A síntese e caracterização de sistemas hetero-híbridos gerados a partir da 3,6-bi-2-piridil-1,2,4,5-tetrazina (bptz) e interações com ouro nanoparticulado são abordados nesta tese. O bptz foi estudado por meio de métodos espectroscópicos e teóricos, focalizando principalmente o efeito SERS associado à adsorção em nanopartículas de ouro. O mecanismo de transferência de carga para metais macroscópicos foi transposto para a condição nanoparticulada, envolvendo ligações químicas entre bptz e as nanopartículas. Os complexos estudados possuem fórmula geral [LmRu(µ-bptz)RuLm]Xn, com “L” indicando os ligantes periféricos 5-cloro-1,10-fenantrolina (Clphen) ou 4’-(fenil)-2,2&#8217:6&#8217,2&#8221-terpirdina (ptpy) e “X” os contra-íons. Foram investigadas suas espectroeletroquímicas eletrônica e SERS, e as mudanças de perfil vibracional foram modeladas, incorporando o mecanismo de transferências de carga entre complexo e o ouro, além dos mecanismos ressonantes e eletromagnéticos / The synthesis and investigation of heterohybrid systems encompassing 3,6-bi-2-pyridyl-1,2,4,5-tetrazine (bptz) and its ruthenium complexes associated with gold nanoparticles are dealt with in this thesis. Bptz was characterized by spectroscopic and theoretical techniques, focusing on its SERS spectra after the adsorption onto nanoparticles. The charge transfer mechanism in the SERS spectra of macroscopic metals was transposed to the nanoparticle condition, assuming the formation of chemical bonds between bptz and the nanoparticles. Complexes of general formula [LmRu(µ--bptz)RuLm]Xn, “L” the peripheric ligants 5-chlorine-1,10-phenantroline or 4’-(phenyl)-2,2&#8217:6&#8217,2&#8221-terpyrdine (ptpy), and “X” counter-ions were also investigated, with special emphasis on their electronic and SERS spectroelectrochemistry. The changes in the vibrational profiles were successfully explained by the occurrence of charge transfer between the adsorbed complex and gold, in addition to the electromagnetic and resonance mechanisms.

Este trabalho utiliza a experiência do Laboratório de Sistemas Fotovoltaicos do Instituto de Energia e Ambiente da Universidade de São Paulo (LSF-IEE-USP) para propor meios efetivos para qualificação de recursos humanos, dentro de laboratórios com qualidade reconhecida, com o intuito de aumentar a quantidade de especialistas na área. Para tanto, foi criado um local, na forma de laboratório, denominado Unidade de Capacitação Tecnológica, composto por sistemas fotovoltaicos isolados e conectados à rede e por duas minirredes híbridas de geração de energia (solar, diesel e rede elétrica), com sistemas de monitoramento próprios, que permitem a avaliação de diferentes estratégias de operação de sistemas fotovoltaicos. Tal Unidade foi concebida sob uma perspectiva didática, para possibilitar a apropriação das habilidades técnicas e conhecimentos tecnológicos necessários para: a) atuar nas diversas ocupações demandadas pelo setor (instaladores, projetistas e engenheiros); b) desenvolver pesquisas na área (especializações, mestrados e doutorados); e c) prestar suporte para iniciativas interessadas na aplicação da tecnologia fotovoltaica (ensaios, consultorias e treinamentos). A apresentação da Unidade conta com a descrição dos materiais, ferramentas, instrumentos e procedimentos utilizados para a acreditação dos laboratórios que a compõem, permitindo demonstrar a confiabilidade, credibilidade e universalidade de seus processos, especialmente no que se refere à realização de ensaios de conformidade em equipamentos fotovoltaicos. O trabalho também investiga iniciativas de capacitação que estão sendo realizadas em outras universidades, escolas técnicas e iniciativa privada, para compreender o perfil dos profissionais atuantes no mercado. A ideia é demonstrar o quanto é fundamental a criação de uma forma de certificação ou uma política instrutiva para a capacitação dos profissionais de sistemas fotovoltaicos, de forma a promover as boas práticas e inibir aquelas que comprometam a credibilidade da tecnologia. Esta tese demonstra que laboratórios capacitados, como a Unidade descrita neste trabalho, apresentam os elementos necessários para produção e divulgação de conhecimentos, desenvolvimento de produtos, prestação de serviços e treinamento de profissionais requeridos para a expansão do setor, podendo colaborar para a consolidação da energia fotovoltaica como uma alternativa eficaz e confiável no cenário energético brasileiro. / This work uses the experience of the Photovoltaic Systems Laboratory of the Institute for Energy and Environment of the University of São Paulo (LSF-IEE-USP) to propose effective ways for the qualification of human resources within laboratories with recognized quality, in order to increase the amount of experts. Thus, a site was created in the form of laboratory, named Technology Skills Unit, composed of individual photovoltaic systems and two hybrid power systems (solar, diesel and power grid), with monitoring systems that allows evaluation of different operating of photovoltaic systems. This unit is designed in a didactic perspective to enable the appropriation of technical skills and technological knowledge necessary for: a) act in different occupations demanded by the sector (installers, designers and engineers), b) develop research in the area and c) provide support for initiatives interested in the application of photovoltaic technology. The presentation of the Unit has the description of the materials, tools, instruments and procedures for the accreditation of laboratories that comprise it, allowing demonstrate the reliability, credibility and universality of its processes, especially with regard to the testing of conformity in photovoltaic equipment. This study also investigates training initiatives being undertaken at other universities, technical schools, and private initiative to understand the profile of the professionals working in the market. The idea is to demonstrate how essential is the creation of a form of certification or an instructive policy for the professional of photovoltaic in order to promote good practice and inhibit those that undermine the credibility of technology. This thesis demonstrates that trained laboratory personnel with the structure proposed in this paper and accredited as is described, presents the necessary elements for the dissemination of technical and scientific knowledge required to qualify professionals specializing in photovoltaic applications, and may contribute to the consolidation of photovoltaic solar energy as effective and reliable alternative to the energy scenario that is imposed in Brazil today.

