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Adaptive filters play an important role in the fields related to digital signal processing and communication, such as system identification, noise cancellation, channel equalization, and beamforming. In practical applications, the computational complexity of an adaptive filter is an important consideration. The Least Mean Square (LMS) algorithm is widely used because of its low computational complexity (O(N)) and simplicity in implementation. The least squares algorithms, such as Recursive Least Squares (RLS), Conjugate Gradient (CG), and Euclidean Direction Search (EDS), can converge faster and have lower steady-state mean square error (MSE) than LMS. However, their high computational complexity ($O(N^2)$) makes them unsuitable for many real-time applications. A well-known approach to controlling computational complexity is applying partial update (PU) method to adaptive filters. A partial update method can reduce the adaptive algorithm complexity by updating part of the weight vector instead of the entire vector or by updating part of the time. An analysis for different PU adaptive filter algorithms is necessary and meaningful. The deficient-length adaptive filter addresses a situation in system identification where the length of the estimated filter is shorter than the length of the actual unknown system. It is related to the partial update adaptive filter, but has different performance. It can be viewed as a PU adaptive filter, in that the deficient-length adaptive filter also updates part of the weight vector. However, it updates the same part of the weight vector for each iteration, while the partial update adaptive filter updates a different part of the weight vector for each iteration. In this work, basic PU methods are applied to the adaptive filter algorithms which have not been fully addressed in the literature, including CG, EDS, and Constant Modulus Algorithm (CMA) based algorithms. A new PU method, the selective-sequential method, is developed for LSCMA. Mathematical analysis is shown including convergence condition, steady-state performance, and tracking performance. Computer simulation with proper examples is also shown to further help study the performance. The performance is compared among different PU methods or among different adaptive filtering algorithms. Computational complexity is calculated for each PU method and each adaptive filter algorithm. The deficient-length RLS and EDS are also analyzed and compared to the performance of the PU adaptive filter. In this dissertation, basic partial-update methods are applied to adaptive filter algorithms including CMA1-2, NCMA, Least Squares CMA (LSCMA), EDS, and CG. A new PU method, the selective-sequential method, is developed for LSCMA. Mathematical derivation and performance analysis are provided including convergence condition, steady-state mean and mean-square performance for a time-invariant system. The steady-state mean and mean-square performance are also presented for a time-varying system. Computational complexity is calculated for each adaptive filter algorithm. Numerical examples are shown to compare the computational complexity of the PU adaptive filters with the full-update filters. Computer simulation examples, including system identification and channel equalization, are used to demonstrate the mathematical analysis and show the performance of PU adaptive filter algorithms. They also show the convergence performance of PU adaptive filters. The performance is compared between the original adaptive filter algorithms and different partial-update methods. The performance is also compared among similar PU least-squares adaptive filter algorithms, such as PU RLS, PU CG, and PU EDS. Deficient-length RLS and EDS are studied. The performance of the deficient-length filter is also compared with the partial update filter. In addition to the generic applications of system identification and channel equalization, two special applications of using partial update adaptive filters are also presented. One application is using PU adaptive filters to detect Global System for Mobile Communication (GSM) signals in a local GSM system using the Open Base Transceiver Station (OpenBTS) and Asterisk Private Branch Exchange (PBX). The other application is using PU adaptive filters to do image compression in a system combining hyperspectral image compression and classification. Overall, the PU adaptive filters can usually achieve comparable performance to the full-update filters while reducing the computational complexity significantly. The PU adaptive filters can achieve similar steady-state MSE to the full-update filters. Among different PU methods, the MMax method has a convergence rate very close to the full-update method. The sequential and stochastic methods converge slower than the MMax method. However, the MMax method does not always perform well with the LSCMA algorithm. The sequential LSCMA has the best performance among the PU LSCMA algorithms. The PU CMA may perform better than the full-update CMA in tracking a time-varying system. The MMax EDS can converge faster than the MMax RLS and CG. It can converge to the same steady-state MSE as the MMax RLS and CG, while having a lower computational complexity. The PU LMS and PU EDS can also perform a little better in a system combining hyperspectral image compression and classification. / Ph. D.

This work describes and implementing method for volume data rendering. Main purpose of this work is visualization of scanned 3D data with some current method used for the 3D volumetric scanning. The 3D volumetric scanning is mainly used in medicine and chemistry. System is using programmable pipeline of current graphic cards, which provides us fast parallel work with large volumetric data. This paper introduces some basics about the volumetric rendering and scanning, describes design and at the end, the implementation steps. Result of this project is application which renders volumetric data with OpenGL.

