982 resultados para Photochemical Rearrangements


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O interesse pelo relacionamento entre humanos e cães tem sido crescentemente refletido em produções científicas, apesar destas ainda se mostrarem incipientes no contexto latino-americano, e, por conseguinte, no brasileiro. Nestes termos, quando se toma como foco o relacionamento específico entre cães e pessoas em situação de rua, a incipiência se mostra ainda mais notória, apesar de se tratar de fenômeno que abarca questões interessantes, tanto de cunho individual quanto social e de políticas públicas. Diante disto, a realização do presente estudo se justificou por contribuir com a elucidação da temática, haja vista que teve por objetivo geral: investigar, apontar e compreender relacionamentos estabelecidos por pares que se caracterizem por pertencerem às espécies em questão e por fazerem das ruas espaços para estabelecimento de suas rotinas. Sendo estes critérios de seleção de participantes somados a idade mínima de 18 anos, foram entrevistadas 12 pessoas que nas ocasiões se encontravam em logradouros públicos dos municípios de Vitória, Serra e Vila Velha. Para guiar as entrevistas, foi utilizado roteiro semiestruturado com o intuito de coletar: dados sociais e econômicos dos participantes; conhecer aspectos dos relacionamentos interpessoais dos participantes; acessar relatos que dissessem respeito a partes das histórias de vida de moradores de rua que envolvessem relacionamento com cães; e por fim, recolher informações acerca do uso de serviços de assistência à população de rua, seja na presença ou na ausência do(s) cão(es). Em adição, foram utilizados dados provenientes de conversa informal e voluntária entre a pesquisadora e três funcionárias do Serviço Especializado em Abordagem Social do município de Vitória. A partir daí, os dados coletados foram organizados em cinco grandes itens, nos quais foram detalhadamente analisados e discutidos. Estes itens são: Caracterização sociodemográfica e econômica dos participantes; Caracterização geral dos relacionamentos; Concepções dos participantes acerca dos cães em suas vidas; Repercussões individuais e sociais do relacionamento; e “Sobre pessoas em situação de rua e cães: o "último vínculo"?”. Diante da análise destes, então, tornou-se possível inferir que o relacionamento entre humanos e cães, apesar de manter semelhanças que, por vezes, fazem com que sejam comparados ou equiparados a amizades ou a relacionamentos familiares, se trata de um tipo a parte. Além disto, quando o humano do par homem-cão se encontra em situação de rua, algumas peculiaridades se fazem bastante evidentes, dentre as quais a dificuldade de afastamento do animal, quando em situações momentâneas (por exemplo, em ocasiões de deslocamentos pelas cidades) ou duradouras (como quando por motivos de idas a instituições de abrigamento), em que não é possível tê-lo junto. Por fim, aponta-se como ponderável a recorrente colocação de que o cão seria o único e/ou último vínculo da pessoa em situação de rua com que convive, já que não raramente os participantes mencionaram rearranjos relacionais com humanos posteriores ao início da situação em questão.

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O objetivo principal deste trabalho foi o estudo do transporte atmosférico de PM10 e SO2 em regiões costeiras urbanas usando modelos WRF/CMAQ. Duas regiões foram contempladas neste estudo. Uma é a Região da Grande Vitória (RGV), no estado do Espírito Santo, Brasil; a outra é a Região da Grande Dunkerque (RGD), no Departamento Nord Pas-de-Calais, França. A RGV é cercada por uma cadeia de montanhas paralela à costa, resultando num topografia complexa e acidentada. Já a RGD possui uma topografia muito mais suave. As entradas de dados para os modelos WRF/CMAQ englobaram o inventário de emissões de poluentes atmosféricos do IEMA-ES para a RGV, e o inventário de emissões no nível do solo de Nord Pas-de-Calais denominado ―Cadastre_totaux_3km_A2008 _M2010_V2_SNAPN2‖ para a RGD. Ambos os inventários apresentaram restrições, todavia. O inventário da RGV apresentou valores de ressuspensão em vias de tráfego elevados, em comparação com diversos estudos, e teve esses dados modificados. Os dados no nível do solo e a grande área de das células da grade (9 km2) do inventário da RGD não permitiram resultados satisfatórios de modelagem. A validação dos modelos foi realizada por comparação com resultados obtidos em duas campanhas experimentais: uma na cidade de Dunkerque, no norte da França, em setembro de 2009; a outra na cidade de Vitória, no sudeste do Brasil, em julho de 2012. Esses dados foram obtidos pelo uso de sistemas de Light Detection and Ranging (LIDAR) e Sonic Detection and Ranging (SODAR), bem como de Estações Meteorológicas de Superfície (EMS) e de monitoramento atmosférico. Os resultados deste trabalho mostraram que: a) existe uma necessidade de melhorias contínuas nos inventários regionais de emissões, adaptando-os para condições locais específicas e focando na obtenção de parâmetros necessários para modelagem fotoquímica; b) os valores de módulo e direção das velocidades obtidas na modelagem meteorológica influenciam fortemente os resultados da modelagem de concentração de poluentes; c) a qualidade do ar tanto na RGV quanto na RGD merece atenção, sobretudo no que diz respeito às concentrações de MP10. De acordo com os dados das estações de monitoramento, a situação parece mais crítica na RGD; d) a modelagem da RGV apresentou resultados mais satisfatórios do que a da RGD, de acordo com os resultados das validações; e) a entrada da brisa do mar provocou alterações significativas na concentração dos poluentes, o que pôde ser observado na análise da dinâmica da dispersão de MP10 e SO2. Esse fenômeno foi mais marcante na RGV, onde a entrada da brisa marítima provocou um movimento oscilatório na pluma de poluição, levando-a para os bairros mais densamente povoados do conglomerado urbano. Na RGD, a entrada da brisa não foi cotidiana e, no dia em que ela aconteceu, houve uma alteração de quase 180º na direção do movimento da pluma de poluição. Além do aumento da turbulência vertical, o qual já foi estudado por diversos autores, este estudo focou também na influência brisa do mar na dinâmica da pluma de dispersão de poluentes atmosféricos em regiões costeiras.

