Mn(II) complexes of some acylhydrazones with NNO donor sites: Syntheses, a spectroscopic view on their coordination possibilities and crystal structures

Mn(II) complexes derived from a set of acylhydrazones were synthesised and characterized by elemental analyzes, IR, UV–vis and X-band EPR spectral studies as well as conductivity and magnetic susceptibility measurements. In the reported complexes, the hydrazones exist either in the keto or enolate form, as evidenced by IR spectral data. Crystal structures of two complexes are well established using single crystal X-ray diffraction studies. In both of these complexes two equivalent monoanionic ligands are coordinated in a meridional fashion using cis pyridyl, trans azomethine nitrogen and cis enolate oxygen atoms positioned very nearly perpendicular to each other. EPR spectra in DMF solutions at 77 K show hyperfine sextets and in some of the complexes the low intensity forbidden lines lying between each of the two hyperfine lines are also observed

Performance of Supply Chain when using selected Coordination Mechanisms

Coordination among supply chain members is essential for better supply chain performance. An effective method to improve supply chain coordination is to implement proper coordination mechanisms. The primary objective of this research is to study the performance of a multi-level supply chain while using selected coordination mechanisms separately, and in combination, under lost sale and back order cases. The coordination mechanisms used in this study are price discount, delay in payment and different types of information sharing. Mathematical modelling and simulation modelling are used in this study to analyse the performance of the supply chain using these mechanisms. Initially, a three level supply chain consisting of a supplier, a manufacturer and a retailer has been used to study the combined effect of price discount and delay in payment on the performance (profit) of supply chain using mathematical modelling. This study showed that implementation of individual mechanisms improves the performance of the supply chain compared to ‘no coordination’. When more than one mechanism is used in combination, performance in most cases further improved. The three level supply chain considered in mathematical modelling was then extended to a three level network supply chain consisting of a four retailers, two wholesalers, and a manufacturer with an infinite part supplier. The performance of this network supply chain was analysed under both lost sale and backorder cases using simulation modelling with the same mechanisms: ‘price discount and delay in payment’ used in mathematical modelling. This study also showed that the performance of the supply chain is significantly improved while using combination of mechanisms as obtained earlier. In this study, it is found that the effect (increase in profit) of ‘delay in payment’ and combination of ‘price discount’ & ‘delay in payment’ on SC profit is relatively high in the case of lost sale. Sensitivity analysis showed that order cost of the retailer plays a major role in the performance of the supply chain as it decides the order quantity of the other players in the supply chain in this study. Sensitivity analysis also showed that there is a proportional change in supply chain profit with change in rate of return of any player. In the case of price discount, elasticity of demand is an important factor to improve the performance of the supply chain. It is also found that the change in permissible delay in payment given by the seller to the buyer affects the SC profit more than the delay in payment availed by the buyer from the seller. In continuation of the above, a study on the performance of a four level supply chain consisting of a manufacturer, a wholesaler, a distributor and a retailer with ‘information sharing’ as coordination mechanism, under lost sale and backorder cases, using a simulation game with live players has been conducted. In this study, best performance is obtained in the case of sharing ‘demand and supply chain performance’ compared to other seven types of information sharing including traditional method. This study also revealed that effect of information sharing on supply chain performance is relatively high in the case of lost sale than backorder. The in depth analysis in this part of the study showed that lack of information sharing need not always be resulting in bullwhip effect. Instead of bullwhip effect, lack of information sharing produced a huge hike in lost sales cost or backorder cost in this study which is also not favorable for the supply chain. Overall analysis provided the extent of improvement in supply chain performance under different cases. Sensitivity analysis revealed useful insights about the decision variables of supply chain and it will be useful for the supply chain management practitioners to take appropriate decisions.

