Physiological and behavioural effects of dextroamphetamine on Beagle dogs : a placebo controlled study

Plusieurs articles scientifiques et manuels de référence en médecine comportementale distinguent l'hyperactivité ou hyperkinésie de l’activité excessive en évaluant la réponse physiologique et comportementale des chiens suite à l’administration per os de 0.2 à 1.0 mg/kg de dextroamphétamine. Selon ces références, le chien atteint d’un syndrome hyperactif ou hyperkinésie, répondra de façon paradoxale à cette médication par une diminution de l’activité motrice accompagnée d’une réduction minimale de 15% de la fréquence respiratoire et de la fréquence cardiaque. L’objectif de la présente étude était de mesurer la variation de la température corporelle, de la fréquence cardiaque, de l’activité motrice et de différents comportements spécifiques chez un groupe de Beagles ayant reçu de la dextroamphétamine. La fiabilité d'un accéléromètre comme mesure objective d’activité motrice a aussi été évaluée. Dans le cadre de cette étude croisée contrôlée par placebo, douze Beagles de la colonie de recherche âgés entre 13 et 20 mois ont reçu une dose orale de 0.2 mg/kg de dextroamphétamine. Le moniteur cardiaque Polar® et un accéléromètre Actical® ont été utilisés pour enregistrer la fréquence cardiaque et l’activité motrice avant et après l’administration de la médication. La durée de chacun des comportements spécifiques a été compilée à l’aide du logiciel Noldus® et la température corporelle a été prise par thermomètre rectal. Le modèle équilibré de mesures répétées indique que les sujets ayant reçu la dextroamphétamine montrent une réduction significative (p = 0.044) de leur fréquence cardiaque comparativement aux chiens ayant reçu le placebo. Aucune variation significative n'a été observée concernant la température corporelle, l'activité motrice, et les autres comportements (léchage des babines, halètements, et bâillements) suite à l’administration de la dextroamphétamine. Une corrélation significative, linéaire et positive (p < 0,0001) entre les périodes de mouvements observées (vidéo) et les mesures d’activité enregistrées par l’accéléromètre a été observée. Les résultats de cette étude indiquent que les Beagles peuvent afficher des effets paradoxaux dans les 90 minutes suivant l’administration per os de dextroamphétamine à raison de 0.2 mg/kg.

Study of the diffusion in polymer solutions and hydrogels by NMR spectroscopy and NMR imaging

Afin d'étudier la diffusion et la libération de molécules de tailles inférieures dans un gel polymère, les coefficients d'auto-diffusion d'une série de polymères en étoile avec un noyau d'acide cholique et quatre branches de poly(éthylène glycol) (PEG) ont été déterminés par spectroscopie RMN à gradient de champ pulsé dans des solutions aqueuses et des gels de poly(alcool vinylique). Les coefficients de diffusion obtenus ont été comparés avec ceux des PEGs linéaires et dendritiques pour étudier l'effet de l'architecture des polymères. Les polymères en étoile amphiphiles ont des profils de diffusion en fonction de la concentration similaires à leurs homologues linéaires dans le régime dilué. Ils diffusent plus lentement dans le régime semi-dilué en raison de leur noyau hydrophobe. Leurs conformations en solution ont été étudiées par des mesures de temps de relaxation spin-réseau T1 du noyau et des branches. L'imagerie RMN a été utilisée pour étudier le gonflement des comprimés polymères et la diffusion dans la matrice polymère. Les comprimés étaient constitués d'amidon à haute teneur en amylose et chargés avec de l'acétaminophène (de 10 à 40% en poids). Le gonflement des comprimés, ainsi que l'absorption et la diffusion de l'eau, augmentent avec la teneur en médicament, tandis que le pourcentage de libération du médicament est similaire pour tous les comprimés. Le gonflement in vitro des comprimés d'un complexe polyélectrolyte à base d'amidon carboxyméthylé et de chitosane a également été étudié par imagerie RMN. Ces comprimés sont sensibles au pH : ils gonflent beaucoup plus dans les milieux acides que dans les milieux neutres en raison de la dissociation des deux composants et de la protonation des chaînes du chitosane. La comparaison des résultats avec ceux d'amidon à haute teneur en amylose indique que les deux matrices ont des gonflements et des profils de libération du médicament semblables dans les milieux neutres, alors que les comprimés complexes gonflent plus dans les milieux acides en raison de la dissociation du chitosane et de l'amidon.

