Investigations on polyaniline based systems for technologically important applications and some novel polymers as prospective candidates for fabricating polymer light emitting diodes

Light emitting polymers (LEP) have drawn considerable attention because of their numerous potential applications in the field of optoelectronic devices. Till date, a large number of organic molecules and polymers have been designed and devices fabricated based on these materials. Optoelectronic devices like polymer light emitting diodes (PLED) have attracted wide-spread research attention owing to their superior properties like flexibility, lower operational power, colour tunability and possibility of obtaining large area coatings. PLEDs can be utilized for the fabrication of flat panel displays and as replacements for incandescent lamps. The internal efficiency of the LEDs mainly depends on the electroluminescent efficiency of the emissive polymer such as quantum efficiency, luminance-voltage profile of LED and the balanced injection of electrons and holes. Poly (p-phenylenevinylene) (PPV) and regio-regular polythiophenes are interesting electro-active polymers which exhibit good electrical conductivity, electroluminescent activity and high film-forming properties. A combination of Red, Green and Blue emitting polymers is necessary for the generation of white light which can replace the high energy consuming incandescent lamps. Most of these polymers show very low solubility, stability and poor mechanical properties. Many of these light emitting polymers are based on conjugated extended chains of alternating phenyl and vinyl units. The intra-chain or inter-chain interactions within these polymer chains can change the emitted colour. Therefore an effective way of synthesizing polymers with reduced π-stacking, high solubility, high thermal stability and high light-emitting efficiency is still a challenge for chemists. New copolymers have to be effectively designed so as to solve these issues. Hence, in the present work, the suitability of a few novel copolymers with very high thermal stability, excellent solubility, intense light emission (blue, cyan and green) and high glass transition temperatures have been investigated to be used as emissive layers for polymer light emitting diodes.

Information discovery in distributed systems - A novel concept based on modelling of information elements

This thesis attempts to investigate the problems associated with such schemes and suggests a software architecture, which is aimed towards achieving a meaningful discovery. Usage of information elements as a modelling base for efficient information discovery in distributed systems is demonstrated with the aid of a novel conceptual entity called infotron. The investigations are focused on distributed systems and their associated problems. The study was directed towards identifying suitable software architecture and incorporating the same in an environment where information growth is phenomenal and a proper mechanism for carrying out information discovery becomes feasible. An empirical study undertaken with the aid of an election database of constituencies distributed geographically, provided the insights required. This is manifested in the Election Counting and Reporting Software (ECRS) System. ECRS system is a software system, which is essentially distributed in nature designed to prepare reports to district administrators about the election counting process and to generate other miscellaneous statutory reports.

“Urban Water Supply Management: A Study Of Centralised And Community Based Systems In Calicut City

Studies in urban water supply system are few in the state of Kerala. It is a little researched area. In the case of water pricing a number of studies are available. In Kerala state, exception to Jacob John’s study on “Economics of Public Water Supply System”, which is a case study of Trivandrum Water Supply System in 1997, no exhaustive research work has so far come out in this field. loreover no indepth research study has come up, so far, relating to household ater demand analysis and the distribution system of urban piped water supply. he proposed study is first of its kind, which focuses on the distributional and Iailability problems of piped water supply in an urban centre in Kerala state. Hence there is a felt need for enquiring into the sufficiency of )table water supplied to people in urban areas and the efficiency maintained in roviding the scarce resource and preventing its misuse by the consumers. It is in llS backdrop that this study was undertaken and its empirical part was conducted |Calicut city in the state of Kerala. Study is confined to the water supply system ithe city of Calicut

“Studies on short polyester fiber - polyurethane elastomer composite with different interfacial bonding agents”