Infectious disease models with switching are constructed and investigated in detail. Modelling infectious diseases as switched systems, which are systems that combine continuous dynamics with discrete logic, allows for the use of methods from switched systems theory. These methods are used to analyze the stability and long-term behaviour of the proposed switched epidemiological models. Switching is first incorporated into epidemiological models by assuming the contact rate to be time-dependent and better approximated by a piecewise constant. Epidemiological models with switched incidence rates are also investigated. Threshold criteria are established that are sufficient for the eradication of the disease, and, hence, the stability of the disease-free solution. In the case of an endemic disease, some criteria are developed that establish the persistence of the disease. Lyapunov function techniques, as well as techniques for stability of impulsive or non-impulsive switched systems with both stable and unstable modes are used. These methods are first applied to switched epidemiological models which are intrinsically one-dimensional. Multi-dimensional disease models with switching are then investigated in detail. An important part of studying epidemiology is to construct control strategies in order to eradicate a disease, which would otherwise be persistent. Hence, the application of controls schemes to switched epidemiological models are investigated. Finally, epidemiological models with switched general nonlinear incidence rates are considered. Simulations are given throughout to illustrate our results, as well as to make some conjectures. Some conclusions are made and future directions are given.

Neuroprosthetics is at the intersection of neuroscience, biomedical engineering, and physics. A biocompatible neuroprosthesis contains artificial neurons exhibiting biophysically plausible dynamics. Hybrid systems analysis could be used to prototype such artificial neurons. Biohybrid systems are composed of artificial and living neurons coupled via real-time computing and dynamic clamp. Model neurons must be thoroughly tested before coupled with a living cell. We use bifurcation theory to identify hazardous regimes of activity that may compromise biocompatibility and to identify control strategies for regimes of activity desirable for functional behavior. We construct real-time artificial neurons for the analysis of hybrid systems and demonstrate a mechanism through which an artificial neuron could maintain duty cycle independent of variations in period.