Eye disease and mobility limitations in older adults

Objectif: Évaluer les défis de la mobilité chez les personnes âgées atteintes de dégénérescence maculaire reliée à l’âge (DMLA), de glaucome ou de dystrophie cornéenne de Fuchs et les comparer avec les personnes âgées n’ayant pas de maladie oculaire. Devis: Étude transversale de population hospitalière Participants: 253 participants (61 avec la DMLA, 45 avec la dystrophie cornéenne de Fuchs, 79 avec le glaucome et 68 contrôles) Méthodes: Nous avons recruté les patients parmi ceux qui se font soigner dans les cliniques d’ophtalmologie de l’Hôpital Maisonneuve-Rosemont (Montréal, Canada) de septembre 2009 à octobre 2010. Les patients atteints de la DMLA ou de la maladie de Fuchs ont une acuité visuelle inférieure à 20/40 dans les deux yeux, tandis que les patients avec du glaucome ont un champ visuel dans le pire oeil inférieur ou égal à -4dB. Les patients contrôles, qui ont été recrutés à partir des mêmes cliniques, ont une acuité visuelle et un champ visuel normaux. Nous avons colligé des données concernant la mobilité à partir des questionnaires (aire de mobilité et chutes) et des tests (test de l’équilibre monopodal, timed Up and Go (TUG) test). Pour mesurer la fonction visuelle nous avons mesuré l’acuité visuelle, la sensibilité au contraste et le champ visuel. Nous avons également révisé le dossier médical. Pour les analyses statistiques nous avons utilisé les régressions linéaire et logistique. Critères de jugement principaux: aire de mobilité, équilibre, test timed Up and Go, chutes Résultats: Les trois maladies oculaires ont été associées à des patrons différents de limitation de la mobilité. Les patients atteints de glaucome ont eu le type le plus sévère de restriction de mobilité; ils ont une aire de mobilité plus réduite, des scores plus bas au test TUG et ils sont plus enclins à avoir un équilibre faible et à faire plus de chutes que les contrôles (p < 0.05). De plus, comparativement aux contrôles, les patients ayant de la DMLA ou la dystrophie cornéenne de Fuchs ont eu une aire de mobilité réduite (p < 0.05). Les chutes n’ont pas été associées aux maladies oculaires dans cette étude. Conclusions: Nos résultats suggèrent que les maladies oculaires, et surtout le glaucome, limitent la mobilité chez les personnes âgées. De futures études sont nécessaires pour évaluer l’impact d’une mobilité restreinte chez cette population pour pouvoir envisager des interventions ciblées qui pourraient les aider à maintenir leur indépendance le plus longtemps possible.

Tarification logit dans un réseau

Le problème de tarification qui nous intéresse ici consiste à maximiser le revenu généré par les usagers d'un réseau de transport. Pour se rendre à leurs destinations, les usagers font un choix de route et utilisent des arcs sur lesquels nous imposons des tarifs. Chaque route est caractérisée (aux yeux de l'usager) par sa "désutilité", une mesure de longueur généralisée tenant compte à la fois des tarifs et des autres coûts associés à son utilisation. Ce problème a surtout été abordé sous une modélisation déterministe de la demande selon laquelle seules des routes de désutilité minimale se voient attribuer une mesure positive de flot. Le modèle déterministe se prête bien à une résolution globale, mais pèche par manque de réalisme. Nous considérons ici une extension probabiliste de ce modèle, selon laquelle les usagers d'un réseau sont alloués aux routes d'après un modèle de choix discret logit. Bien que le problème de tarification qui en résulte est non linéaire et non convexe, il conserve néanmoins une forte composante combinatoire que nous exploitons à des fins algorithmiques. Notre contribution se répartit en trois articles. Dans le premier, nous abordons le problème d'un point de vue théorique pour le cas avec une paire origine-destination. Nous développons une analyse de premier ordre qui exploite les propriétés analytiques de l'affectation logit et démontrons la validité de règles de simplification de la topologie du réseau qui permettent de réduire la dimension du problème sans en modifier la solution. Nous établissons ensuite l'unimodalité du problème pour une vaste gamme de topologies et nous généralisons certains de nos résultats au problème de la tarification d'une ligne de produits. Dans le deuxième article, nous abordons le problème d'un point de vue numérique pour le cas avec plusieurs paires origine-destination. Nous développons des algorithmes qui exploitent l'information locale et la parenté des formulations probabilistes et déterministes. Un des résultats de notre analyse est l'obtention de bornes sur l'erreur commise par les modèles combinatoires dans l'approximation du revenu logit. Nos essais numériques montrent qu'une approximation combinatoire rudimentaire permet souvent d'identifier des solutions quasi-optimales. Dans le troisième article, nous considérons l'extension du problème à une demande hétérogène. L'affectation de la demande y est donnée par un modèle de choix discret logit mixte où la sensibilité au prix d'un usager est aléatoire. Sous cette modélisation, l'expression du revenu n'est pas analytique et ne peut être évaluée de façon exacte. Cependant, nous démontrons que l'utilisation d'approximations non linéaires et combinatoires permet d'identifier des solutions quasi-optimales. Finalement, nous en profitons pour illustrer la richesse du modèle, par le biais d'une interprétation économique, et examinons plus particulièrement la contribution au revenu des différents groupes d'usagers.