La résistance multi-drogue (MDR) est un facteur majeur de l'échec partiel de nombreuses chimiothérapies anticancéreuses, antiparasitaires ou antibactériennes. Dans le but d’inhiber ce phénomène, de nouvelles molécules au pouvoir reversant ont été découvertes. Ainsi une série de molécules, basée sur un squelette pyrido[3,2-g]quinoléine, portant différentes chaînes alkylamines et diversement substituées sur le motif hétérocyclique, a été synthétisée et montré in vitro une activité reversante de la résistance multiple aux médicaments. Afin de démontré le processus suivi par une molécule biologiquement active de sa synthèse à sa mise en forme galénique, le 4,6-Bis[2’(diéthylamino)éthoxy]2,8,10-triméthylpyrido[3,2-g]quinoléine (BG 637) a été choisi. Nous avons procédé dans un premier temps à la caractérisation physicochimique du BG 637 par des techniques telles que l’analyse calorimétrique différentielle (DSC), la spectroscopie UV-VIS, la spectrométrie de masse (CG/SM) couplée à la chromatographie de gaz, la spectroscopie Infra Rouge à Transformée de Fourrier (IRTF), la résonance magnétique nucléaire (RMN), la diffraction aux rayons X et la cristallographie. Des études stabilité ont également été menées sous différentes conditions de stockage. Des études d’interactions entre différents excipients et le BG 637 ont été réalisées et analysées par DSC, IRTF et UV. Les résultats ont montré que le BG 637 est un composé stable et compatible avec les excipients choisis. Enfin, la mise en forme galénique orale, le comprimé, a été réalisée. / Multi-drug resistance represent a major problem for chemotherapy unsuccessful in oncology, parasitoly and bacteriology. The new molecules which reverse this phenomenon were discovered.The pyrido[3,2-g]quinolines family which are substituted by various alkylamine side chains and various substituents on the heterocyclic moiety was prepared and the in vitro activity against the multi-drug resistance was showed.With the aim to show the processes of the new biological compound from his synthesis to the galenic form, the 4,6-Bis[2’(diéthylamino)éthoxy]2,8,10-triméthylpyrido[3,2-g]quinoline (BG 637) was chosen. To characterize BG 637, techniques such as Differentiel Scanning Calorimetry (DSC), Fourier Transform Infrared spectrometry (FT-IR), Ultra Violet spectrometry (UV), Mass spectrometry (GC/MS) coupled with Gas Chromatography, Nuclear Magnetic Resonance (NMR) and X-Ray Powder Diffraction (XRPD) were used. Several of them were also used to show the stability of the drug during various storage conditions.DSC supported by FT-IR and UV were used as the screening techniques for assessing the compatibility of BG 637 with several commonly used pharmaceutical excipients. These results showed that BG 637 is a very stable compound and compatible with several pharmaceutical excipients. Finally, the appropriate formulation for direct compression was determined.

A preocupação com os danos provocados à saúde do trabalhador rural e ao meio ambiente devido ao uso indiscriminado de agrotóxicos tem aumentado nos últimos anos. O uso generalizado e intensivo destas substâncias tem gerado diversos problemas relacionados à saúde pública e ao desequilíbrio ambiental, incluindo: intoxicações de agricultores, contaminação de alimentos, água e solos. O tomate é hoje, uma hortaliça bastante conhecida e de elevado consumo no mundo. Sua cultura é bastante afetada por quebras de rendimento e depreciação da qualidade de matéria- prima, em razão da ocorrência de doenças, pragas e estresses abióticos. Apesar da preocupação com o monitoramento dos resíduos de agrotóxicos nos alimentos, poucas metodologias analíticas podem alcançar resultados de alta qualidade simultaneamente para uma gama extensiva de agrotóxicos. No presente estudo, foi desenvolvida e validada a metodologia de análise de multirresíduos QuEChERS (quick, easy, cheap, effective, rugged, and safe) para quantificação de resíduos de agrotóxicos em tomate. Este método provê resultados de forma rápida, fácil, com custo acessível e com alta qualidade. Foram analisados agrotóxicos utilizados principalmente no controle de insetos, sendo: buprofezina, carbofurano, \'alfa\'-endossulfam, \'beta\'-endossulfam, sulfato de endossulfam e monocrotofós. Para isso, realizou-se a fortificação do tomate, previamente homogeneizado, com soluções contendo os agrotóxicos em 3 níveis de fortificação (0,0625; 0,25 e 1,00 mg/Kg). A purificação dos extratos foi realizada através de clean-up dispersivo, e em seguida os extratos foram analisados por CG-EM modo SIM. Neste estudo avaliaram-se os seguintes parâmetros de validação do método: linearidade da curva analítica, sensibilidade, limite de detecção (LD), limite de quantificação (LQ), o efeito matriz, bem como a precisão e a exatidão (em termos de percentual de recuperação). A faixa linear de concentração das curvas analíticas situou-se entre 0,25 a 4,0 ng.