Queues with inter- ruption in Random/ Markovian Environment

In many situations probability models are more realistic than deterministic models. Several phenomena occurring in physics are studied as random phenomena changing with time and space. Stochastic processes originated from the needs of physicists.Let X(t) be a random variable where t is a parameter assuming values from the set T. Then the collection of random variables {X(t), t ∈ T} is called a stochastic process. We denote the state of the process at time t by X(t) and the collection of all possible values X(t) can assume, is called state space

Ferrocene-Based Pyridylphosphine Ligands – Coordination Chemistry of Group 10, 11 and 12 Metals

English: The present thesis describes the synthesis of 1,1’-ferrocendiyl-based pyridylphosphine ligands, the exploration of their fundamental coordination chemistry and preliminary experiments with selected complexes aimed at potential applications. One main aspect is the synthesis of the bidentate ferrocene-based pyridylphosphine ligands 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene, 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene and 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. A specific feature of these ligands is the ball-bearing like flexibility of the ferrocenebased backbone. An additional flexibility element is the rotation around the C–C single bonds. Consequently, the donor atoms can realise a wide range of positions with respect to each other and are therefore able to adapt to the coordination requirements of different metal centres. The flexibility of the ligand also plays a role in another key aspect of this work, which concerns the coordination mode, i. e. bridging vs. chelating. In addition to the flexibility, also the position of the donor atoms to each other is important. This is largely affected by the position of the pyridyl nitrogen (pyrid-2-yl vs. pyrid-3-yl) and the methylen group in 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. Another interesting point is the combination of a soft phosphorus donor atom with a harder nitrogen donor atom, according to the HSAB principle. This combination generates a unique binding profile, since the pi-acceptor character of the P site is able to stabilise a metal centre in a low oxidation state, while the nitrogen sigma-donor ability can make the metal more susceptible to oxidative addition reactions. A P,N-donor combination can afford hemilabile binding profiles, which would be ideal for catalysis. Beyond 1,2-substituted ferrocene derivatives, which are quite successful in catalytic applications, 1,1’-derivatives are rather underrepresented. While a low-yield synthetic pathway to 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene was already described in the literature [I. R. Butler, Organometallics 1992, 11, 74.], it was possible to find a new, improved and simplified synthetic pathway. Both other ligands were unknown prior to this work. Satisfactory results in the synthesis of 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene could be achieved by working in analogy to the new synthetic procedure for 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene. The synthesis of 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene has been handled by the group of Prof. Petr Stepnicka from Charles University, Prague, Czech Republic. The synthesis of tridentate ligands with an analogous heterodentate arrangement, was investigated briefly as a sideline of this study. The major part of this thesis deals with the fundamental coordination chemistry towards transition metals of the groups 10, 11 and 12. Due to the well-established catalytic properties of analogous palladium complexes, the coordination chemistry towards palladium (group 10) is of particular interest. The metals zinc and cadmium (group 12) are also of substantial importance because they are redox-inert in their divalent state. This is relevant in view of electrochemical investigations concerning the utilisation of the ligands as molecular redox sensors. Also mercury and the monovalent metals silver and gold (group 11) are included because of their rich coordination chemistry. It is essential to answer questions concerning aspects of the ligands’ coordination mode bearing in mind the HSAB principle.

The prediction of seasonal and inter-annual climate variations and their impacts on the water resources in the eastern seaboard of Thailand