Influvence of Alloying Additions on the Structure and Properties of Ai-7Si-0.3Mg Alloy

Cast Ai-Si alloys are widely used in the automotive, aerospace and general engineering industries due to their excellent combination of properties such as good castability, low coefficient of thermal expansion, high strength-to-weight ratio and good corrosion resistance. The present investigation is on the influence of alloying additions on the structure and properties of Ai-7Si-0.3Mg alloy. The primary objective of this present investigation is to study these beneficial effects of calcium on the structure and properties of Ai-7Si-0.3Mg-xFe alloys. The second objective of this work is to study the effects of Mn,Be and Sr addition as Fe neutralizers and also to study the interaction of Mn,Be,Sr and Ca in Ai-7Si-0.3Mg-xFe alloys. In this study the duel beneficial effects of Ca viz;modification and Fe-neutralization, comparison of the effects of Ca and Sr with common Fe neutralizers. The casting have been characterized with respect to their microstructure, %porosity and electrical conductivity, solidification behaviour and mechanical properties. One of the interesting observations in the present work is that a low level of calcium reduces the porosity compared to the untreated alloy. However higher level of calcium addition lead to higher porosity in the casting. An empirical analysis carried out for comparing the results of the present work with those of the other researchers on the effect of increasing iron content on UTS and % elongation of Ai-Si-Mg and Ai-Si-Cu alloys has shown a linear and an inverse first order polynomial relationships respectively.

Modeling and Analysis of Some Heavy Tailed Time Series

The thesis has covered various aspects of modeling and analysis of finite mean time series with symmetric stable distributed innovations. Time series analysis based on Box and Jenkins methods are the most popular approaches where the models are linear and errors are Gaussian. We highlighted the limitations of classical time series analysis tools and explored some generalized tools and organized the approach parallel to the classical set up. In the present thesis we mainly studied the estimation and prediction of signal plus noise model. Here we assumed the signal and noise follow some models with symmetric stable innovations.We start the thesis with some motivating examples and application areas of alpha stable time series models. Classical time series analysis and corresponding theories based on finite variance models are extensively discussed in second chapter. We also surveyed the existing theories and methods correspond to infinite variance models in the same chapter. We present a linear filtering method for computing the filter weights assigned to the observation for estimating unobserved signal under general noisy environment in third chapter. Here we consider both the signal and the noise as stationary processes with infinite variance innovations. We derived semi infinite, double infinite and asymmetric signal extraction filters based on minimum dispersion criteria. Finite length filters based on Kalman-Levy filters are developed and identified the pattern of the filter weights. Simulation studies show that the proposed methods are competent enough in signal extraction for processes with infinite variance.Parameter estimation of autoregressive signals observed in a symmetric stable noise environment is discussed in fourth chapter. Here we used higher order Yule-Walker type estimation using auto-covariation function and exemplify the methods by simulation and application to Sea surface temperature data. We increased the number of Yule-Walker equations and proposed a ordinary least square estimate to the autoregressive parameters. Singularity problem of the auto-covariation matrix is addressed and derived a modified version of the Generalized Yule-Walker method using singular value decomposition.In fifth chapter of the thesis we introduced partial covariation function as a tool for stable time series analysis where covariance or partial covariance is ill defined. Asymptotic results of the partial auto-covariation is studied and its application in model identification of stable auto-regressive models are discussed. We generalize the Durbin-Levinson algorithm to include infinite variance models in terms of partial auto-covariation function and introduce a new information criteria for consistent order estimation of stable autoregressive model.In chapter six we explore the application of the techniques discussed in the previous chapter in signal processing. Frequency estimation of sinusoidal signal observed in symmetric stable noisy environment is discussed in this context. Here we introduced a parametric spectrum analysis and frequency estimate using power transfer function. Estimate of the power transfer function is obtained using the modified generalized Yule-Walker approach. Another important problem in statistical signal processing is to identify the number of sinusoidal components in an observed signal. We used a modified version of the proposed information criteria for this purpose.