\'mü\'L-1 com valores de r2 maiores que 0,99 (na matriz). A técnica CG-EM modo SIM promoveu a quantificação (critérios de recuperação entre 70 e 120% e valores de CV% menores que 20%) de todos os agrotóxicos estudados. Portanto, conclui-se que o método mostrou-se adequado às análises multirresíduos dos agrotóxicos em tomate, apresentando sensibilidade e seletividade adequadas, e todos os parâmetros de validação encontram-se de acordo com os limites sugeridos para validação de métodos cromatográficos. Foram coletadas amostras (n=33) em varejões na cidade de Piracicaba e os níveis residuais de agrotóxicos apresentaram-se abaixo dos limites de detecção para os produtos analisados. Os produtos acefato, deltametrina, difenoconazole e fenpropatrina foram avaliados no sistema CG-EM e não apresentaram sensibilidade e seletividade nas condições cromatográficas aplicadas. A implementação de novos métodos cromatográficos para análise de resíduos de agrotóxicos em alimentos devem ser fomentados para contribuir com o monitoramento eficiente, visando avaliar a qualidade e segurança dos alimentos consumidos pela população, caracterizar as fontes de contaminação e proporcionar uma avaliação quanto ao uso inadequado e não autorizado dos agrotóxicos / The concernment about the damage caused to the health of rural workers and the environment due to indiscriminate use of pesticides has increased in recent years. The commonly and intensive use of these substances has created several problems related to public health and environmental disequilibrium, including poisoning of farmers, contamination of food, water and soil. Nowadays, the tomato is a well known vegetables and high consumption in the world. Its culture is highly affected by loss of yield and depreciation of the quality of raw material, due to the occurrence of diseases, pests and abiotic stresses. Considering the concernment about the monitoring of pesticide residues in food, few analytical methods can achieve high quality results for both a wide range of pesticides. In this study, was developed and validated the methodology of multiresidue analysis QuEChERS (quick, easy, cheap, effective, rugged, and safe) for quantification of residues of pesticides in tomatoes. This method provides results quick, easy, inexpensive and high quality. Were analyzed mainly pesticides used to control insects, are: buprofezina, carbofuran, \'alfa\'-endossulfam, \'beta\'- endossulfam, sulphate endossulfam and monocrotophos. Then, performed a spiking of tomatoes homogenized previously, with solutions containing pesticides, in 3 of fortification levels (0.0625, 0.25 and 1.00 mg/kg). The purification of the extracts was performed by dispersive clean-up, and then the extracts were analyzed by GC-MS using SIM mode. This study evaluated the following parameters for validation of the method: linearity, sensitivity, limit of detection (LOD), limit of quantification (LOQ), matrix effect, precision and accuracy (in terms of percentage of recovery). The linear range of concentration of the analytical curves was between 0.25 to 4.0 ng.\'mü\'L-1 with r2 values of greater than 0.99 (in the matrix). The technique GC-MS SIM mode promoted quantification (criteria of recovery between 70 and 120% and RSD% values of less than 20%) of all pesticides studied. Therefore, concluded that the method proved to be appropriate for multiresidue analysis of pesticides in tomatoes, showing sensitivity and selectivity adequate, and all parameters of validation are according with the limits suggested for validation of chromatographic methods. Samples were collected (n = 33) in the Piracicaba city in local market and the levels of pesticide residues were below the limits of detection for the products analyzed. The products acephate, deltamethrin, difenoconazole and fenpropathrin were evaluated in the GC-MS and showed no sensitivity and selectivity in the chromatographic conditions applied. The implementation of new chromatographic methods for analysis of pesticide residues in food should be encouraged to contribute to efficient monitoring to evaluate the quality and safety of food consumed by the population, identify the sources of contamination and provide an assessment as to the misuse and use unauthorized pesticides