Infectious disease models with switching are constructed and investigated in detail. Modelling infectious diseases as switched systems, which are systems that combine continuous dynamics with discrete logic, allows for the use of methods from switched systems theory. These methods are used to analyze the stability and long-term behaviour of the proposed switched epidemiological models. Switching is first incorporated into epidemiological models by assuming the contact rate to be time-dependent and better approximated by a piecewise constant. Epidemiological models with switched incidence rates are also investigated. Threshold criteria are established that are sufficient for the eradication of the disease, and, hence, the stability of the disease-free solution. In the case of an endemic disease, some criteria are developed that establish the persistence of the disease. Lyapunov function techniques, as well as techniques for stability of impulsive or non-impulsive switched systems with both stable and unstable modes are used. These methods are first applied to switched epidemiological models which are intrinsically one-dimensional. Multi-dimensional disease models with switching are then investigated in detail. An important part of studying epidemiology is to construct control strategies in order to eradicate a disease, which would otherwise be persistent. Hence, the application of controls schemes to switched epidemiological models are investigated. Finally, epidemiological models with switched general nonlinear incidence rates are considered. Simulations are given throughout to illustrate our results, as well as to make some conjectures. Some conclusions are made and future directions are given.

In light of the complex and highly uncertain nature of dynamical systems requiring controls, it is not surprising that reliable system models for many high performance engineering and life science applications are unavailable. In the face of such high levels of system uncertainty, robust controllers may unnecessarily sacrifice system performance whereas adaptive controllers are clearly appropriate since they can tolerate far greater system uncertainty levels to improve system performance. In this dissertation, we develop a Lyapunov-based direct adaptive and neural adaptive control framework that addresses parametric uncertainty, unstructured uncertainty, disturbance rejection, amplitude and rate saturation constraints, and digital implementation issues. Specifically, we consider the following research topics: direct adaptive control for nonlinear uncertain systems with exogenous disturbances; robust adaptive control for nonlinear uncertain systems; adaptive control for nonlinear uncertain systems with actuator amplitude and rate saturation constraints; adaptive reduced-order dynamic compensation for nonlinear uncertain systems; direct adaptive control for nonlinear matrix second-order dynamical systems with state-dependent uncertainty; adaptive control for nonnegative and compartmental dynamical systems with applications to general anesthesia; direct adaptive control of nonnegative and compartmental dynamical systems with time delay; adaptive control for nonlinear nonnegative and compartmental dynamical systems with applications to clinical pharmacology; neural network adaptive control for nonlinear nonnegative dynamical systems; passivity-based neural network adaptive output feedback control for nonlinear nonnegative dynamical systems; neural network adaptive dynamic output feedback control for nonlinear nonnegative systems using tapped delay memory units; Lyapunov-based adaptive control framework for discrete-time nonlinear systems with exogenous disturbances; direct discrete-time adaptive control with guaranteed parameter error convergence; and hybrid adaptive control for nonlinear uncertain impulsive dynamical systems.

The objective of this dissertation is to incorporate the concept of optimality to multi-modal control and apply the theoretical results to obtain successful navigation strategies for autonomous mobile robots. The main idea in multi-modal control is to breakup a complex control task into simpler tasks. In particular, number of control modes are constructed, each with respect to a particular task, and these modes are combined according to some supervisory control logic in order to complete the overall control task. This way of modularizing the control task lends itself particularly well to the control of autonomous mobile robot, as evidenced by the success of behavior-based robotics. Many challenging and interesting research issues arise when employing multi-modal control. This thesis aims to address these issues within an optimal control framework. In particular, the contributions of this dissertation are as follows: We first addressed the problem of inferring global behaviors from a collection of local rules (i.e., feedback control laws). Next, we addressed the issue of adaptively varying the multi-modal control system to further improve performance. Inspired by adaptive multi-modal control, we presented a constructivist framework for the learning from example problem. This framework was applied to the DARPA sponsored Learning Applied to Ground Robots (LAGR) project. Next, we addressed the optimal control of multi-modal systems with infinite dimensional constraints. These constraints are formulated as multi-modal, multi-dimensional (M3D) systems, where the dimensions of the state and control spaces change between modes to account for the constraints, to ease the computational burdens associated with traditional methods. Finally, we used multi-modal control strategies to develop effective navigation strategies for autonomous mobile robots. The theoretical results presented in this thesis are verified by conducting simulated experiments using Matlab and actual experiments using the Magellan Pro robot platform and the LAGR robot. In closing, the main strength of multi-modal control lies in breaking up complex control task into simpler tasks. This divide-and-conquer approach helps modularize the control system. This has the same effect on complex control systems that object-oriented programming has for large-scale computer programs, namely it allows greater simplicity, flexibility, and adaptability.