Investigations on some technologically important polymer nanocomposite films and semi crystalline Polypyrrole films

The present work deals with investigations on some technologically important polymer nanocomposite films and semi crystalline polypyrrole films.The work presented in the thesis deals with the realization of novel polymer nanocomposites with enhanced functionalities and prospects of applications in the fields related to nanophotonics. The development of inorganic/polymer nanocomposites is a rapidly expanding multidisciplinary research area with profound industrial applications. The incorporation of suitable inorganic nanoparticles can endow the resulting nanocomposites with excellent electrical, optical and mechanical properties. The first chapter gives a general introduction to nanotechnology, nanocomposites and conducting polymers. It also emphasizes the significance of ZnO among other semiconductor materials, which forms the inorganic filler in the polymer nanocomposites of the present study. This chapter also gives general ideas on the properties and applications of conducting polymers with special reference to polypyrrole. The objectives of the present investigations are also clearly addressed in this chapter. The second chapter deals with the theoretical aspects and details of all the experimental techniques used in the present work for the synthesis of polymer nanocomposites and polypyrrole samples and their various characterizations. Chapter 3 is based on the preparation and properties of ZnO/Polystyrene nanocomposite film samples. The optical properties of these nanocomoposite films are discussed in detail.Chapter 4 deals with the detailed investigations on the dependence of the optical properties of ZnO/PS nanocomposite films on the size of the nanostructured ZnO filler material. The excellent UV shielding properties of these nanocomposite films form the highlight of this chapter. Chapter 5 gives a detailed analysis of the nonlinear optical properties of ZnO/PS nanocomposite films using Z scan technique. The effect of ZnO particle size in the composite films on the nonlinear properties is discussed. The present study involves two phases of research activities. In the first phase, the linear and nonlinear optical properties of ZnO/polymer nanocomposites are investigated in detail. The second phase of work is centered on the synthesis and related studies on highly crystalline polypyrrole films. In the present study, nanosized ZnO is synthesized using wet chemical method at two different temperatures

Studies On The Synthesis Of Vitamin A And Related Compounds

In the present work different new approaches for the synthesis of Vitamin A are investigated. In these synthetic schemes, all the twenty carbon atoms of the target molecule are derived either fully from components isolated from common essential oils or partially from commercially available materials. By retrosynthetic analysis, Vitamin A molecule can be disconnected into a cyclic and a linear unit. Different methods for the synthesis of the linear and the cyclic components are described. The monoterpenes, geraniol and citral, major constituents of palmarosa and lemongrass oils, have the required basic carbon framework for consideration as starting materials for the synthesis of Vitamin A. The potential of these easily available naturally occurring compounds as promising starting materials for Vitamin A synthesis is demonstrated. Organoselenium and organosulfur mediated functional group transformations for the synthesis of the functionalised conjugated C10 linear components (ie., the dimethyloctatriene derivatives) are reported. The classical approaches as well as the attempted preparation of cyclic C10 and C13 units employed in the present study as intermediates for Vitamin A synthesis are described. The utility of commercially available materials namely 2-acetylbutyrolactone and levulinic acid in -the preparation of C5 intermediates for Vitamin A synthesis is demonstrated.

" Studies on Laser induced Phatothermal Phenomena in Selected Organic Compounds and Fullerenes"