The research of this thesis dissertation covers developments and applications of short-and long-term climate predictions. The short-term prediction emphasizes monthly and seasonal climate, i.e. forecasting from up to the next month over a season to up to a year or so. The long-term predictions pertain to the analysis of inter-annual- and decadal climate variations over the whole 21st century. These two climate prediction methods are validated and applied in the study area, namely, Khlong Yai (KY) water basin located in the eastern seaboard of Thailand which is a major industrial zone of the country and which has been suffering from severe drought and water shortage in recent years. Since water resources are essential for the further industrial development in this region, a thorough analysis of the potential climate change with its subsequent impact on the water supply in the area is at the heart of this thesis research. The short-term forecast of the next-season climate, such as temperatures and rainfall, offers a potential general guideline for water management and reservoir operation. To that avail, statistical models based on autoregressive techniques, i.e., AR-, ARIMA- and ARIMAex-, which includes additional external regressors, and multiple linear regression- (MLR) models, are developed and applied in the study region. Teleconnections between ocean states and the local climate are investigated and used as extra external predictors in the ARIMAex- and the MLR-model and shown to enhance the accuracy of the short-term predictions significantly. However, as the ocean state – local climate teleconnective relationships provide only a one- to four-month ahead lead time, the ocean state indices can support only a one-season-ahead forecast. Hence, GCM- climate predictors are also suggested as an additional predictor-set for a more reliable and somewhat longer short-term forecast. For the preparation of “pre-warning” information for up-coming possible future climate change with potential adverse hydrological impacts in the study region, the long-term climate prediction methodology is applied. The latter is based on the downscaling of climate predictions from several single- and multi-domain GCMs, using the two well-known downscaling methods SDSM and LARS-WG and a newly developed MLR-downscaling technique that allows the incorporation of a multitude of monthly or daily climate predictors from one- or several (multi-domain) parent GCMs. The numerous downscaling experiments indicate that the MLR- method is more accurate than SDSM and LARS-WG in predicting the recent past 20th-century (1971-2000) long-term monthly climate in the region. The MLR-model is, consequently, then employed to downscale 21st-century GCM- climate predictions under SRES-scenarios A1B, A2 and B1. However, since the hydrological watershed model requires daily-scale climate input data, a new stochastic daily climate generator is developed to rescale monthly observed or predicted climate series to daily series, while adhering to the statistical and geospatial distributional attributes of observed (past) daily climate series in the calibration phase. Employing this daily climate generator, 30 realizations of future daily climate series from downscaled monthly GCM-climate predictor sets are produced and used as input in the SWAT- distributed watershed model, to simulate future streamflow and other hydrological water budget components in the study region in a multi-realization manner. In addition to a general examination of the future changes of the hydrological regime in the KY-basin, potential future changes of the water budgets of three main reservoirs in the basin are analysed, as these are a major source of water supply in the study region. The results of the long-term 21st-century downscaled climate predictions provide evidence that, compared with the past 20th-reference period, the future climate in the study area will be more extreme, particularly, for SRES A1B. Thus, the temperatures will be higher and exhibit larger fluctuations. Although the future intensity of the rainfall is nearly constant, its spatial distribution across the region is partially changing. There is further evidence that the sequential rainfall occurrence will be decreased, so that short periods of high intensities will be followed by longer dry spells. This change in the sequential rainfall pattern will also lead to seasonal reductions of the streamflow and seasonal changes (decreases) of the water storage in the reservoirs. In any case, these predicted future climate changes with their hydrological impacts should encourage water planner and policy makers to develop adaptation strategies to properly handle the future water supply in this area, following the guidelines suggested in this study.

Intelligence by Design: Principles of Modularity and Coordination for Engineerin

All intelligence relies on search --- for example, the search for an intelligent agent's next action. Search is only likely to succeed in resource-bounded agents if they have already been biased towards finding the right answer. In artificial agents, the primary source of bias is engineering. This dissertation describes an approach, Behavior-Oriented Design (BOD) for engineering complex agents. A complex agent is one that must arbitrate between potentially conflicting goals or behaviors. Behavior-oriented design builds on work in behavior-based and hybrid architectures for agents, and the object oriented approach to software engineering. The primary contributions of this dissertation are: 1.The BOD architecture: a modular architecture with each module providing specialized representations to facilitate learning. This includes one pre-specified module and representation for action selection or behavior arbitration. The specialized representation underlying BOD action selection is Parallel-rooted, Ordered, Slip-stack Hierarchical (POSH) reactive plans. 2.The BOD development process: an iterative process that alternately scales the agent's capabilities then optimizes the agent for simplicity, exploiting tradeoffs between the component representations. This ongoing process for controlling complexity not only provides bias for the behaving agent, but also facilitates its maintenance and extendibility. The secondary contributions of this dissertation include two implementations of POSH action selection, a procedure for identifying useful idioms in agent architectures and using them to distribute knowledge across agent paradigms, several examples of applying BOD idioms to established architectures, an analysis and comparison of the attributes and design trends of a large number of agent architectures, a comparison of biological (particularly mammalian) intelligence to artificial agent architectures, a novel model of primate transitive inference, and many other examples of BOD agents and BOD development.

