Automatic learning for the classification of chemical reactions and in statistical thermodynamics

This Thesis describes the application of automatic learning methods for a) the classification of organic and metabolic reactions, and b) the mapping of Potential Energy Surfaces(PES). The classification of reactions was approached with two distinct methodologies: a representation of chemical reactions based on NMR data, and a representation of chemical reactions from the reaction equation based on the physico-chemical and topological features of chemical bonds. NMR-based classification of photochemical and enzymatic reactions. Photochemical and metabolic reactions were classified by Kohonen Self-Organizing Maps (Kohonen SOMs) and Random Forests (RFs) taking as input the difference between the 1H NMR spectra of the products and the reactants. The development of such a representation can be applied in automatic analysis of changes in the 1H NMR spectrum of a mixture and their interpretation in terms of the chemical reactions taking place. Examples of possible applications are the monitoring of reaction processes, evaluation of the stability of chemicals, or even the interpretation of metabonomic data. A Kohonen SOM trained with a data set of metabolic reactions catalysed by transferases was able to correctly classify 75% of an independent test set in terms of the EC number subclass. Random Forests improved the correct predictions to 79%. With photochemical reactions classified into 7 groups, an independent test set was classified with 86-93% accuracy. The data set of photochemical reactions was also used to simulate mixtures with two reactions occurring simultaneously. Kohonen SOMs and Feed-Forward Neural Networks (FFNNs) were trained to classify the reactions occurring in a mixture based on the 1H NMR spectra of the products and reactants. Kohonen SOMs allowed the correct assignment of 53-63% of the mixtures (in a test set). Counter-Propagation Neural Networks (CPNNs) gave origin to similar results. The use of supervised learning techniques allowed an improvement in the results. They were improved to 77% of correct assignments when an ensemble of ten FFNNs were used and to 80% when Random Forests were used. This study was performed with NMR data simulated from the molecular structure by the SPINUS program. In the design of one test set, simulated data was combined with experimental data. The results support the proposal of linking databases of chemical reactions to experimental or simulated NMR data for automatic classification of reactions and mixtures of reactions. Genome-scale classification of enzymatic reactions from their reaction equation. The MOLMAP descriptor relies on a Kohonen SOM that defines types of bonds on the basis of their physico-chemical and topological properties. The MOLMAP descriptor of a molecule represents the types of bonds available in that molecule. The MOLMAP descriptor of a reaction is defined as the difference between the MOLMAPs of the products and the reactants, and numerically encodes the pattern of bonds that are broken, changed, and made during a chemical reaction. The automatic perception of chemical similarities between metabolic reactions is required for a variety of applications ranging from the computer validation of classification systems, genome-scale reconstruction (or comparison) of metabolic pathways, to the classification of enzymatic mechanisms. Catalytic functions of proteins are generally described by the EC numbers that are simultaneously employed as identifiers of reactions, enzymes, and enzyme genes, thus linking metabolic and genomic information. Different methods should be available to automatically compare metabolic reactions and for the automatic assignment of EC numbers to reactions still not officially classified. In this study, the genome-scale data set of enzymatic reactions available in the KEGG database was encoded by the MOLMAP descriptors, and was submitted to Kohonen SOMs to compare the resulting map with the official EC number classification, to explore the possibility of predicting EC numbers from the reaction equation, and to assess the internal consistency of the EC classification at the class level. A general agreement with the EC classification was observed, i.e. a relationship between the similarity of MOLMAPs and the similarity of EC numbers. At the same time, MOLMAPs were able to discriminate between EC sub-subclasses. EC numbers could be assigned at the class, subclass, and sub-subclass levels with accuracies up to 92%, 80%, and 70% for independent test sets. The correspondence between chemical similarity of metabolic reactions and their MOLMAP descriptors was applied to the identification of a number of reactions mapped into the same neuron but belonging to different EC classes, which demonstrated the ability of the MOLMAP/SOM approach to verify the internal consistency of classifications in databases of metabolic reactions. RFs were also used to assign the four levels of the EC hierarchy from the reaction equation. EC numbers were correctly assigned in 95%, 90%, 85% and 86% of the cases (for independent test sets) at the class, subclass, sub-subclass and full EC number level,respectively. Experiments for the classification of reactions from the main reactants and products were performed with RFs - EC numbers were assigned at the class, subclass and sub-subclass level with accuracies of 78%, 74% and 63%, respectively. In the course of the experiments with metabolic reactions we suggested that the MOLMAP / SOM concept could be extended to the representation of other levels of metabolic information such as metabolic pathways. Following the MOLMAP idea, the pattern of neurons activated by the reactions of a metabolic pathway is a representation of the reactions involved in that pathway - a descriptor of the metabolic pathway. This reasoning enabled the comparison of different pathways, the automatic classification of pathways, and a classification of organisms based on their biochemical machinery. The three levels of classification (from bonds to metabolic pathways) allowed to map and perceive chemical similarities between metabolic pathways even for pathways of different types of metabolism and pathways that do not share similarities in terms of EC numbers. Mapping of PES by neural networks (NNs). In a first series of experiments, ensembles of Feed-Forward NNs (EnsFFNNs) and Associative Neural Networks (ASNNs) were trained to reproduce PES represented by the Lennard-Jones (LJ) analytical potential function. The accuracy of the method was assessed by comparing the results of molecular dynamics simulations (thermal, structural, and dynamic properties) obtained from the NNs-PES and from the LJ function. The results indicated that for LJ-type potentials, NNs can be trained to generate accurate PES to be used in molecular simulations. EnsFFNNs and ASNNs gave better results than single FFNNs. A remarkable ability of the NNs models to interpolate between distant curves and accurately reproduce potentials to be used in molecular simulations is shown. The purpose of the first study was to systematically analyse the accuracy of different NNs. Our main motivation, however, is reflected in the next study: the mapping of multidimensional PES by NNs to simulate, by Molecular Dynamics or Monte Carlo, the adsorption and self-assembly of solvated organic molecules on noble-metal electrodes. Indeed, for such complex and heterogeneous systems the development of suitable analytical functions that fit quantum mechanical interaction energies is a non-trivial or even impossible task. The data consisted of energy values, from Density Functional Theory (DFT) calculations, at different distances, for several molecular orientations and three electrode adsorption sites. The results indicate that NNs require a data set large enough to cover well the diversity of possible interaction sites, distances, and orientations. NNs trained with such data sets can perform equally well or even better than analytical functions. Therefore, they can be used in molecular simulations, particularly for the ethanol/Au (111) interface which is the case studied in the present Thesis. Once properly trained, the networks are able to produce, as output, any required number of energy points for accurate interpolations.