In the pre—laser era it was difficult to believe that the optical properties of a medium depend upon the intensity of the radiation incident on it. The basis for this conclusion is that the electric field strength associated with the conventional light sources used before the advent of lasers was much smaller than (103 V/cm) the field sttrengths of atomic or interatomic fields (2 107 —- 10” V/cm). The radiation with such low intensity is not able to affect atomic fields to the extent of changing optical parameters. The invention of laser in 1960 was a turning point. The high degree of coherence of the laser radiation provides high spatial concentration of optical power. With the availability of the femtosecond lasers it has become possible to get extremely high peak powers 2 1013 W/cmz). At such high fields, the relationship between electric ‘polarization P and the electric field strength E ceases to be linear and several nonlinear effects begin to occur. Nonlinear absorption, a branch of nonlinear optics, refers to the interaction between radiation and matter accompanied by absorption of more than one photon. Nonlinear absorption has acquired great importance after the invention of high power lasers. One of the objectives of the present work is to investigate the nonlinear absorption processes occurring in fullerene, selected organic solvents and laser dyes. Fullerenes and laser dyes were chosen because of their highly nonlinear behaviour. Fullerenes, the most beautiful among molecules, offer fascinating field of research owinglto their significant structural properties. As toluene, benzene and carbon disulphide are themost widely used solvents for fullerenes, it seems important to study the nonlinear properties of these liquids as well. Like fullerenes, laser dyes also possess highly delocalized 7r electrons which are responsible for their nonlinear absorption. Dye lasers were the fulfillment of an experimenter’s pipe dream - to have a laser that is easily tunable over a wide range of wavelengths. A better understandingof the photophysical properties of laser dyes can significantly enhance the development and technology of dye lasers. We studied the nonlinear absorption properties of two rhodamine dyes to have some insight into their nonlinear optical properties.

Length-weight relationship, relative condition factor (Kn) and morphometry of Arius subrostratus (Valenciennes, 1840) from a coastal wetland in Kerala

The length – weight relationship and relative condition factor of the shovel nose catfish, Arius subrostratus (Valenciennes, 1840) from Champakkara backwater were studied by examination of 392 specimens collected during June to September 2008. These fishes ranged from 6 to 29 cm in total length and 5.6 to 218 g in weight. The relation between the total length and weight of Arius subrostratus is described as Log W = -1.530+2.6224 log L for males, Log W = - 2.131 + 3.0914 log L for females and Log W = - 1.742 + 2.8067 log L for sexes combined. The mean relative condition factor (Kn) values ranged from 0.75 to 1.07 for males, 0.944 to 1.407 for females and 0.96 to 1.196 for combined sexes. The length-weight relationship and relative condition factor showed that the well-being of A. subrostratus is good. The morphometric measurements of various body parts and meristic counts were recorded. The morphometric measurements were found to be non-linear and there is no significant difference observed between the two sexes. From the present investigation, the fin formula can be written as D: I, 7; P: I, 12; A: 17 – 20; C: 26 – 32. There is no change in meristic counts with the increase in body length.

Preparation and Study of Optical Properties of CdS, CdS-TiO2 and CdS-Au Nanocomposites for Photonic Applications