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ABSTRACT Sorghum arundinaceum (Desv.) Stapf is a weed that belongs to the Poaceae family and is widespread throughout Brazil. Despite the frequent occurrence, infesting cultivated areas, there is little research concerning the biology and physiology of this species. The objective of this research was to evaluate the growth, carbon partitioning and physiological characteristics of the weed Sorghum arundinaceum in greenhouse. Plants were collected at regular intervals of seven days, from 22 to 113 days after transplanting (DAT). In each sample, we determined plant height, root volume, leaf area and dry matter, and subsequently we perfomed the growth analysis, we have determined the dry matter partitioning among organs, the accumulation of dry matter, the specific leaf area, the relative growth rate and leaf weight ratio. At 36, 78 and 113 DAT, the photosynthetic and transpiration rates, stomatal conductance, CO2 concentration and chlorophyll fluorescence were evaluated. The Sorghum arundinaceum reached 1.91 in height, with slow initial growth and allocated much of the biomass in the roots. The photosynthetic rate and the maximum quantum yield of FSII are similar throughout the growth cycle. At maturity the Sorghum arundinaceum presents higher values of transpiration rate, stomatal conductance and non-photochemical quenching coefficient (NPQ).

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Fluorescent protein microscopy imaging is nowadays one of the most important tools in biomedical research. However, the resulting images present a low signal to noise ratio and a time intensity decay due to the photobleaching effect. This phenomenon is a consequence of the decreasing on the radiation emission efficiency of the tagging protein. This occurs because the fluorophore permanently loses its ability to fluoresce, due to photochemical reactions induced by the incident light. The Poisson multiplicative noise that corrupts these images, in addition with its quality degradation due to photobleaching, make long time biological observation processes very difficult. In this paper a denoising algorithm for Poisson data, where the photobleaching effect is explicitly taken into account, is described. The algorithm is designed in a Bayesian framework where the data fidelity term models the Poisson noise generation process as well as the exponential intensity decay caused by the photobleaching. The prior term is conceived with Gibbs priors and log-Euclidean potential functions, suitable to cope with the positivity constrained nature of the parameters to be estimated. Monte Carlo tests with synthetic data are presented to characterize the performance of the algorithm. One example with real data is included to illustrate its application.