Safe Distributed Coordination of Heterogeneous Robots through Dynamic Simple Temporal Networks

Research on autonomous intelligent systems has focused on how robots can robustly carry out missions in uncertain and harsh environments with very little or no human intervention. Robotic execution languages such as RAPs, ESL, and TDL improve robustness by managing functionally redundant procedures for achieving goals. The model-based programming approach extends this by guaranteeing correctness of execution through pre-planning of non-deterministic timed threads of activities. Executing model-based programs effectively on distributed autonomous platforms requires distributing this pre-planning process. This thesis presents a distributed planner for modelbased programs whose planning and execution is distributed among agents with widely varying levels of processor power and memory resources. We make two key contributions. First, we reformulate a model-based program, which describes cooperative activities, into a hierarchical dynamic simple temporal network. This enables efficient distributed coordination of robots and supports deployment on heterogeneous robots. Second, we introduce a distributed temporal planner, called DTP, which solves hierarchical dynamic simple temporal networks with the assistance of the distributed Bellman-Ford shortest path algorithm. The implementation of DTP has been demonstrated successfully on a wide range of randomly generated examples and on a pursuer-evader challenge problem in simulation.

Suppliers' Associations in the Japanese Automobile Industry

This paper analyzes the structure and functions of suppliers' associations (kyoryokukai) in the automobile industry in Japan. The bilateral assembler-supplier relationship has received much attention recently as a source of Japanese industrial competitiveness. However, this paper argues that the hitherto neglected area of inter-supplier coordination in technology diffusion is at least as important as the bilateral assembler-supplier relationship in accounting for the overall performance of the Japanese automotive industry. On the basis of company visits and a largescale survey of first-tier suppliers conducted by the author, the paper analyzes the reasons why suppliers' associations were established, why they continue to exist today, and their effects on economic performance.

Estudio sobre las inteligencias inter-e intrapersonales como instrumentos de desarrollo de la disposición a comunicarse en el aula de inglés.