Nanophotonics can be regarded as a fusion of nanotechnology and photonics and it is an emerging field providing researchers opportunities in fundamental science and new technologies. In recent times many new methodsand techniques have been developed to prepare materials at nanoscale dimensions. Most of these materials exhibit unique and interesting optical properties and behavior. Many of these have been found to be very useful to develop new devices and systems such as tracers in biological systems, optical limiters, light emitters and energy harvesters. This thesis presents a summary of the work done by the author in the field by choosing a few semiconductor systems to prepare nanomaterials and nanocomposites. Results of the study of linear and nonlinear optical properties of materials thus synthesized are also presented in the various chapters of this thesis. CdS is the material chosen here and the methods and the studies of the detailed investigation are presented in this thesis related to the optical properties of CdS nanoparticles and its composites. Preparation and characterization methods and experimental techniques adopted for the investigations were illustrated in chapter 2 of this thesis. Chapter 3 discusses the preparation of CdS, TiO2 and Au nanoparticles. We observed that the fluorescence behaviour of the CdS nanoparticles, prepared by precipitation technique, depends on excitation wavelength. It was found that the peak emission wavelength can be shifted by as much as 147nm by varyingthe excitation wavelengths and the reason for this phenomenon is the selective excitation of the surface states in the nanoparticles. This provided certain amount of tunability for the emission which results from surface states.TiO2 nanoparticle colloids were prepared by hydrothermal method. The optical absorption study showed a blue shift of absorption edge, indicating quantum confinement effect. The large spectral range investigated allows observing simultaneously direct and indirect band gap optical recombination. The emission studies carried out show four peaks, which are found to be generated from excitonic as well as surface state transitions. It was found that the emission wavelengths of these colloidal nanoparticles and annealed nanoparticles showed two category of surface state emission in addition to the excitonic emission. Au nanoparticles prepared by Turkevich method showed nanoparticles of size below 5nm using plasmonic absorption calculation. It was also found that there was almost no variation in size as the concentration of precursor was changed from 0.2mM to 0.4mM.We have observed SHG from CdS nanostructured thin film prepared onglass substrate by chemical bath deposition technique. The results point out that studied sample has in-plane isotropy. The relative values of tensor components of the second-order susceptibility were determined to be 1, zzz 0.14, xxz and 0.07. zxx These values suggest that the nanocrystals are oriented along the normal direction. However, the origin of such orientation remains unknown at present. Thus CdS is a promising nonlinear optical material for photonic applications, particularly for integrated photonic devices. CdS Au nanocomposite particles were prepared by mixing CdS nanoparticles with Au colloidal nanoparticles. Optical absorption study of these nanoparticles in PVA solution suggests that absorption tail was red shifted compared to CdS nanoparticles. TEM and EDS analysis suggested that the amount of Au nanoparticles present on CdS nanoparticles is very small. Fluorescence emission is unaffected indicating the presence of low level of Au nanoparticles. CdS:Au PVA and CdS PVA nanocomposite films were fabricated and optically characterized. The results showed a red-shift for CdS:Au PVA film for absorption tail compared to CdS PVA film. Nonlinear optical analysis showed a huge nonlinear optical absorption for CdS:Au PVA nanocomposite and CdS:PVA films. Also an enhancement in nonlinear optical absorption is found for CdS:Au PVA thin film compared to the CdS PVA thin film. This enhancement is due to the combined effect of plasmonic as well as excitonic contribution at high input intensity. Samples of CdS doped with TiO2 were also prepared and the linear optical absorption spectra of these nanocompositeparticles clearly indicated the influence of TiO2 nanoparticles. TEM and EDS studies have confirmed the presence of TiO2 on CdS nanoparticles. Fluorescence studies showed that there is an increase in emission peak around 532nm for CdS nanoparticles. Nonlinear optical analysis of CdS:TiO2 PVA nanocomposite films indicated a large nonlinear optical absorption compared to that of CdS:PVA nanocomposite film. The values of nonlinear optical absorption suggests that these nanocomposite particles can be employed for optical limiting applications. CdSe-CdS and CdSe-ZnS core-shell QDs with varying shell size were characterized using UV–VIS spectroscopy. Optical absorption and TEM analysis of these QDs suggested a particle size around 5 nm. It is clearly shown that the surface coating influences the optical properties of QDs in terms of their size. Fluorescence studies reveal the presence of trap states in CdSe-CdS and CdSe- ZnS QDs. Trap states showed an increase as a shell for CdS is introduced and increasing the shell size of CdS beyond a certain value leads to a decrease in the trap state emission. There is no sizeable nonlinear optical absorption observed. In the case of CdSe- ZnS QDs, the trap state emission gets enhanced with the increase in ZnS shell thickness. The enhancement of emission from trap states transition due to the increase in thickness of ZnS shell gives a clear indication of distortion occurring in the spherical symmetry of CdSe quantum dots. Consequently the nonlinear optical absorption of CdSe-ZnS QDs gets increased and the optical limiting threshold is decreased as the shell thickness is increased in respect of CdSe QDs. In comparison with CdSe-CdS QDs, CdSe-ZnS QDs possess much better optical properties and thereby CdSe-ZnS is a strong candidate for nonlinear as well as linear optical applications.

New studies on the versatile roles of Polyaniline and its composites in polymer based optoelectronic and energy storage devices