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O rearranjo [3,3]-sigmatrópico térmico (180ºC) de diferentes N-alil-N-sililoxi enaminas foi estudado. Os respectivos produtos de rearranjo (éteres de óxima) foram obtidos com rendimentos elevados (80%). A regiosselectividade, [3,3] vs [1,3], e a diastereosselectividade do processo foram elevadas, superior a 99% e aproximadamente 80%, respectivamente. Foi demonstrada a importância do grupo sililoxilo na promoção do rearranjo face a substratos sem este tipo de substituição. Posteriormente, foi estudada a possibilidade de aceleração aniónica deste tipo de rearranjo por formação de oxianião ligado ao átomo de azoto. A estratégia seguida para a formação do mesmo, consistiu na O-dessililação de diferentes N-alil-N-sililoxi enaminas tendo-se obtido as nitronas correspondentes ou produtos de ciclização. Num exemplo envolvendo um derivado de isoxazole-5-(2H)-ona foi observado um aumento de velocidade do rearranjo por reacção com ião etoxilo. Este aumento de velocidade foi atribuído à abertura de anel do N-O éster cíclico para o N-oxianião, seguida de rearranjo e posterior fecho. Métodos alternativos de aceleração do rearranjo por geração de carga positiva, parcial ou completa, no átomo de azoto levaram apenas à dessililação das N-alil-N-sililoxi enaminas. ABSTRACT - [3,3]-sigmatropic rearrangement of a variety of N-allyl-N-silyloxy enamines was studied. The corresponding rearrangement products (oxime-ethers) were obtained in high yields (80%). High regioselectivity, [3,3] vs [1,3] (> 99%) and in appropriate cases, diastereoselectivity (80%) were observed. The importance of the silyloxy group in promoting the rearrangement, in relation to substrates lacking this functionality, is underlined. The possible anionic acceleration of the rearrangements was next examined by O-desilylation the N-silyloxy group bonded to the nitrogen. Attempted generation of these species however, was found to lead either to the corresponding nitrones or to cyclization products. In one particular example involving an isoxazol-5-(2H)-one derivative rate enhancement of rearrangement was indeed observed with ethoxide ion. It is tentatively attributed to ring opening of the cyclic N-O ester to the N-oxyanion ethyl ester followed by rearrangement and subsequent reclosure. Alternative methods to accelerate the process by generating a partial or complete positive charge on the nitrogen atom led only to desilylation.

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Abstract - Recently, long noncoding RNAs have emerged as pivotal molecules for the regulation of coding genes' expression. These molecules might result from antisense transcription of functional genes originating natural antisense transcripts (NATs) or from transcriptional active pseudogenes. TBCA interacts with β-tubulin and is involved in the folding and dimerization of new tubulin heterodimers, the building blocks of microtubules. Methodology/Principal findings: We found that the mouse genome contains two structurally distinct Tbca genes located in chromosomes 13 (Tbca13) and 16 (Tbca16). Interestingly, the two Tbca genes albeit ubiquitously expressed, present differential expression during mouse testis maturation. In fact, as testis maturation progresses Tbca13 mRNA levels increase progressively, while Tbca16 mRNA levels decrease. This suggests a regulatory mechanism between the two genes and prompted us to investigate the presence of the two proteins. However, using tandem mass spectrometry we were unable to identify the TBCA16 protein in testis extracts even in those corresponding to the maturation step with the highest levels of Tbca16 transcripts. These puzzling results led us to re-analyze the expression of Tbca16. We then detected that Tbca16 transcription produces sense and natural antisense transcripts. Strikingly, the specific depletion by RNAi of these transcripts leads to an increase of Tbca13 transcript levels in a mouse spermatocyte cell line. Conclusions/Significance: Our results demonstrate that Tbca13 mRNA levels are post-transcriptionally regulated by the sense and natural antisense Tbca16 mRNA levels. We propose that this regulatory mechanism operates during spermatogenesis, a process that involves microtubule rearrangements, the assembly of specific microtubule structures and requires critical TBCA levels.

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The organotin(IV) compounds [Me2Sn(L)(2)] (1), [Et(2)sn(L)(2)] (2), [(Bu2Sn)-Bu-n(L)(2)] (3), [(n)Oct(2)Sn(L)(2)] (4), [Ph2Sn(L)(2)] (5), and [PhOSnL](6) (6) have been synthesized from the reactions of 1-(4-chlorophenyl)-1-cyclopentanecarboxylic acid (HL) with the corresponding diorganotin(IV) oxide or dichloride. They were characterized by IR and multinuclear NMR spectroscopies, elemental analysis, cyclic voltammetry, and, for 2, 3, 4 and 6, single crystal X-ray diffraction analysis. While 1-5 are mononuclear diorganotin (IV) compounds, the X-ray diffraction of 6 discloses a hexameric drumlike structure with a prismatic Sn6O6 core. All these complexes undergo irreversible reductions and were screened for their in vitro antitumor activities toward HL-60, BGC-823, Bel-7402, and KB human cancer cell lines. Within the mononuclear compounds, the most active ones (3, 5) are easiest to reduce (least cathodic reduction potentials), while the least active ones (1, 4) are the most difficult to reduce. Structural rearrangements (i.e., Sn-O bond cleavages and trans-to-cis isomerization) induced by reduction, which eventually can favor the bioactivity, are disclosed by theoretical/electrochemical studies.