Os extratos vegetais amazônicos para uso em beneficiamento têxtil podem ser uma alternativa sustentável e ecológica em relação às atuais matérias-primas utilizadas pelo mercado. Este estudo teve como objetivo efetuar a caracterização físicoquímica de extratos vegetais amazônicos (óleo-resina de copaíba, óleo de castanha do Brasil, óleo de buriti, manteiga de cacau, manteiga de tucumã e manteiga de cupuaçu), preparar emulsões e realizar aplicações preliminares destas em têxteis. A caracterização físico-química foi realizada através das técnicas instrumentais analíticas de espectroscopia de infravermelho por transformada de Fourrier (FTIR) e cromatografia a gás com detecção por ionização de chama (CG-FID). Além disso, foi realizada a determinação do Equilíbrio Hidrófilo-Lipófilo (EHL) das emulsões preparadas a partir dos extratos estudados; seleção da emulsão mais estável por extrato para aplicação por foulardagem; avaliação da oxidação das emulsões aplicadas sobre o material têxtil em diferentes temperaturas (120 a 200ºC); e avaliação sensorial de toque proporcionado pelas emulsões em comparação a um amaciante de uso industrial. Os principais resultados foram que o óleo de castanha do Brasil e as manteigas de cacau, tucumã e cupuaçu apresentaram resultados próximos nas análises por FTIR; a distribuição graxa por cromatografia a gás mostrou-se útil para a caracterização destes extratos vegetais; os valores de referência de EHL para os extratos analisados foram de 7,51 a 10,72 e estão de acordo com a literatura científica (de 6 a 12); os extratos estudados emulsionados nas condições do estudo não possuem tendência à oxidação por temperatura; as médias globais das análises sensoriais de toque indicam um resultado inferior ao padrão comercial, porém, as manteigas de cacau, cupuaçu e o óleo de castanha do Brasil apresentaram os melhores resultados, com notas entre 2,8 e 2,9 (numa escala de 1 a 5). Assim, nota-se que, os resultados obtidos podem ser utilizados como base para pesquisas futuras no sentido de melhorar as formulações das emulsões para a produção de amaciantes ou outros produtos / The Amazonian plant extracts for use in textile processing can be a sustainable and environmentally friendly alternative to the current raw materials used by the market. This study aimed to make the physicochemical characterization of Amazonian plant extracts (copaiba oleoresin, Brazil nut oil, buriti oil, cocoa butter, tucumã butter and cupuaçu butter), prepare emulsions and perform preliminary applications in textile. The physicochemical characterization was performed by analytical instrumental techniques, such as FTIR spectroscopy and gas chromatography with FID detection (GC-FID). Furthermore, the determination of the Hydrophile-Lipophile Balance (HLB) was performed of the emulsions prepared from the extracts studied; the emulsion more stable for selection extract for application by padding; evaluation of the oxidation of emulsions applied to the textile material at different temperatures (120 to 200C); and sensory evaluation provided by the touch emulsions compared to a industrial softener. The main results were that the Brazil nut oil and cocoa, tucumã and cupuaçu butters showed similar results in the analysis by FTIR; grease distribution by gas chromatography proved to be useful for the characterization of plant extracts; the HLB values for the reference analyzed the extracts were 7.51 to 10.72 are consistent with the literature (6 to 12); the extracts studied emulsified in the study conditions have no tendency to oxidation temperature; the global average of sensory analysis touch indicate somewhat lower than the commercial standard, however, cocoa and cupuaçu butter and Brazil nut oil showed the best results, with grades between 2.8 and 2.9 (on a scale of 1 to 5). Thus, it is noted that the results obtained can be used as the basis for further research in order to improve the formulations of emulsions for the production of fabric softeners or other products