The work presented in this thesis is regarding the development and evaluation of new bonding agents for short polyester fiber - polyurethane elastomer composites. The conventional bonding system based on hexamethylenetetramine, resorcinol and hydrated silica was not effective as a bonding agent for the composite, as the water eliminated during the formation of the RF resin hydrolysed the urethane linkages. Four bonding agents based on MDI/'I‘DI and polypropyleneglycol, propyleneglycol and glycerol were prepared and the composite recipe was optimised with respect to the cure characteristics and mechanical properties. The flow properties, stress relaxation pattern and the thermal degradation characteristics of the composites containing different bonding agents were then studied in detail to evaluate the new bonding systems. The optimum loading of resin was 5 phr and the ratio of the -01 to isocyanate was 1:1. The cure characteristics showed that the optimum combination of cure rate and processability was given by the composite with the resin based on polypropyleneglycol/ glycerol/ 4,4’diphenylmethanediisocynate (PPG/GL/MDI). From the rheological studies of the composites with and without bonding agents it was observed that all the composites showed pseudoplastic nature and the activation energy of flow of the composite was not altered by the presence of bonding agents. Mechanical properties such as tensile strength, modulus, tear resistance and abrasion resistance were improved in the presence of bonding agents and the effect was more pronounced in the case of abrasion resistance. The composites based on MDI/GL showed better initial properties while composites with resins based on MDI/PPG showed better aging resistance. Stress relaxation showed a multistage relaxation behaviour for the composite. Within the-strain levels studied, the initial rate of relaxation was higher and the cross over time was lesser for the composite containing bonding agents. The bonding agent based on MDI/PPG/GL was found to be a better choice for improving stress relaxation characteristics with better interfacial bonding. Thennogravimetirc analysis showed that the presence of fiber and bonding agents improved the thennal stability of the polyurethane elastomer marginally and it was maximum in the case of MDI / GL based bonding agents. The kinetics of degradation was not altered by the presence of bonding agents

Design and study of self-assembled functional organic and hybrid systems for biological applications