Object transportation by multiple mobile robots controlled by attractor dynamics: theory and implementation

Dynamical systems theory is used as a theoretical language and tool to design a distributed control architecture for teams of mobile robots, that must transport a large object and simultaneously avoid collisions with (either static or dynamic) obstacles. Here we demonstrate in simulations and implementations in real robots that it is possible to simplify the architectures presented in previous work and to extend the approach to teams of n robots. The robots have no prior knowledge of the environment. The motion of each robot is controlled by a time series of asymptotical stable states. The attractor dynamics permits the integration of information from various sources in a graded manner. As a result, the robots show a strikingly smooth an stable team behaviour.

Using attractor dynamics to generate decentralized motion control of two mobile robots transporting a long object in coordination

Dynamical systems theory is used here as a theoretical language and tool to design a distributed control architecture for a team of two mobile robots that must transport a long object and simultaneously avoid obstacles. In this approach the level of modeling is at the level of behaviors. A “dynamics” of behavior is defined over a state space of behavioral variables (heading direction and path velocity). The environment is also modeled in these terms by representing task constraints as attractors (i.e. asymptotically stable states) or reppelers (i.e. unstable states) of behavioral dynamics. For each robot attractors and repellers are combined into a vector field that governs the behavior. The resulting dynamical systems that generate the behavior of the robots may be nonlinear. By design the systems are tuned so that the behavioral variables are always very close to one attractor. Thus the behavior of each robot is controled by a time series of asymptotically stable states. Computer simulations support the validity of our dynamic model architectures.