Os hormônios tireoidianos estão envolvidos em vários efeitos regulatórios, em órgãos diversos. Suas variações no organismo estão relacionadas a quadros clínicos de grande relevância. A presente dissertação trata do estudo de duas proteínas diretamente relacionadas ao complexo sistema regulatório associado a tais hormônios. A primeira delas é a globulina de ligação à tiroxina (TBG), responsável pelo transporte da grande maioria dos hormônios tireoidianos circulantes, e cujas alterações estão relacionadas a falhas na interpretação de testes de avaliação da função tireoidiana, podendo levar a tratamentos desnecessários. A segunda proteína é o receptor tireoidiano (TR), responsável pela mediação dos efeitos regulatórios do hormônio tireoidiano, tendo sua estimulação de atividade transcricional relacionada à ligação do hormônio em um de seus domínios. A TBG foi estudada através da técnica computacional conhecida como modelagem molecular por homologia, aplicada à proteína em sua forma selvagem e a mutantes observados no Brasil, com o intuito de relacionar a inviabilidade de tais mutantes a aspectos estruturais. Foi proposto que, para dois dos mutantes estudados, a formação das estruturas secundárias como na forma nativa da proteína seria inviável, enquanto que para o terceiro mutante a inviabilidade poderia ser causada por enovelamento incorreto causado por uma possível interação entre um resíduo de cisteína adveniente da mutação e outros resíduos do mesmo aminoácido em posição fisicamente próxima. O estudo do TR teve como base as estruturas cristalográficas das duas isoformas humanas do receptor (hTR α e hTR β) quando ligadas ao tiromimético GC-1. Esse composto tem a propriedade de ligar-se preferencialmente à isoforma β, o que pode ter interessantes aplicações farmacológicas. A análise comparativa da ligação do GC-1 às duas isoformas mostrou que, para tal composto, a seletividade se deve a mudanças consideráveis no modo de ligação ao hTR α e hTR β. Para a isoforma , há dois modos de ligação, envolvendo conformações alternativas de ligante e proteína, onde em uma delas a ligação é mais favorável e semelhante à ligação do composto à isoforma , enquanto no outro modo de ligação há a perda de uma interação direta entre composto e proteína, explicando a mais baixa afinidade do GC-1 à isoforma quando comparado à isoforma . O mecanismo de -seletividade para esse composto está relacionado a um átomo de oxigênio específico que não existe no ligante natural do receptor, o que fornece úteis informações para a criação de novos compostos. / The thyroid hormones are involved in various regulatory effects, on diverse organs. Their fluctuations on the body are related to clinical scenarios of great relevance. This work deals with the study of two proteins which are directly related to the regulatory system associated to these hormones. The first one is the thyroxine-binding globulin (TBG), responsible for the transport of a large part of the thyroid hormones in serum, and whose variations are related to misinterpretation of thyroid function tests. The second protein is the thyroid receptor (TR), responsible for the mediation of the thyroid hormone regulatory effects . the transcriptional activity being related to ligand binding to one of the protein domains. The wild-type TBG and three mutants discovered in Brazil were studied by the computational technique known as homology modeling. The purpose of this investigation was to relate protein unviability to structural aspects. It was proposed that, for two mutants, the unviability was related to the impossibility of secondary structure formation as needed to form the native folding, while the third mutant the cause could be the formation of an incorrect folding due to possible interactions involving a cysteine residue created by the mutation and other nearby cysteine residues. The thyroid receptor was studied in the light of the x-ray structures of the two isoforms of the protein (hTR α and hTRβ) bound to GC-1, a synthesized compound which resembles the thyroid hormones. This ligand binds preferably the isoform, a feature that may have interesting pharmacological applications. The comparative analysis of GC-1 binding to the two isoforms allowed the construction of a structural basis of its -selectivity property, which is due to considerable differences in the binding modes for the two isoforms. This involves two different configurations of ligand and protein conformations for the isoform - on one of them, the ligand docks to the molecule the same way it docks to hTRβ, while on the second configuration it loses one direct interaction to the protein, explaining its lower affinity to hTR α when compared to hTRβ. The -selectivity mechanism for this compound is related to a specific oxygen atom which doesn?t exist on the receptor endogenous ligand, providing useful information for the development of new compounds.