The focus of self-assembly as a strategy for the synthesis has been confined largely to molecules, because of the importance of manipulating the structure of matter at the molecular scale. We have investigated the influence of temperature and pH, in addition to the concentration of the capping agent used for the formation of the nano-bio conjugates. For example, the formation of the narrower size distribution of the nanoparticles was observed with the increase in the concentration of the protein, which supports the fact that γ-globulin acts both as a controller of nucleation as well as stabiliser. As analyzed through various photophysical, biophysical and microscopic techniques such as TEM, AFM, C-AFM, SEM, DLS, OPM, CD and FTIR, we observed that the initial photoactivation of γ-globulin at pH 12 for 3 h resulted in small protein fibres of ca. Further irradiation for 24 h, led to the formation of selfassembled long fibres of the protein of ca. 5-6 nm and observation of surface plasmon resonance band at around 520 nm with the concomitant quenching of luminescence intensity at 680 nm. The observation of light triggered self-assembly of the protein and its effect on controlling the fate of the anchored nanoparticles can be compared with the naturally occurring process such as photomorphogenesis.Furthermore,our approach offers a way to understand the role played by the self-assembly of the protein in ordering and knock out of the metal nanoparticles and also in the design of nano-biohybrid materials for medicinal and optoelectronic applications. Investigation of the potential applications of NIR absorbing and water soluble squaraine dyes 1-3 for protein labeling and anti-amyloid agents forms the subject matter of the third chapter of the thesis. The study of their interactions with various proteins revealed that 1-3 showed unique interactions towards serum albumins as well as lysozyme. 69%, 71% and 49% in the absorption spectra as well as significant quenching in the fluorescence intensity of the dyes 1-3, respectively. Half-reciprocal analysis of the absorption data and isothermal titration calorimetric (ITC) analysis of the titration experiments gave a 1:1 stoichiometry for the complexes formed between the lysozyme and squaraine dyes with association constants (Kass) in the range 104-105 M-1. We have determined the changes in the free energy (ΔG) for the complex formation and the values are found to be -30.78, -32.31 and -28.58 kJmol-1, respectively for the dyes 1, 2 and 3. Furthermore, we have observed a strong induced CD (ICD) signal corresponding to the squaraine chromophore in the case of the halogenated squaraine dyes 2 and 3 at 636 and 637 nm confirming the complex formation in these cases. To understand the nature of interaction of the squaraine dyes 1-3 with lysozyme, we have investigated the interaction of dyes 1-3 with different amino acids. These results indicated that the dyes 1-3 showed significant interactions with cysteine and glutamic acid which are present in the side chains of lysozyme. In addition the temperature dependent studies have revealed that the interaction of the dye and the lysozyme are irreversible. Furthermore, we have investigated the interactions of these NIR dyes 1-3 with β- amyloid fibres derived from lysozyme to evaluate their potential as inhibitors of this biologically important protein aggregation. These β-amyloid fibrils were insoluble protein aggregates that have been associated with a range of neurodegenerative diseases, including Huntington, Alzheimer’s, Parkinson’s, and Creutzfeldt-Jakob diseases. We have synthesized amyloid fibres from lysozyme through its incubation in acidic solution below pH 4 and by allowing to form amyloid fibres at elevated temperature. To quantify the binding affinities of the squaraine dyes 1-3 with β-amyloids, we have carried out the isothermal titration calorimetric (ITC) measurements. The association constants were determined and are found to be 1.2 × 105, 3.6× 105 and 3.2 × 105 M-1 for the dyes, 1-3, respectively. To gain more insights into the amyloid inhibiting nature of the squaraine dyes under investigations, we have carried out thioflavin assay, CD, isothermal titration calorimetry and microscopic analysis. The addition of the dyes 1-3 (5μM) led to the complete quenching in the apparent thioflavin fluorescence, thereby indicating the destabilization of β-amyloid fibres in the presence of the squaraine dyes. Further, the inhibition of the amyloid fibres by the squaraine dyes 1-3, has been evidenced though the DLS, TEM AFM and SAED, wherein we observed the complete destabilization of the amyloid fibre and transformation of the fibre into spherical particles of ca. These results demonstrate the fact that the squaraine dyes 1-3 can act as protein labeling agents as well as the inhibitors of the protein amyloidogenesis. The last chapter of the thesis describes the synthesis and investigation of selfassembly as well as bio-imaging aspects of a few novel tetraphenylethene conjugates 4-6.Expectedly, these conjugates showed significant solvatochromism and exhibited a hypsochromic shift (negative solvatochromism) as the solvent polarity increased, and these observations were justified though theoretical studies employing the B3LYP/6-31g method. We have investigated the self-assembly properties of these D-A conjugates though variation in the percentage of water in acetonitrile solution due to the formation of nanoaggregates. Further the contour map of the observed fluorescence intensity as a function of the fluorescence excitation and emission wavelength confirmed the formation of J-type aggregates in these cases. To have a better understanding of the type of self-assemblies formed from the TPE conjugates 4-6, we have carried out the morphological analysis through various microscopic techniques such as DLS, SEM and TEM. 70%, we observed rod shape architectures having ~ 780 nm in diameter and ~ 12 μM in length as evidenced through TEM and SEM analysis. We have made similar observations with the dodecyl conjugate 5 at ca. 70% and 50% water/acetonitrile mixtures, the aggregates formed from 4 and 5 were found to be highly crystalline and such structures were transformed to amorphous nature as the water fraction was increased to 99%. To evaluate the potential of the conjugate as bio-imaging agents, we have carried out their in vitro cytotoxicity and cellular uptake studies though MTT assay, flow cytometric and confocal laser scanning microscopic techniques. Thus nanoparticle of these conjugates which exhibited efficient emission, large stoke shift, good stability, biocompatibility and excellent cellular imaging properties can have potential applications for tracking cells as well as in cell-based therapies. In summary we have synthesized novel functional organic chromophores and have studied systematic investigation of self-assembly of these synthetic and biological building blocks under a variety of conditions. The investigation of interaction of water soluble NIR squaraine dyes with lysozyme indicates that these dyes can act as the protein labeling agents and the efficiency of inhibition of β-amyloid indicate, thereby their potential as anti-amyloid agents.