In this work, hybrid systems with regional dynamics are considered. These are systems where transitions between different dynamical regimes occur as the continuous state of the system reaches given switching surfaces. In particular, the attention is focused on the optimal control problem associated with such systems. More precisely, given a specific cost function, the goal is to determine the optimal path of going from a given starting point to a fixed final state during an a priori specified time horizon. The key characteristic of the approach presented in this thesis is a hierarchical decomposition of the hybrid optimal control problem, yielding to a framework which allows a solution on different levels of control. On the highest level of abstraction, the regional structure of the state space is taken into account and a discrete representation of the connections between the different regions provides global accessibility relations between regions. These are used on a lower level of control to formulate the main theorem of this work, namely, the Hybrid Bellman Equation for multimodal systems, which, in fact, provides a characterization of global optimality, given an upper bound on the number of transitions along a hybrid trajectory. Not surprisingly, the optimal solution is hybrid in nature, in that it depends on not only the continuous control signals, but also on discrete decisions as to what domains the system's continuous state should go through in the first place. The main benefit with the proposed approach lies in the fact that a hierarchical Dynamic Programming algorithm can be used to representing both a theoretical characterization of the hybrid solution's structural composition and, from a more application-driven point of view, a numerically implementable calculation rule yielding to globally optimal solutions in a regional dynamics framework. The operation of the recursive algorithm is highlighted by the consideration of numerous examples, among them, a heterogeneous multi-agent problem.

Le secteur du bâtiment est un consommateur énergétique majeur, par conséquent, un cadre d’actions a été décidé au niveau international dans le but de limiter son impact. Afin de mettre en œuvre ces mesures, il est nécessaire d’avoir à disposition des modèles offrants une description fiable du comportement thermique des bâtiments. A cet effet, cette thèse propose l’application d’une nouvelle technique guidée par les données pour la modélisation thermique des bâtiments en se basant sur l’approche des systèmes hybrides, caractérisés par des dynamiques continues et événementielles. Ce choix est motivé par le fait qu’un bâtiment est un système complexe caractérisé par des phénomènes non-linéaires et l’apparition de différents événements. On utilise les modèles affines par morceaux ou PWARX pour l’identification de systèmes hybrides. C’est une collection de sous-modèles affines représentant chacun une configuration caractérisée par une dynamique particulière. Le manuscrit commence par un état de l’art sur les principales techniques de modélisation thermique des bâtiments. Ensuite, le choix d’une approche hybride est motivé par une interprétation mathématique basée sur les équations d’un circuit thermique. Ceci est suivi par une brève présentation des modèles hybrides et une description détaillée de la méthodologie utilisée. On montre ensuite comment utiliser la technique SVM pour classifier les nouvelles données. Enfin, l’intégration des modèles PWARX dans une boucle de contrôle hybride afin d’estimer le gain en performance énergétique d’un bâtiment après rénovation est présentée. La méthodologie est validée en utilisant des données issues de cas d’études variés. / The building sector is a major energy consumer, therefore, a framework of actions has been decided on by countries worldwide to limit its impact. For implementing such actions, the availability of models providing an accurate description of the thermal behavior of buildings is essential. For this purpose, this thesis proposes the application of a new data-driven technique for modeling the thermal behavior of buildings based on a hybrid system approach. Hybrid systems exhibit both continuous and discrete dynamics. This choice is motivated by the fact that a building is a complex system characterized by nonlinear phenomena and the occurrence of different events. We use a PieceWise AutoRegressive eXogeneous inputs (PWARX) model for the identification of hybrid systems. It is a collection of sub-models where each sub-model is an ARX equation representing a certain configuration in the building characterized by its own dynamics. This thesis starts with a state-of-the-art on building thermal modeling. Then, the choice of a hybrid system approach is motivated by a mathematical interpretation based on the equations derived from an RC thermal circuit of a building zone. This is followed by a brief background about hybrid system identification and a detailed description of the PWARX methodology. For the prediction phase, it is shown how to use the Support Vector Machine (SVM) technique to classify new data to the right sub-model. Then, it is shown how to integrate these models in a hybrid control loop to estimate the gain in the energy performance for a building after insulation work. The performance of the proposed technique is validated using data collected from various test cases.