Hegel führt die traditionelle formale Logik, wie sie in Kants Konzept der reinen allgemeinen Logik ihre für ihn abschließende Gestalt erfahren hat, innerhalb seiner Systematik auf die Psychologie der produktiven Einbildungskraft und des Denkens zurück. Kants Konzeption der transzendentalen Logik, und mit ihr die neuzeitliche Erkenntnistheorie, wird aus gesamtsystematischer Hinsicht in der Philosophie des subjektiven Geistes verortet, und insbesondere in der Phänomenologie des Geistes und der Psychologie der Anschauung und Vorstellung. In logischer Hinsicht leistet Kant nach Hegel nur eine Übersetzung phänomenologischer Inhalte der psychologischen Vorstellung in relativ unterentwickelte und isolierte objektivlogische Strukturen (reine Reflexions- und wesentliche Verhältnisbestimmungen), wodurch er über den psychologischen Reflex des Begriffs nicht hinauskommt. Der logische Inhalt bzw. der objektive Gedanke dagegen basiert in seiner formalen Dimension auf die Realisierung des Begriffs im Prozess der endlichen Teleologie, aus deren Perspektive auch phänomenologische und logische Dimensionen von Struktur- und Verhältnisbestimmungen differenziert werden können (Inhalte der kontemplative Erwägung der Konstruktionsbedingungen des unausgeführten subjektiven Zwecks im ersten Fall, Funktionalität von Strukturverhältnissen im Prozess der Ausführung des subjektiven Zwecks im zweiten Fall). Der logische Inhalt ist konkret im Vergleich zum phänomenologischen Inhalt der psychologischen Vorstellung und abstrakt im Vergleich zum realsystematischen Inhalt als Korrelat der absoluten Methode. / Within his system Hegel relegates traditional formal logic, as it found its fulfillment in Kant´s concept of pure general logic, to the psychology of productive imagination and thought. Kant´s conception of transcendental logic, and with it a modern epistemological standpoint more generally, is also allocated in the philosophy of subjective spirit, and more specifically in the phenomenology and the psychology of intuition and representation. From a logical standpoint Kant does not, according to Hegel, go beyond translating phenomenological contents of the psychological representation into the relatively simple structures of the determinations of reflection and essential relations, thereby staying within the realm of the mere psychological reflex of the concept. Determinate logical content or objective thought on the contrary is based in its formal dimension on the actualization of the concept in the process of finite teleology. From this perspective it is possible to coherently distinguish between phenomenological and logical dimensions of structural and relational determinations (contents of the contemplative assessment of the conditions of construction of the yet unexecuted subjective finite end on the one hand, functionality of structural relations in the process of executing this end on the other). The logical content is concrete compared to the phenomenological one and abstract compared to the content of the real parts of the system as the correlate of absolute logical method.

A literatura relata variações espaciais e rítmicas para diferentes classes de metabólitos secundários, entretanto os dados são consistentes apenas para espécies que ocorrem em áreas temperadas. Lychnophora ericoides Mart. tem sido muito empregada popularmente como antiinflamatório e analgésico. É relatado o uso de suas partes aéreas pela população que vive nas proximidades de seu habitat em tratamentos de lesões cutâneas. L. eriocides representa uma das várias espécies da família Asteraceae endêmicas ao cerrado que biossintetizam uma ampla gama de terpenoides. Embora pouco estudada, sabe-se que a fração volátil de suas partes aéreas apresenta constituição terpênica. O presente estudo tem como objetivo determinar a constituição química desta fração volátil por meio de técnicas brandas de pré-concentração dos analitos e avaliar a variabilidade química desta fração a nível intraespecífico e temporal. Dessa forma, as coletas foram realizadas durante um período de 15 meses e utilizou-se HSSPME e CG-EM para avaliar as amostras coletadas. Um método para pré-concentração dos compostos voláteis (COVs) foi desenvolvido a partir da otimização dos parâmetros para obtenção do equilíbrio termodinâmico em HS-SPME. A obtenção de cromatogramas, determinação de índices de retenção relativos e aquisição de espectros de massas com ionização por elétrons possibilitaram a identificação de 7 monoterpenos majoritários e 1 sesquiterpeno também majoritário. Foi detectada a presença de um sesquiterpeno em amostras analisadas por HS-SPME que não se faz presente, de forma majoritária, nos óleos essenciais. Foram também realizados processos de hidrodestilação para obtenção dos óleos essenciais. A partir dos óleos essenciais foi possível isolar 3 sesquiterpenos por meio de CCDP e, para duas dentre estas substâncias, foram