Fractional order control on a wind turbine benchmark

This paper is about a hierarchical structure with an event-based supervisor in a higher level and a fractional-order proportional integral (FOPI) in a lower level applied to a wind turbine. The event-based supervisor analyzes the operation conditions to determine the state of the wind turbine. This controller operate in the full load region and the main objective is to capture maximum power generation while ensuring the performance and reliability required for a wind turbine to be integrated into an electric grid. The main contribution focus on the use of fractional-order proportional integral controller which benefits from the introduction of one more tuning parameter, the integral fractional-order, taking advantage over integer order proportional integral (PI) controller. Comparisons between fractional-order pitch control and a default proportional integral pitch controller applied to a wind turbine benchmark are given and simulation results by Matlab/Simulink are shown in order to prove the effectiveness of the proposed approach.

Fractional control of dynamic systems

The concepts involved with fractional calculus (FC) theory are applied in almost all areas of science and engineering. Its ability to yield superior modeling and control in many dynamical systems is well recognized. In this article, we will introduce the fundamental aspects associated with the application of FC to the control of dynamic systems.

Control and dynamics of fractional order systems

Fractional Calculus (FC) goes back to the beginning of the theory of differential calculus. Nevertheless, the application of FC just emerged in the last two decades due to the progress in the area of nonlinear dynamics. This article discusses several applications of fractional calculus in science and engineering, namely: the control of heat systems, the tuning of PID controllers based on fractional calculus concepts and the dynamics in hexapod locomotion.

Theory and phenomenology of two-higgs-doublet models

We discuss theoretical and phenomenological aspects of two-Higgs-doublet extensions of the Standard Model. In general, these extensions have scalar mediated flavour changing neutral currents which are strongly constrained by experiment. Various strategies are discussed to control these flavour changing scalar currents and their phenomenological consequences are analysed. In particular, scenarios with natural flavour conservation are investigated, including the so-called type I and type II models as well as lepton-specific and inert models. Type III models are then discussed, where scalar flavour changing neutral currents are present at tree level, but are suppressed by either a specific ansatz for the Yukawa couplings or by the introduction of family symmetries leading to a natural suppression mechanism. We also consider the phenomenology of charged scalars in these models. Next we turn to the role of symmetries in the scalar sector. We discuss the six symmetry-constrained scalar potentials and their extension into the fermion sector. The vacuum structure of the scalar potential is analysed, including a study of the vacuum stability conditions on the potential and the renormalization-group improvement of these conditions is also presented. The stability of the tree level minimum of the scalar potential in connection with electric charge conservation and its behaviour under CP is analysed. The question of CP violation is addressed in detail, including the cases of explicit CP violation and spontaneous CP violation. We present a detailed study of weak basis invariants which are odd under CP. These invariants allow for the possibility of studying the CP properties of any two-Higgs-doublet model in an arbitrary Higgs basis. A careful study of spontaneous CP violation is presented, including an analysis of the conditions which have to be satisfied in order for a vacuum to violate CP. We present minimal models of CP violation where the vacuum phase is sufficient to generate a complex CKM matrix, which is at present a requirement for any realistic model of spontaneous CP violation.

Adapted Control Methods for Cerebral Palsy Users of an Intelligent Wheelchair

The development of an intelligent wheelchair (IW) platform that may be easily adapted to any commercial electric powered wheelchair and aid any person with special mobility needs is the main objective of this project. To be able to achieve this main objective, three distinct control methods were implemented in the IW: manual, shared and automatic. Several algorithms were developed for each of these control methods. This paper presents three of the most significant of those algorithms with emphasis on the shared control method. Experiments were performed by users suffering from cerebral palsy, using a realistic simulator, in order to validate the approach. The experiments revealed the importance of using shared (aided) controls for users with severe disabilities. The patients still felt having complete control over the wheelchair movement when using a shared control at a 50% level and thus this control type was very well accepted. Thus it may be used in intelligent wheelchairs since it is able to correct the direction in case of involuntary movements of the user but still gives him a sense of complete control over the IW movement.

Health care marketing: the theory of planned behavior applied to patients' choise between private and public providers in the portuguese health care system.

