magnitude and spatial variation of contaminant storage and deposition on channel beds and floodplains are also controlled by the amount of <63 μm sediment stored on the channel bed and deposited on the floodplain during overbank events. Consequently, contaminant deposition and storage are strongly influenced by the surface area of the floodplain and channel bed. Contaminant storage on the channel beds of the study rivers is, therefore, generally greatest in the middle and lower reaches of the rivers, since channel width increases downstream. Comparisons of the estimates of total storage of specific contaminants on the channel beds of the main channel systems of the study rivers with the annual contaminant flux at the catchment outlets indicate that channel storage represents <3% of the outlet flux and is, therefore, of limited importance in regulating that flux. Similar comparisons between the annual deposition flux of specific contaminants to the floodplains of the study rivers and the annual contaminant flux at the catchment outlet, emphasise the potential importance of floodplain deposition as a conveyance loss. In the case of the River Aire the floodplain deposition flux is equivalent to between ca. 2% (PCBs) and 36% (Pb) of the outlet flux. With the exception of PCBs, for which the value is ≅0, the equivalent values for the River Swale range between 18% (P) and 95% (Pb). The study emphasises that knowledge of the fine-grained sediment delivery system operating in a river basin is an essential prerequisite for understanding the transport and storage of sediment-associated contaminants in river systems and that conveyance losses associated with floodplain deposition exert an important control on downstream contaminant fluxes and the fate of such contaminants. © 2003 Elsevier Science Ltd. All rights reserved.

Study of oxidation and non-enzymatic glycosylation posttranslational modifications using a proteomic approach

A glicosilação não-enzimática e o stress oxidativo representam dois processos importantes visto desempenharem um papel importante no que respeita às complicações de vários processos patofisiológicos. No presente, a associação entre a glicosilação não-enzimática e a oxidação de proteínas é reconhecida como sendo um dos principais responsáveis pela acumulação de proteínas não-funcionais que, por sua vez, promove uma contínua sensibilização para um aumento do stress oxidativo ao nível celular. Embora esteja disponível bastante informação no que respeita aos dois processos e suas consequências ao nível estrutural e funcional, permanecem questões por esclarecer acerca do que se desenvolve ao nível molecular. Com o objectivo de contribuir para uma melhor compreensão da relação entre a glicosilação não-enzimática e a oxidação, proteínas modelo (albumina, insulina e histonas H2B e H1) foram submetidas a sistemas in vitro de glicosilação não-enzimática e oxidação em condições controladas e durante um período de tempo específico. A identificação dos locais de glicosilação e oxidação foi realizada através de uma abordagem proteómica, na qual após digestão enzimática se procedeu à análise por cromatografia líquida acoplada a espectrometria de massa tandem (MALDI-TOF/TOF). Esta abordagem permitiu a obtenção de elevadas taxas de cobertura das sequências proteicas, permitindo a identificação dos locais preferenciais de glicosilação e oxidação nas diferentes proteínas estudadas. Como esperado, os resíduos de lisina foram os preferencialmente glicosilados. No que respeita à oxidação, além das modificações envolvendo hidroxilações e adições de oxigénio, foram identificadas deamidações, carbamilações e conversões oxidativas específicas de vários aminoácidos. No geral, os resíduos mais afectados pela oxidação foram os resíduos de cisteína, metionina, triptofano, tirosina, prolina, lisina e fenilalanina. Ao longo do período de tempo estudado, os resultados indicaram que a oxidação teve início em zonas expostas da proteína e/ou localizadas na vizinhança de resíduos de cisteína e metionina, ao invés de exibir um comportamente aleatório, ocorrendo de uma forma nãolinear por sua vez dependente da estabilidade conformacional da proteína. O estudo ao longo do tempo mostrou igualmente que, no caso das proteínas préglicosiladas, a oxidação das mesmas ocorreu de forma mais rápida e acentuada, sugerindo que as alterações estruturais induzidas pela glicosilação promovem um estado pro-oxidativo. No caso das proteínas pré-glicosiladas e oxidadas, foi identificado um maior número de modificações oxidativas assim como de resíduos modificados na vizinhança de resíduos glicosilados. Com esta abordagem é realizada uma importante contribuição na investigação das consequências do dano ‘glico-oxidativo’ em proteínas ao nível molecular através da combinação da espectrometria de massa e da bioinformática.

Optimal alarms systems and its application to financial time series

This thesis focuses on the application of optimal alarm systems to non linear time series models. The most common classes of models in the analysis of real-valued and integer-valued time series are described. The construction of optimal alarm systems is covered and its applications explored. Considering models with conditional heteroscedasticity, particular attention is given to the Fractionally Integrated Asymmetric Power ARCH, FIAPARCH(p; d; q) model and an optimal alarm system is implemented, following both classical and Bayesian methodologies. Taking into consideration the particular characteristics of the APARCH(p; q) representation for financial time series, the introduction of a possible counterpart for modelling time series of counts is proposed: the INteger-valued Asymmetric Power ARCH, INAPARCH(p; q). The probabilistic properties of the INAPARCH(1; 1) model are comprehensively studied, the conditional maximum likelihood (ML) estimation method is applied and the asymptotic properties of the conditional ML estimator are obtained. The final part of the work consists on the implementation of an optimal alarm system to the INAPARCH(1; 1) model. An application is presented to real data series.