adquiridos dados de IES-EM, IES-EM/EM e RMN uni e bidimensionais. Um sesquiterpeno inédito na literatura, o acetato de bisabolila, teve sua estrutura elucidada por meio dos espectros adquiridos a partir de material isolado. Este sesquiterpeno, que está presente em preparados hidroalcoólicos utilizados na medicina popular, foi submetido a ensaios para avaliação do potencial anti-nociceptivo in vitro utilizando-se macrófagos peritoneais de ratos Wistar. Os resultados sugerem um efeito analgésico, devido à redução dos mediadores IL-1X e TNF-Y, os quais estão envolvidos no processo da dor inflamatória. É possível observar uma uniformidade intraespecífica nos níveis de COVs e uma tendência de comportamento a nível intraplanta e a nível circadiano de apresentar percentuais mais elevados de sesquiterpenos em épocas chuvosas e quentes (verão) e, analogamente, menos elevados em períodos de menor temperatura ambiente (durante a noite). Nas folhas mais jovens há uma têndencia destes valores relativos serem mais elevados / Literature does report spatial and time-scale shifting on several secondary metabolites, despite such data are relevant just for those species which occurs within a temperate clime region. Lychnophora ericoides Mart. has been widely used as a folk medicine against pain and inflammation process. Off the region where is located L. ericoidess habitat there is an evident and extensive use of its aerial parts by the people which live there in order to treat several types of skin wound. In Brazilian Cerrado, tropical savanna, there a large numbers of endemic Asteraceae species, including L. ericoides, which are capable of biosynthesizing a wide variety of terpenoids. Considering the poor number of studies carried out concerning the L. ericoides volatile fraction it can be said that this fraction is quite formed by different classes of terpenes. This work aims to find the chemical composition of L. ericoides volatile fraction by using soft pre concentration techniques of compounds and investigate the chemical variability at time-scale and intraspecific levels. Thus, harvests were done throughout a 15 months period and HS-SPME & GC-MS were used to analyze the samples. A pre concentration method was developed by reaching optimum values for parameters involving the ideal thermodynamic equilibrium in HSSPME. The chromatograms acquisition, relative retention index calculations and electron ionization mass spectra acquisition, combined, made possible the identification of 7 monoterpenoids and 1 sesquiterpenoid. A particular sesquiterpene could have been identified only by using HS-SPME pre concentration and not by essential oils analysis. Using prep-TLC of the essential oils, 3 sesquiterpenes were isolated. The ESI-MS, ESI-MS/MS as well as 1D and 2D NMR spectra of two of these three isolated terpenes were acquired. One new sesquiterpene, bisabolyl acetate, had his structure elucidated at the end of this process. This sesquiterpene is displayed in hydro alcoholic extracts used in folk medicine. Bioassays for in vitro antinociceptive investigations using peritoneal macrophages isolated of Wistar rats were done using the bisabolyl acetate. Results on this investigation may suggest that a pain relief effect could be described for this compound, every since it was possible to notice a reducing on IL-1X and TNF-Y levels. These two cytokines are involved in inflammatory pain. A regular pattern on volatile levels within the samples couldve been noticed, and it is what could be called an intraspecific uniformity. A trend on both intraplant and circadian investigations couldve been observed and what tends to happen is a rising on sesquiterpenes level by the period of year which the rainy and warm summer is governing the weather. In an opposite way these levels tend to diminish by the period in which the lower temperatures are registered (throughout the night time). Among the younger leaves there is also a trend on higher sesquiterpenes levels to occur.

O estilbeno resveratrol é um composto fenólico potencialmente benéfico à saúde, principalmente devido a sua atividade cardioprotetora. Apesar de abundante em uvas e vinhos tintos, o resveratrol encontra-se ausente na maioria das frutas e vegetais que compõe a dieta humana. Recentemente, este estilbeno foi detectado em cacau e chocolates da Europa e Estados Unidos, configurando-os como sua segunda maior fonte comestível. A escassez de estudos acerca da ocorrência de resveratrol em alimentos consumidos pela população brasileira torna evidente a importância da investigação por fontes que o contenham. Este estudo teve como objetivos avaliar o conteúdo de compostos fenólicos totais, a atividade antioxidante de extratos aquosos e alcoólicos de cacau e derivados produzidos no Brasil, além do teor de resveratrol. Foram analisados 14 produtos que incluíram nibs de cacau, chocolates 70% e 56% de