Applicability of Emergence Engineering to Distributed Systems Scenarios

Genetic Programming can be effectively used to create emergent behavior for a group of autonomous agents. In the process we call Offline Emergence Engineering, the behavior is at first bred in a Genetic Programming environment and then deployed to the agents in the real environment. In this article we shortly describe our approach, introduce an extended behavioral rule syntax, and discuss the impact of the expressiveness of the behavioral description to the generation success, using two scenarios in comparison: the election problem and the distributed critical section problem. We evaluate the results, formulating criteria for the applicability of our approach.

Decision‐Making in Public Good Dilemmas: Theory and Agent‐Based Simulation

In many real world contexts individuals find themselves in situations where they have to decide between options of behaviour that serve a collective purpose or behaviours which satisfy one’s private interests, ignoring the collective. In some cases the underlying social dilemma (Dawes, 1980) is solved and we observe collective action (Olson, 1965). In others social mobilisation is unsuccessful. The central topic of social dilemma research is the identification and understanding of mechanisms which yield to the observed cooperation and therefore resolve the social dilemma. It is the purpose of this thesis to contribute this research field for the case of public good dilemmas. To do so, existing work that is relevant to this problem domain is reviewed and a set of mandatory requirements is derived which guide theory and method development of the thesis. In particular, the thesis focusses on dynamic processes of social mobilisation which can foster or inhibit collective action. The basic understanding is that success or failure of the required process of social mobilisation is determined by heterogeneous individual preferences of the members of a providing group, the social structure in which the acting individuals are contained, and the embedding of the individuals in economic, political, biophysical, or other external contexts. To account for these aspects and for the involved dynamics the methodical approach of the thesis is computer simulation, in particular agent-based modelling and simulation of social systems. Particularly conductive are agent models which ground the simulation of human behaviour in suitable psychological theories of action. The thesis develops the action theory HAPPenInGS (Heterogeneous Agents Providing Public Goods) and demonstrates its embedding into different agent-based simulations. The thesis substantiates the particular added value of the methodical approach: Starting out from a theory of individual behaviour, in simulations the emergence of collective patterns of behaviour becomes observable. In addition, the underlying collective dynamics may be scrutinised and assessed by scenario analysis. The results of such experiments reveal insights on processes of social mobilisation which go beyond classical empirical approaches and yield policy recommendations on promising intervention measures in particular.

Model-Based Troubleshooting of Digital Systems

This thesis describes a methodology, a representation, and an implemented program for troubleshooting digital circuit boards at roughly the level of expertise one might expect in a human novice. Existing methods for model-based troubleshooting have not scaled up to deal with complex circuits, in part because traditional circuit models do not explicitly represent aspects of the device that troubleshooters would consider important. For complex devices the model of the target device should be constructed with the goal of troubleshooting explicitly in mind. Given that methodology, the principal contributions of the thesis are ways of representing complex circuits to help make troubleshooting feasible. Temporally coarse behavior descriptions are a particularly powerful simplification. Instantiating this idea for the circuit domain produces a vocabulary for describing digital signals. The vocabulary has a level of temporal detail sufficient to make useful predictions abut the response of the circuit while it remains coarse enough to make those predictions computationally tractable. Other contributions are principles for using these representations. Although not embodied in a program, these principles are sufficiently concrete that models can be constructed manually from existing circuit descriptions such as schematics, part specifications, and state diagrams. One such principle is that if there are components with particularly likely failure modes or failure modes in which their behavior is drastically simplified, this knowledge should be incorporated into the model. Further contributions include the solution of technical problems resulting from the use of explicit temporal representations and design descriptions with tangled hierarchies.