From the early stages of the twentieth century, polyaniline (PANI), a well-known and extensively studied conducting polymer has captured the attention of scientific community owing to its interesting electrical and optical properties. Starting from its structural properties, to the currently pursued optical, electrical and electrochemical properties, extensive investigations on pure PANI and its composites are still much relevant to explore its potentialities to the maximum extent. The synthesis of highly crystalline PANI films with ordered structure and high electrical conductivity has not been pursued in depth yet. Recently, nanostructured PANI and the nanocomposites of PANI have attracted a great deal of research attention owing to the possibilities of applications in optical switching devices, optoelectronics and energy storage devices. The work presented in the thesis is centered around the realization of highly conducting and structurally ordered PANI and its composites for applications mainly in the areas of nonlinear optics and electrochemical energy storage. Out of the vast variety of application fields of PANI, these two areas are specifically selected for the present studies, because of the following observations. The non-linear optical properties and the energy storing properties of PANI depend quite sensitively on the extent of conjugation of the polymer structure, the type and concentration of the dopants added and the type and size of the nano particles selected for making the nanocomposites. The first phase of the work is devoted to the synthesis of highly ordered and conducting films of PANI doped with various dopants and the structural, morphological and electrical characterization followed by the synthesis of metal nanoparticles incorporated PANI samples and the detailed optical characterization in the linear and nonlinear regimes. The second phase of the work comprises the investigations on the prospects of PANI in realizing polymer based rechargeable lithium ion cells with the inherent structural flexibility of polymer systems and environmental safety and stability. Secondary battery systems have become an inevitable part of daily life. They can be found in most of the portable electronic gadgets and recently they have started powering automobiles, although the power generated is low. The efficient storage of electrical energy generated from solar cells is achieved by using suitable secondary battery systems. The development of rechargeable battery systems having excellent charge storage capacity, cyclability, environmental friendliness and flexibility has yet to be realized in practice. Rechargeable Li-ion cells employing cathode active materials like LiCoO2, LiMn2O4, LiFePO4 have got remarkable charge storage capacity with least charge leakage when not in use. However, material toxicity, chance of cell explosion and lack of effective cell recycling mechanism pose significant risk factors which are to be addressed seriously. These cells also lack flexibility in their design due to the structural characteristics of the electrode materials. Global research is directed towards identifying new class of electrode materials with less risk factors and better structural stability and flexibility. Polymer based electrode materials with inherent flexibility, stability and eco-friendliness can be a suitable choice. One of the prime drawbacks of polymer based cathode materials is the low electronic conductivity. Hence the real task with this class of materials is to get better electronic conductivity with good electrical storage capability. Electronic conductivity can be enhanced by using proper dopants. In the designing of rechargeable Li-ion cells with polymer based cathode active materials, the key issue is to identify the optimum lithiation of the polymer cathode which can ensure the highest electronic conductivity and specific charge capacity possible The development of conducting polymer based rechargeable Li-ion cells with high specific capacity and excellent cycling characteristics is a highly competitive area among research and development groups, worldwide. Polymer based rechargeable batteries are specifically attractive due to the environmentally benign nature and the possible constructional flexibility they offer. Among polymers having electrical transport properties suitable for rechargeable battery applications, polyaniline is the most favoured one due to its tunable electrical conducting properties and the availability of cost effective precursor materials for its synthesis. The performance of a battery depends significantly on the characteristics of its integral parts, the cathode, anode and the electrolyte, which in turn depend on the materials used. Many research groups are involved in developing new electrode and electrolyte materials to enhance the overall performance efficiency of the battery. Currently explored electrolytes for Li ion battery applications are in liquid or gel form, which makes well-defined sealing essential. The use of solid electrolytes eliminates the need for containment of liquid electrolytes, which will certainly simplify the cell design and improve the safety and durability. The other advantages of polymer electrolytes include dimensional stability, safety and the ability to prevent lithium dendrite formation. One of the ultimate aims of the present work is to realize all solid state, flexible and environment friendly Li-ion cells with high specific capacity and excellent cycling stability. Part of the present work is hence focused on identifying good polymer based solid electrolytes essential for realizing all solid state polymer based Li ion cells.The present work is an attempt to study the versatile roles of polyaniline in two different fields of technological applications like nonlinear optics and energy storage. Conducting form of doped PANI films with good extent of crystallinity have been realized using a level surface assisted casting method in addition to the generally employed technique of spin coating. Metal nanoparticles embedded PANI offers a rich source for nonlinear optical studies and hence gold and silver nanoparticles have been used for making the nanocomposites in bulk and thin film forms. These PANI nanocomposites are found to exhibit quite dominant third order optical non-linearity. The highlight of these studies is the observation of the interesting phenomenon of the switching between saturable absorption (SA) and reverse saturable absorption (RSA) in the films of Ag/PANI and Au/PANI nanocomposites, which offers prospects of applications in optical switching. The investigations on the energy storage prospects of PANI were carried out on Li enriched PANI which was used as the cathode active material for assembling rechargeable Li-ion cells. For Li enrichment or Li doping of PANI, n-Butyllithium (n-BuLi) in hexanes was used. The Li doping as well as the Li-ion cell assembling were carried out in an argon filled glove box. Coin cells were assembled with Li doped PANI with different doping concentrations, as the cathode, LiPF6 as the electrolyte and Li metal as the anode. These coin cells are found to show reasonably good specific capacity around 22mAh/g and excellent cycling stability and coulombic efficiency around 99%. To improve the specific capacity, composites of Li doped PANI with inorganic cathode active materials like LiFePO4 and LiMn2O4 were synthesized and coin cells were assembled as mentioned earlier to assess the electrochemical capability. The cells assembled using the composite cathodes are found to show significant enhancement in specific capacity to around 40mAh/g. One of the other interesting observations is the complete blocking of the adverse effects of Jahn-Teller distortion, when the composite cathode, PANI-LiMn2O4 is used for assembling the Li-ion cells. This distortion is generally observed, near room temperature, when LiMn2O4 is used as the cathode, which significantly reduces the cycling stability of the cells.

