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.

Design and implementation of a behaviorally typed programming system for web services

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para a obtenção do Grau de Mestre em Engenharia Informática.

A Logic and tool for local reasoning about security protocols

Trabalho apresentado no âmbito do Mestrado em Engenharia Informática, como requisito parcial para obtenção do grau de Mestre em Engenharia Informática

Towards a GIS-T database design and implementation for public transit planning: the case study of Dar-Es-salaam metropolitan city, Tanzania.

Dissertation submitted in partial fulfilment of the requirements for the Degree of Master of Science in Geospatial Technologies

On the fractional order control of heat systems

The differentiation of non-integer order has its origin in the seventeenth century, but only in the last two decades appeared the first applications in the area of control theory. In this paper we consider the study of a heat diffusion system based on the application of the fractional calculus concepts. In this perspective, several control methodologies are investigated namely the fractional PID and the Smith predictor. Extensive simulations are presented assessing the performance of the proposed fractional-order algorithms.

Particle swarm design of digital circuits

Swarm Intelligence (SI) is the property of a system whereby the collective behaviors of (unsophisticated) agents interacting locally with their environment cause coherent functional global patterns to emerge. Particle swarm optimization (PSO) is a form of SI, and a population-based search algorithm that is initialized with a population of random solutions, called particles. These particles are flying through hyperspace and have two essential reasoning capabilities: their memory of their own best position and knowledge of the swarm's best position. In a PSO scheme each particle flies through the search space with a velocity that is adjusted dynamically according with its historical behavior. Therefore, the particles have a tendency to fly towards the best search area along the search process. This work proposes a PSO based algorithm for logic circuit synthesis. The results show the statistical characteristics of this algorithm with respect to number of generations required to achieve the solutions. It is also presented a comparison with other two Evolutionary Algorithms, namely Genetic and Memetic Algorithms.

Real time manufacturing systems simulator

A área da simulação computacional teve um rápido crescimento desde o seu apareciment, sendo actualmente uma das ciências de gestão e de investigação operacional mais utilizadas. O seu princípio baseia-se na replicação da operação de processos ou sistemas ao longo de períodos de tempo, tornando-se assim uma metodologia indispensável para a resolução de variados problemas do mundo real, independentemente da sua complexidade. Das inúmeras áreas de aplicação, nos mais diversos campos, a que mais se destaca é a utilização em sistemas de produção, onde o leque de aplicações disponível é muito vasto. A sua aplicação tem vindo a ser utilizada para solucionar problemas em sistemas de produção, uma vez que permite às empresas ajustar e planear de uma maneira rápida, eficaz e ponderada as suas operações e os seus sistemas, permitindo assim uma rápida adaptação das mesmas às constantes mudanças das necessidades da economia global. As aplicações e packages de simulação têm seguindo as tendências tecnológicas pelo que é notório o recurso a tecnologias orientadas a objectos para o desenvolvimento das mesmas. Este estudo baseou-se, numa primeira fase, na recolha de informação de suporte aos conceitos de modelação e simulação, bem como a respectiva aplicação a sistemas de produção em tempo real. Posteriormente centralizou-se no desenvolvimento de um protótipo de uma aplicação de simulação de ambientes de fabrico em tempo real. O desenvolvimento desta ferramenta teve em vista eventuais fins pedagógicos e uma utilização a nível académico, sendo esta capaz de simular um modelo de um sistema de produção, estando também dotada de animação. Sem deixar de parte a possibilidade de integração de outros módulos ou, até mesmo, em outras plataformas, houve ainda a preocupação acrescida de que a sua implementação recorresse a metodologias de desenvolvimento orientadas a objectos.