Dissertation submitted in partial fulfillment of the requirements for degree of Master in Statistics and Information Management.

Control and Dynamics of Fractional Order Systems

Fractional Calculus (FC) goes back to the beginning of the theory of differential calculus. Nevertheless, the application of FC just emerged in the last two decades due to the progress in the area of nonlinear dynamics. This article discusses several applications of fractional calculus in science and engineering, namely: the control of heat systems, the tuning of PID controllers based on fractional calculus concepts and the dynamics in hexapod locomotion.

Fractional Dynamics and Control of Distributed Parameter Systems

Fractional Calculus (FC) goes back to the beginning of the theory of differential calculus. Nevertheless, the application of FC just emerged in the last two decades, due to the progress in the area of chaos that revealed subtle relationships with the FC concepts. In the field of dynamical systems theory some work has been carried out but the proposed models and algorithms are still in a preliminary stage of establishment. Having these ideas in mind, the paper discusses a FC perspective in the study of the dynamics and control of some distributed parameter systems.

System Modeling and Control Through Fractional-Order Algorithms

The theory of fractional calculus goes back to the beginning of thr throry of differential calculus but its inherent complexity postponed the applications of the associated concepts. In the last decade the progress in the areas of chaos and fractals revealed subtle relationships with the fractional calculus leading to an increasing interest in the development of the new paradigm. In the area of automaticcontrol preliminary work has already been carried out but the proposed algorithms are restricted to the frequency domain. The paper discusses the design of fractional-order discrete-time controllers. The algorithms studied adopt the time domein, which makes them suited for z-transform analusis and discrete-time implementation. The performance of discrete-time fractional-order controllers with linear and non-linear systems is also investigated.

Successful control program to implement the appropriate antibiotic prophylaxis for cesarean section

OBJECTIVE: Describe implementation of a successful program to reduce doses (cefazolin 2 to 1 g) used for antimicrobial prophylaxis. METHODS: Evaluation of an intervention program to reduce prophylactic antimicrobial doses. The intervention included weekly staff discussions, automatic dispensation of 1g-vial of cefazolin by the pharmacy unless expressly requested by surgeon and increase in post-discharge surveillance as a strategy to reassure surgeons of the safety of the reduction. In the pre and post intervention periods, a prospective study of antimicrobial consumption and surgical site infections were measured. RESULTS: There were 5,164 and 5,204 deliveries in 2001-2002 and 2003-2004, respectively; 1,524 (29.5%) and 1,363 (26%) were cesarean sections. There was a 45% decrease in cefazolin vials used on average per cesarean section (2.29 to 1.25). Patients evaluated increased from 16% to 67% and the SSI rates in both periods were 3.34% to 2.42%, respectively. CONCLUSION: An ample intervention, including administrative and educational measures, led to high compliance with dose reduction and saved more than US$4,000 in cefazolin, considered important because government reimbursement in Brazil for cesarean section is $80.

Robot Manipulator Systems: Analysis and Control

Manipulator systems are rather complex and highly nonlinear which makes difficult their analysis and control. Classic system theory is veil known, however it is inadequate in the presence of strong nonlinear dynamics. Nonlinear controllers produce good results [1] and work has been done e. g. relating the manipulator nonlinear dynamics with frequency response [2–5]. Nevertheless, given the complexity of the problem, systematic methods which permit to draw conclusions about stability, imperfect modelling effects, compensation requirements, etc. are still lacking. In section 2 we start by analysing the variation of the poles and zeros of the descriptive transfer functions of a robot manipulator in order to motivate the development of more robust (and computationally efficient) control algorithms. Based on this analysis a new multirate controller which is an improvement of the well known “computed torque controller” [6] is announced in section 3. Some research in this area was done by Neuman [7,8] showing tbat better robustness is possible if the basic controller structure is modified. The present study stems from those ideas, and attempts to give a systematic treatment, which results in easy to use standard engineering tools. Finally, in section 4 conclusions are presented.

eVentos 2 - Autonomous sailboat control

Dissertação para obtenção do Grau de Mestre em Engenharia Electrotécnica e de Computadores