Keyword Join: Realizing Keyword Search in P2P-based Database Systems

In this paper, we present a P2P-based database sharing system that provides information sharing capabilities through keyword-based search techniques. Our system requires neither a global schema nor schema mappings between different databases, and our keyword-based search algorithms are robust in the presence of frequent changes in the content and membership of peers. To facilitate data integration, we introduce keyword join operator to combine partial answers containing different keywords into complete answers. We also present an efficient algorithm that optimize the keyword join operations for partial answer integration. Our experimental study on both real and synthetic datasets demonstrates the effectiveness of our algorithms, and the efficiency of the proposed query processing strategies.

Multidimensional Adaptations for Open Learning Management Systems

Our work is focused on alleviating the workload for designers of adaptive courses on the complexity task of authoring adaptive learning designs adjusted to specific user characteristics and the user context. We propose an adaptation platform that consists in a set of intelligent agents where each agent carries out an independent adaptation task. The agents apply machine learning techniques to support the user modelling for the adaptation process

A Negotiation Style Recommender Based on Computational Ecology in Open Negotiation Environments

The system described herein represents the first example of a recommender system in digital ecosystems where agents negotiate services on behalf of small companies. The small companies compete not only with price or quality, but with a wider service-by-service composition by subcontracting with other companies. The final result of these offerings depends on negotiations at the scale of millions of small companies. This scale requires new platforms for supporting digital business ecosystems, as well as related services like open-id, trust management, monitors and recommenders. This is done in the Open Negotiation Environment (ONE), which is an open-source platform that allows agents, on behalf of small companies, to negotiate and use the ecosystem services, and enables the development of new agent technologies. The methods and tools of cyber engineering are necessary to build up Open Negotiation Environments that are stable, a basic condition for predictable business and reliable business environments. Aiming to build stable digital business ecosystems by means of improved collective intelligence, we introduce a model of negotiation style dynamics from the point of view of computational ecology. This model inspires an ecosystem monitor as well as a novel negotiation style recommender. The ecosystem monitor provides hints to the negotiation style recommender to achieve greater stability of an open negotiation environment in a digital business ecosystem. The greater stability provides the small companies with higher predictability, and therefore better business results. The negotiation style recommender is implemented with a simulated annealing algorithm at a constant temperature, and its impact is shown by applying it to a real case of an open negotiation environment populated by Italian companies

Embodied Autonomy in Digital Ecosystems: From Bio-Inspired Agents to Cognitive Systems

This paper proposes to promote autonomy in digital ecosystems so that it provides agents with information to improve the behavior of the digital ecosystem in terms of stability. This work proposes that, in digital ecosystems, autonomous agents can provide fundamental services and information. The final goal is to run the ecosystem, generate novel conditions and let agents exploit them. A set of evaluation measures must be defined as well. We want to provide an outline of some global indicators, such as heterogeneity and diversity, and establish relationships between agent behavior and these global indicators to fully understand interactions between agents, and to understand the dependence and autonomy relations that emerge between the interacting agents. Individual variations, interaction dependencies, and environmental factors are determinants of autonomy that would be considered. The paper concludes with a discussion of situations when autonomy is a milestone

Studies about the atomic capabilities concept for linear control systems in physical multi-agent environments

This paper shows the impact of the atomic capabilities concept to include control-oriented knowledge of linear control systems in the decisions making structure of physical agents. These agents operate in a real environment managing physical objects (e.g. their physical bodies) in coordinated tasks. This approach is presented using an introspective reasoning approach and control theory based on the specific tasks of passing a ball and executing the offside manoeuvre between physical agents in the robotic soccer testbed. Experimental results and conclusions are presented, emphasising the advantages of our approach that improve the multi-agent performance in cooperative systems

A contrastive analysis of non-native interlanguage english intonation systems and their implication in the organisation of information from a functional perspectiva : a study based on a computerized corpus of spanish learners of english