Integration of e-learning systems with repositories of learning objects

This paper describes a communication model to integrate repositories of programming problems with other e-Learning software components. The motivation for this work comes from the EduJudge project that aims to connect an existing repository of programming problems to learning management systems. When trying to use the existing repositories of learning objects we realized that they are mainly specialized search engines and lack features for integration with other e-Learning systems. With this model we intend to clarify the main features of a programming problem repository, in order to enable the design and development of software components that use it. The two main points of this model are the definition of programming problems as learning objects and the definition of the core functions exposed by the repository. In both cases, this model follows the existing specifications of the IMS standard and proposes extensions to deal with the special requirements of automatic evaluation and grading of programming exercises. In the definition of programming problems as learning objects we introduced a new schema for meta-data. This schema is used to represent meta-data related to automatic evaluation that cannot be conveniently represented using the standard: the type of automatic evaluation; the requirements of the evaluation engine; or the roles of different assets - tests cases, program solutions, etc. In the definition of the core functions we used two different web services flavours - SOAP and REST - and described each function as an operation for each type of interface. We describe also the data types of the arguments of each operation. These data types consist mainly on learning objects and their identifications, but include also usage reports and queries using XQuery.

Fractional control of heat diffusion systems

The concept of differentiation and integration to non-integer order has its origins in the seventeen century. However, only in the second-half of the twenty century appeared the first applications related to the area of control theory. In this paper we consider the study of a heat diffusion system based on the application of the fractional calculus concepts. In this perspective, several control methodologies are investigated and compared. Simulations are presented assessing the performance of the proposed fractional-order algorithms.

Curso E-learning de sistemas multicorpo (multibody systems) para engenheiros mecânicos

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica

Argumentation as Distributed Belief Revision: Conflict Resolution in Decentralised Multi-agent Systems

Decentralised co-operative multi-agent systems are computational systems where conflicts are frequent due to the nature of the represented knowledge. Negotiation methodologies, in this case argumentation based negotiation methodologies, were developed and applied to solve unforeseeable and, therefore, unavoidable conflicts. The supporting computational model is a distributed belief revision system where argumentation plays the decisive role of revision. The distributed belief revision system detects, isolates and solves, whenever possible, the identified conflicts. The detection and isolation of the conflicts is automatically performed by the distributed consistency mechanism and the resolution of the conflict, or belief revision, is achieved via argumentation. We propose and describe two argumentation protocols intended to solve different types of identified information conflicts: context dependent and context independent conflicts. While the protocol for context dependent conflicts generates new consensual alternatives, the latter chooses to adopt the soundest, strongest argument presented. The paper shows the suitability of using argumentation as a distributed decentralised belief revision protocol to solve unavoidable conflicts.

Belief Revision in Multi-Agent Systems

The ability to respond sensibly to changing and conflicting beliefs is an integral part of intelligent agency. To this end, we outline the design and implementation of a Distributed Assumption-based Truth Maintenance System (DATMS) appropriate for controlling cooperative problem solving in a dynamic real world multi-agent community. Our DATMS works on the principle of local coherence which means that different agents can have different perspectives on the same fact provided that these stances are appropriately justified. The belief revision algorithm is presented, the meta-level code needed to ensure that all system-wide queries can be uniquely answered is described, and the DATMS’ implementation in a general purpose multi-agent shell is discussed.

On a self-start Darrieus wind turbine: blade design and field tests

This paper is about a design of an urban area Darrieus VAWT, having self-start ability due to an innovative profile design named EN0005, avoiding the need of extra components or external electricity feed-in. An approach is presented to study the ability of a blade profile to offer self-start ability. Methodologies applied for the blade body and for profile development are reported. Field tests and main conclusions are presented to persuade for the arrangement of this design. (C) 2015 Elsevier Ltd. All rights reserved.

Six sigma methodologies: implementation and impacts on Portuguese small and medium companies (SMES)

Artigo elaborador no âmbito dos trabalhos decorrentes à dissertação de Mestrado do Aluno David Leite, no Mestrado em Gestão Integrada Qualidade, Ambiente e Segurança, ESTGF-IPP, Oreintados pelos Professores Luís Fonseca (ISEP-IPP) e Vanda Lima (ESTGF-IPP).

Análise sísmica e proposta de reforço de uma estrutura do séc. XIX sujeita a uma reabilitação parcial

Trabalho final de Mestrado para a obtenção do grau de mestre em Engenharia Civil