Saber si a través de un programa que potencie el uso de actividades relacionadas con las inteligencias intra e interpersonales, aumenta la disposición a comunicarse en inglés de alumnos españoles estudiantes de inglés del primer curso de la Educación Secundaria Obligatoria, y si de alguna forma mejora la inteligencia emocional de éstos. La falta de investigación sobre la relación que existe entre la competencia emocional del alumnado y su disposición a comunicarse en un idioma extranjero en clase, unido a la evidencia de la falta de prácticas orales reales dentro del aula, ayudaron a formular las siguientes preguntas de investigación que han guiado el presente estudio: 1.¿Facilita la instrucción de la inteligencia emocional la disposición a comunicarse del alumnado? 2.¿Tiene el tratamiento en competencia emocional incidencia sobre el interés de los alumnos en la lengua meta? 3.¿Aumenta la competencia emocional del alumnado tras el tratamiento?. Plantea un diseño experimental se realiza con alumnos de dos cursos de primero de E.S.O, y en el centro privado concertado con mayor población infantil y juvenil de la provincia de Huelva (excluida la capital) con dos grupos, control y experimenta. De esta forma se cuenta al principio de la investigación con una variada muestra de población (60 alumnos) de distintas zonas geográficas y diferentes entornos educativos. El grupo experimental estaba formado por 16 niñas y 14 niños, no siendo ninguno de ellos alumnos con necesidades educativas especiales, aunque sí había tres alumnos que necesitaban refuerzos educativos en algunas áreas (matemáticas, lengua e inglés). El grupo control estaba formado por 15 niñas y 15 niños, y cuatro alumnos necesitaban igualmente refuerzo educativo. El grupo experimental contaba con 11 alumnos procedentes del mismo centro escolar, 4 alumnos de distintas poblaciones y 6 procedentes de la misma población pero de otros centros escolares de primaria. El grupo control contaba con 11 alumnos procedentes del mismo centro escolar, 4 alumnos de distintas poblaciones y 6 procedentes de otros centros de primaria, con lo que la variedad de la muestra está garantizada. Se utilizan procedimientos de recogida de datos con un nivel alto de detalle: cuestionarios para obtener información específica y la escala que mide la disposición a comunicarse del alumnado. Por otro lado, se emplean otros procedimientos con un bajo nivel de detalle en cuanto a la información que recogen: observación directa de la profesora y entrevistas informales recogidas en las fichas de seguimiento de las actividades. Son muchas más las actividades que podrían haberse planteado en este estudio y que se podrían llevar a cabo en cualquier clase de secundaria. Sólo haría falta un profesor capaz de confiar plenamente en el rendimiento académico y afectivo de sus alumnos y sobre todo capaz de originar en el aula un clima de aceptación y tolerancia. Creer que todo alumno es capaz de aprender es empezar a proporcionarle los medios para hacerlo. Los esquemas y programas diseñados en la escuela de la segunda década del siglo XXI para los adolescentes no deberían ser configurados sólo y exclusivamente por las exigencias de los estudios posteriores, tal y como sucede, sino que principalmente deberían ayudar a los alumnos a transformar su educación en un proceso evolutivo que haga frente a sus necesidades sociales, personales, físicas e intelectuales. Se podría continuar con tratamientos similares, en cursos superiores de la Educación Secundaria, y ver qué consecuencias tiene en un alumnado de más edad. El mayor reto educativo de los docentes es tratar de desarrollar en el alumnado aquellas capacidades que no lo estén y el presente estudio abre nuevas vías de investigación para desarrollar en el alumnado las habilidades necesarias para empezar a comunicarse en un segundo idioma, para favorecer el trabajo colaborativo en el aula y para mejorar y ampliar su competencia emocional.

An hybrid methodology for RL-based behavior coordination in a target following mission with an AUV

Proposes a behavior-based scheme for high-level control of autonomous underwater vehicles (AUVs). Two main characteristics can be highlighted in the control scheme. Behavior coordination is done through a hybrid methodology, which takes in advantages of the robustness and modularity in competitive approaches, as well as optimized trajectories

Hybrid coordination of reinforcement learning-based behaviors for AUV control

This paper proposes a hybrid coordination method for behavior-based control architectures. The hybrid method takes advantages of the robustness and modularity in competitive approaches as well as optimized trajectories in cooperative ones. This paper shows the feasibility of applying this hybrid method with a 3D-navigation to an autonomous underwater vehicle (AUV). The behaviors are learnt online by means of reinforcement learning. A continuous Q-learning implemented with a feed-forward neural network is employed. Realistic simulations were carried out. The results obtained show the good performance of the hybrid method on behavior coordination as well as the convergence of the behaviors

Test de favoritismo endogrupal inter??tnico adaptado al modelo ampliado de aculturaci??n relativa : fiabilidad y evidencias de validez

Resumen tomado de la publicaci??n

Educació intercultural : un repte educatiu per al segle XXI. 'Educación inter-cultural : un reto educativo para el siglo XXI'.

La educación inter-cultural es la respuesta al fenómeno socioeducativo de la multiculturalidad. Es la respuesta pedagógica a la necesidad de preparar los futuros ciudadanos para vivir en una sociedad realmente multicultural e idealmente intercultural.

How to make an inter library loan request

The guide takes you through the various steps required to request a book, journal article, conference paper, thesis or other documents that the library does not hold in stock.

University of Southampton Inter-Library Loan (ILL) Form

A form for obtaining material from other libraries or institutions. Any type of material included.