El contexto teórico y empírico de esta investigación sobre entonación, se enmarca dentro de la filosofía lingüística de la teoría sistémico-funcional. El modelo metodológico empleado se basa en la Lingüística de Corpus. La descripción de la adquisición y aprendizaje de la lengua extranjera está justificada dentro del marco teórico de la teoría de interlengua y la adquisición de segundas lenguas y lenguas extranjeras.. El presente estudio del corpus comparativo y longitudinal de aprendices y hablantes nativos de lengua inglesa, tiene como objetivo principal investigar los modelos de entonación producidos por ambos grupos de hablantes. Se pretende demostrar que la diferencia a nivel entonativo entre estos dos grupos no sólo tiene como resultado que los no nativos tengan acento extranjero; sino que puede afectar al mensaje transmitido, en cuanto a la estructura y organización de la información dentro del discurso oral en las metafunciones textual e interpersonal.. Se asume la existencia de un sistema entonativo de interlengua, de esta forma este análisis tiene como objeto no sólo reflejar los errores sino también los posibles sistemas aproximativos de los aprendices mencionados..

A formalization for multi-agent decision support in cooperative environments. A framework for situated agents

La tesis propone un marco de trabajo para el soporte de la toma de decisiones adecuado para soportar la ejecución distribuida de acciones cooperativas en entornos multi-agente dinámicos y complejos. Soporte para la toma de decisiones es un proceso que intenta mejorar la ejecución de la toma de decisiones en escenarios cooperativos. Este proceso ocurre continuamente en la vida diaria. Los humanos, por ejemplo, deben tomar decisiones acerca de que ropa usar, que comida comer, etc. En este sentido, un agente es definido como cualquier cosa que está situada en un entorno y que actúa, basado en su observación, su interpretación y su conocimiento acerca de su situación en tal entorno para lograr una acción en particular.Por lo tanto, para tomar decisiones, los agentes deben considerar el conocimiento que les permita ser consientes en que acciones pueden o no ejecutar. Aquí, tal proceso toma en cuenta tres parámetros de información con la intención de personificar a un agente en un entorno típicamente físico. Así, el mencionado conjunto de información es conocido como ejes de decisión, los cuales deben ser tomados por los agentes para decidir si pueden ejecutar correctamente una tarea propuesta por otro agente o humano. Los agentes, por lo tanto, pueden hacer mejores decisiones considerando y representando apropiadamente tal información. Los ejes de decisión, principalmente basados en: las condiciones ambientales, el conocimiento físico y el valor de confianza del agente, provee a los sistemas multi-agente un confiable razonamiento para alcanzar un factible y exitoso rendimiento cooperativo.Actualmente, muchos investigadores tienden a generar nuevos avances en la tecnología agente para incrementar la inteligencia, autonomía, comunicación y auto-adaptación en escenarios agentes típicamente abierto y distribuidos. En este sentido, esta investigación intenta contribuir en el desarrollo de un nuevo método que impacte tanto en las decisiones individuales como colectivas de los sistemas multi-agente. Por lo tanto, el marco de trabajo propuesto ha sido utilizado para implementar las acciones concretas involucradas en el campo de pruebas del fútbol robótico. Este campo emula los juegos de fútbol real, donde los agentes deben coordinarse, interactuar y cooperar entre ellos para solucionar tareas complejas dentro de un escenario dinámicamente cambiante y competitivo, tanto para manejar el diseño de los requerimientos involucrados en las tareas como para demostrar su efectividad en trabajos colectivos. Es así que los resultados obtenidos tanto en el simulador como en el campo real de experimentación, muestran que el marco de trabajo para el soporte de decisiones propuesto para agentes situados es capaz de mejorar la interacción y la comunicación, reflejando en un adecuad y confiable trabajo en equipo dentro de entornos impredecibles, dinámicos y competitivos. Además, los experimentos y resultados también muestran que la información seleccionada para generar los ejes de decisión para situar a los agentes, es útil cuando tales agentes deben ejecutar una acción o hacer un compromiso en cada momento con la intención de cumplir exitosamente un objetivo colectivo. Finalmente, algunas conclusiones enfatizando las ventajas y utilidades del trabajo propuesto en la mejora del rendimiento colectivo de los sistemas multi-agente en situaciones tales como tareas coordinadas y asignación de tareas son presentadas.