Il s'agit d'une étude menée sur les systèmes cyber-physiques sur trois aspects principaux: la vérification de la stabilité, l'ordonnancement et la synthèse des paramètres. Les systèmes de contrôle embarqués (ECS) agissant dans le cadre de contrats temporels sont la classe considérée de systèmes cyber-physiques dans la thèse. ECS fait référence à des intégrations d'un dispositif informatique avec le système physique. En ce qui concerne les contrats temporels, ils sont des contraintes de temps sur les instants où se produisent certains événements tels que l'échantillonnage, l'actionnement et le calcul. Ces contrats sont utilisés pour modéliser les problèmes qui se posent dans les systèmes de contrôle modernes: incertitudes sur les retards d'actionnement, les périodes d'échantillonnage incertaines et l'interaction de plusieurs systèmes physiques avec des ressources informatiques partagées (CPUs). Maintenant, compte tenu d'un ECS et d'un contrat temporel, nous reformulons le système de manière impulsionnelle et vérifions la stabilité du système, sous toutes les incertitudes bornées et données par le contrat, en utilisant des techniques d'approximation convexe et de nouveaux résultats généralisés pour le problème sur une classe de systèmes modélisés dans le cadre des inclusions différentielles. Deuxièmement, compte tenu d'un ensemble de contrôleurs implémentés sur une plate-forme de calcul commune (CPUs), dont chacun est soumis à un contrat de synchronisation, et à son meilleur et son plus mauvais cas d'exécution dans chaque CPU, nous synthétisons une politique d’ordonnancement dynamique qui garantit que chaque contrat temporel est satisfait et que chacun des CPU partagés est attribué à au plus un contrôleur à tout moment. L'approche est basée sur une reformulation qui nous permet d'écrire le problème d’ordonnancement comme un jeu temporelle avec spécification de sureté. Ensuite, en utilisant l'outil UPPAAL-TIGA, une solution au jeu fournit une politique d’ordonnancement appropriée. En outre, nous fournissons une nouvelle condition nécessaire et suffisante pour l’ordonnancement des tâches de contrôle en fonction d’un jeu temporisé simplifiés. Enfin, nous résolvons un problème de synthèse de paramètres qui consiste à synthétiser une sous-approximation de l'ensemble des contrats de synchronisation qui garantissent en même temps l’ordonnancement et la stabilité des contrôleurs intégrés. La synthèse est basée sur un nouveau paramétrage du contrat temporel pour les rendre monotones, puis sur un échantillonnage à plusieurs reprises de l'espace des paramètres jusqu'à atteindre une précision d'approximation prédéfinie. / This is a study conducted on cyber-physical systems on three main aspects: stability verification, scheduling, and parameter synthesis. Embedded control systems (ECS) acting under timing contracts are the considered class of cyber-physical systems in the thesis. ECS refers to integrations of a computing device with the physical system. As for timing contracts they are time constraints on the instants where some events happen such as sampling, actuation, and computation. These contracts are used to model issues that arise in modern embedded control systems: uncertain sampling to actuation delays, uncertain sampling periods, and interaction of several physical systems with shared computational resources (CPUs). Now given an ECS and a timing contract we reformulate the system into an impulsive one and verifies stability of the system, under all possible bounded uncertainties given by the contract, using safe convex approximation techniques and new generalized results for the problem on a class of systems modeled in the framework of difference inclusions. Second given a set of controllers implemented on a common computational platform (CPUs), each of which is subject to a timing contract, and best and worst case execution times on each CPU, we synthesize a dynamic scheduling policy, which guarantees that each timing contract is satisfied and that each of the shared CPUs are allocated to at most one embedded controller at any time. The approach is based on a timed game formulation that allows us to write the scheduling problem as a timed safety game. Then using the tool UPPAAL-TIGA, a solution to the safety game provides a suitable scheduling policy. In addition, we provide a novel necessary and sufficient condition for schedulability of the control tasks based on a simplified timed game automaton. Last, we solve a parameter synthesis problem which consists of synthesizing an under-approximation of the set of timing contracts that guarantee at the same time the schedulability and stability of the embedded controllers. The synthesis is based on a re-parameterization of the timing contract to make them monotonic, and then on a repeatedly sampling of the parameter space until reaching a predefined precision of approximation.