cacau, chocolates meio amargos, ao leite, brancos, achocolatados em pó e bebidas lácteas achocolatadas, de marcas populares do mercado brasileiro. Os compostos fenólicos totais foram quantificados pelo método Folin-Ciocalteu e a atividade antioxidante foi avaliada pelos métodos DPPH, ABTS, FRAP e auto-oxidação do sistema \'beta\'-caroteno/ácido linoleico. A identificação do resveratrol nas amostras foi confirmada pela técnica de cromatografia gasosa acoplada a espectrometria de massas (CG-EM) e a quantificação foi feita pela técnica de cromatografia líquida de alta eficiência (CLAE). Os extratos aquosos apresentaram teores mais elevados de compostos fenólicos totais (mg AG.g-1), na seguinte ordem: nibs de cacau (21,54) > chocolate 70% (10,45) > chocolate 56% (9,51) > chocolates meio amargos (8,15) > achocolatados em pó (5,91) > chocolates ao leite (3,77) > chocolates brancos (1,22) > bebidas lácteas achocolatadas (0,96). A mesma sequência foi encontrada para a atividade antioxidante obtida pelos métodos indiretos, exceto para chocolates brancos, que exibiram os menores potenciais. Os extratos aquosos apresentaram a maior atividade antioxidante, variando de 86,53 a 1,55% pelo método DPPH; 141,27 a 3,2 \'mü\'m trolox.g-1 pelo método ABTS e 354,42 a 2,27 \'mü\'mol Fe++.g-1 pelo método FRAP. Por meio da auto-oxidação do sistema \'beta\'- caroteno/ácido linoleico, os extratos aquosos e alcoólicos mostraram valores similares para atividade antioxidante, a qual foi maior que 70% para nibs de cacau e chocolates 70% e 56%. O estilbeno resveratrol foi identificado em todas as amostras analisadas por CG-EM, entretanto em virtude da presença de teores abaixo do limite de quantificação, não foi possível a sua quantificação na maioria das amostras pela técnica de CLAE. Chocolates meio amargos exibiram os maiores teores de resveratrol, os quais foram superiores aos relatados para os mesmos produtos europeus e americanos. Apesar do cacau brasileiro não estar entre os de melhor qualidade, os resultados obtidos mostram seu elevado potencial antioxidante e de seus derivados, contribuindo para a ingestão de antioxidantes pela população brasileira, dentre os quais o estilbeno resveratrol / The stilbene resveratrol is a phenolic compound potentially beneficial to human healthy, mainly due it cardioprotector properties. Despite it abundance in grapes and wines, this stilbene lacks in most fruits and vegetables that compose human diet. Recently, resveratrol was detected in cocoa and chocolates commercialized in Europe and United States, making these products the second edible source of resveratrol. The lack of studies about resveratrol occurrence in Brazilian diet makes evident the need for investigation of the stilbene sources. This study aimed at analyzing the amount of total phenolic compounds, the antioxidant activity of aqueous and methanolic extracts of cocoa and cocoa products from Brazil, and the resveratrol level. A total of 14 products were analyzed, including cocoa nibs, chocolates 70% and 56% cocoa, dark, milk and white chocolates, chocolate Milk beverages and chocolate powders, of popular Brazilian trademarks. The total phenolic compounds were quantified by the Folin-Ciocalteu method. The antioxidant activity was determined using the DPPH, ABTS, FRAP and \'beta\'-carotene bleaching assays. Identification of resveratrol in the samples was confirmed by gás chromatography/mass spectrometry method (GC-MS) and quantification was obtained by high performance liquid chromatography (HPLC). Aqueous extracts showed a higher phenolic content (mg GAE.g-1), following the sequence: cocoa nibs (21,54) > chocolate 70% (10,45), chocolate 56% (9,51), dark chocolates (8,15) > chocolate powders (5,91) > milk chocolates (3,77) > white chocolates (1,22) > chocolate milk beverages (0,96). The same sequence was detected for the antioxidant activity obtained by indirect methods, except for white chocolates, which exhibited the lowest antioxidant activity. Aqueous extracts showed a higher antioxidant activity, ranging from 86,53 to 1,55% in the DPPH assay; 141,27 to 3,2 \'mü\'m trolox.g-1 in the ABTS assay and 354,42 to 2,27 \'mü\'mol Fe++.g-1 in the FRAP assay By the \'beta\'-carotene bleaching method, methanolic and aqueous extracts showed similar antioxidant activities, which were higher than 70% for cocoa and chocolates 70% and 56% cocoa. Resveratrol was identified in all the samples analyzed by GCMS, but its presence below the limit of quantification doesnt allow its determination in all samples by HPLC. Dark chocolates exhibited the highest resveratrol levels, which were higher than those related for the same European and American products. Although Brazilian cocoa isnt recognized for its quality, the results obtained show it high antioxidant activity and of its derivatives, contributing for antioxidants intake by Brazilian population, among them the stilbene resveratrol