Relativistic LCAO with Minimax Principle and New Balanced Basis Sets

Relativistic density functional theory is widely applied in molecular calculations with heavy atoms, where relativistic and correlation effects are on the same footing. Variational stability of the Dirac Hamiltonian is a very important field of research from the beginning of relativistic molecular calculations on, among efforts for accuracy, efficiency, and density functional formulation, etc. Approximations of one- or two-component methods and searching for suitable basis sets are two major means for good projection power against the negative continuum. The minimax two-component spinor linear combination of atomic orbitals (LCAO) is applied in the present work for both light and super-heavy one-electron systems, providing good approximations in the whole energy spectrum, being close to the benchmark minimax finite element method (FEM) values and without spurious and contaminated states, in contrast to the presence of these artifacts in the traditional four-component spinor LCAO. The variational stability assures that minimax LCAO is bounded from below. New balanced basis sets, kinetic and potential defect balanced (TVDB), following the minimax idea, are applied with the Dirac Hamiltonian. Its performance in the same super-heavy one-electron quasi-molecules shows also very good projection capability against variational collapse, as the minimax LCAO is taken as the best projection to compare with. The TVDB method has twice as many basis coefficients as four-component spinor LCAO, which becomes now linear and overcomes the disadvantage of great time-consumption in the minimax method. The calculation with both the TVDB method and the traditional LCAO method for the dimers with elements in group 11 of the periodic table investigates their difference. New bigger basis sets are constructed than in previous research, achieving high accuracy within the functionals involved. Their difference in total energy is much smaller than the basis incompleteness error, showing that the traditional four-spinor LCAO keeps enough projection power from the numerical atomic orbitals and is suitable in research on relativistic quantum chemistry. In scattering investigations for the same comparison purpose, the failure of the traditional LCAO method of providing a stable spectrum with increasing size of basis sets is contrasted to the TVDB method, which contains no spurious states already without pre-orthogonalization of basis sets. Keeping the same conditions including the accuracy of matrix elements shows that the variational instability prevails over the linear dependence of the basis sets. The success of the TVDB method manifests its capability not only in relativistic quantum chemistry but also for scattering and under the influence of strong external electronic and magnetic fields. The good accuracy in total energy with large basis sets and the good projection property encourage wider research on different molecules, with better functionals, and on small effects.

Modeling Stock Order Flows and Learning Market-Making from Data

Stock markets employ specialized traders, market-makers, designed to provide liquidity and volume to the market by constantly supplying both supply and demand. In this paper, we demonstrate a novel method for modeling the market as a dynamic system and a reinforcement learning algorithm that learns profitable market-making strategies when run on this model. The sequence of buys and sells for a particular stock, the order flow, we model as an Input-Output Hidden Markov Model fit to historical data. When combined with the dynamics of the order book, this creates a highly non-linear and difficult dynamic system. Our reinforcement learning algorithm, based on likelihood ratios, is run on this partially-observable environment. We demonstrate learning results for two separate real stocks.

Análisis de sensibilidad para un modelo de medición de percepción de marca basado en simulación computacional por agentes

Se presenta el análisis de sensibilidad de un modelo de percepción de marca y ajuste de la inversión en marketing desarrollado en el Laboratorio de Simulación de la Universidad del Rosario. Este trabajo de grado consta de una introducción al tema de análisis de sensibilidad y su complementario el análisis de incertidumbre. Se pasa a mostrar ambos análisis usando un ejemplo simple de aplicación del modelo mediante la aplicación exhaustiva y rigurosa de los pasos descritos en la primera parte. Luego se hace una discusión de la problemática de medición de magnitudes que prueba ser el factor más complejo de la aplicación del modelo en el contexto práctico y finalmente se dan conclusiones sobre los resultados de los análisis.