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New strategies to reduce the environmental and economic costs of pesticides use are currently under study. Microencapsulation has been used as a versatile tool for the production of controlled release agricultural formulations. In this study, the photochemical degradation of the herbicides MCPA and mecoprop has been investigated in different aqueous media such as ultrapure and river water under simulated solar irradiation. To explore the possibility of introducing cyclodextrins in the herbicide formulations, the photodegradation study of the inclusion complexes of MCPA and mecoprop with (2-hydroxypropyl)-β-cyclodextrin (HP-β-CD) was also performed. The half-lives of MCPA and mecoprop inclusion complexes were increased approximately by a factor of three related to the free molecules. Additionally, it has been shown that the photodegradation of MCPA and mecoprop is influenced by their structural features. The additional methyl group existing in mecoprop molecular structure has a positive influence on the stabilization of the radical intermediate formed in the first stage of photodegradation of both herbicides. The results found indicated that MCPA and mecoprop form inclusion complexes with HP-β-CD showing higher photostability compared to free herbicides indicating that HP-β-CD may serve as ingredient in these herbicide formulations.

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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.

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Dynamically reconfigurable systems have benefited from a new class of FPGAs recently introduced into the market, which allow partial and dynamic reconfiguration at run-time, enabling multiple independent functions from different applications to share the same device, swapping resources as needed. When the sequence of tasks to be performed is not predictable, resource allocation decisions have to be made on-line, fragmenting the FPGA logic space. A rearrangement may be necessary to get enough contiguous space to efficiently implement incoming functions, to avoid spreading their components and, as a result, degrading their performance. This paper presents a novel active replication mechanism for configurable logic blocks (CLBs), able to implement on-line rearrangements, defragmenting the available FPGA resources without disturbing those functions that are currently running.

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Fragmentation on dynamically reconfigurable FPGAs is a major obstacle to the efficient management of the logic space in reconfigurable systems. When resource allocation decisions have to be made at run-time a rearrangement may be necessary to release enough contiguous resources to implement incoming functions. The feasibility of run-time relocation depends on the processing time required to set up rearrangements. Moreover, the performance of the relocated functions should not be affected by this process or otherwise the whole system performance, and even its operation, may be at risk. Relocation should take into account not only specific functional issues, but also the FPGA architecture, since these two aspects are normally intertwined. A simple and fast method to assess performance degradation of a function during relocation and to speed up the defragmentation process, based on previous function labelling and on the application of the Euclidian distance concept, is proposed in this paper.

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Reconfigurable computing experienced a considerable expansion in the last few years, due in part to the fast run-time partial reconfiguration features offered by recent SRAM-based Field Programmable Gate Arrays (FPGAs), which allowed the implementation in real-time of dynamic resource allocation strategies, with multiple independent functions from different applications sharing the same logic resources in the space and temporal domains. However, when the sequence of reconfigurations to be performed is not predictable, the efficient management of the logic space available becomes the greatest challenge posed to these systems. Resource allocation decisions have to be made concurrently with system operation, taking into account function priorities and optimizing the space currently available. As a consequence of the unpredictability of this allocation procedure, the logic space becomes fragmented, with many small areas of free resources failing to satisfy most requests and so remaining unused. A rearrangement of the currently running functions is therefore necessary, so as to obtain enough contiguous space to implement incoming functions, avoiding the spreading of their components and the resulting degradation of system performance. A novel active relocation procedure for Configurable Logic Blocks (CLBs) is herein presented, able to carry out online rearrangements, defragmenting the available FPGA resources without disturbing functions currently running.

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Dissertation presented at Faculdade de Ciências e Tecnologia of Universidade Nova de Lisboa to obtain the Degree of Master in Chemical and Biochemical Engineering

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Dissertação apresentada para obtenção do grau de Doutor em Bioquímica - especialidade Biotecnologia, pela Universidade Nova de Lisboa,Faculdade de Ciências e Tecnologia

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Lesions observed in chronic chagasic cardiopathy frequently produce electrocardiographic alterations and affect cardiac function. Through a computerized morphometrical analysis we quantified the areas occupied by cardiac muscle, connective and adipose tissues in the right atrium of dogs experimentally infected with Trypanosoma cruzi. All of the infected dogs showed chronic myocarditis with variable reduction levels of cardiac muscle, fibrosis and adipose tissue replacement. In the atrial myocardium of dogs infected with Be78 and Be62 cardiac muscle represented 34 and 50%, fibrosis 28 and 32% and adipose tissue 38 and 18%, respectively. The fibrosis observed was both diffuse and focal and mostly intrafascicular, either partially or completely interrupting the path of muscle bundles. Such histological alterations probably contributed to the appearance of electrocardiographic disturbances verified in 10 out 11 dogs which are also common in human chronic chagasic cardiopathy. Fibrosis was the most important microscopic occurrence found since it produces rearrangements of collagen fibers in relation to myocardiocytes which causes changes in anatomical physiognomy and mechanical behavior of the myocardium. These abnormalities can contribute to the appearance of cardiac malfunction, arrythmias and congestive cardiac insufficiency as observed in two of the analyzed dogs. Strain Be78 caused destruction of atrial cardiac muscle higher than that induced by strain Be62.