Made available in DSpace on 2016-04-18T21:39:48Z (GMT). No. of bitstreams: 2 Angelo Schranko de Oliveira1.pdf: 925871 bytes, checksum: 812a592f67dbda8b36f5168fbd5f2598 (MD5) Angelo Schranko de Oliveira2.pdf: 2918106 bytes, checksum: 0969a0bf28b426ce84fe4595d80a73c2 (MD5) Previous issue date: 2009-01-28 / Wolfram Research, Inc. / Cellular automata (CAs) can be defined as discrete dynamical systems over n-dimensional networks of locally connected components, whose evolution occur in a discrete, synchronous and homogeneous fashion. Among their several applications, they have been used as a tool for complex systems modeling governed by fundamental laws of conservation (number-conserving cellular automata) or reversibility (reversible cellular automata). Another fundamental property that can be observed in CAs is regarding to their linearity (linear cellular automata) or nonlinearity. Usually, linear phenomena present low dynamic complexity, however, nonlinear phenoma can present complex behaviours like sensitive dependence on initial conditions and routes to chaos. This work focuses on investigating properties of cellular automata belonging to the intersection of those four classes, namely, reversible, number-conserving, and linear or nonlinear cellular automata. After presenting basic definitions, the notions of number-conserving cellular automata, conservation degree and reversibility are reviewed. Following, a dynamical characterisation parameter which relates the reversibility property of a onedimensional cellular automaton and the pre-images of their basic blocks is introduced, and some proofs of its general properties are given. Empirical observations herein suggest that a cellular automaton is reversible and number-conserving if, and only if, its local transition function is a composition of the local transition functions of the reversible, number-conserving cellular automata with neighbourhood size n=2; such an observation was drawn for neighbourhood sizes n∈{2, 3, 4, 5, 6} and number of states q=2; n∈{2, 3} and q=3; n∈{2, 3} and q=4. A proof for such a conjecture would allow the enumeration between neighbourhood lengths and the quantity of reversible, numberconserving cellular automata in the corresponding space, which can be easily identified by working out the compositions of the local transition functions with n=2. Finally, some relationships between reversible, number-conserving, linear and nonlinear CA rules, their spatio-temporal diagrams and basin of attraction fields are presented. / Autômatos celulares (ACs) podem ser definidos como sistemas dinâmicos sobre redes ndimensionais de componentes localmente conectados, cuja evolução ocorre de forma discreta, síncrona e homogênea. Dentre suas diversas aplicações, têm sido utilizados como ferramenta para modelagem de sistemas complexos regidos por leis fundamentais de conservação (autômatos celulares conservativos) ou reversibilidade (autômatos celulares reversíveis). Outra propriedade fundamental que pode ser observada nos ACs diz respeito à sua linearidade (autômatos celulares lineares) ou nãolinearidade. Fenômenos lineares normalmente apresentam menor complexidade dinâmica, enquanto fenômenos não-lineares podem apresentar propriedades tais como sensibilidade às condições iniciais e rotas para caos. O presente trabalho concentra-se na investigação de propriedades de autômatos celulares unidimensionais pertencentes à interseção dessas quatro classes, isto é, autômatos celulares unidimensionais conservativos, reversíveis, e lineares ou não-lineares. Após definições básicas, são revisitados os conceitos de conservabilidade e reversibilidade. Em seguida, introduz-se um parâmetro de caracterização dinâmica que relaciona a distribuição do número de pré-imagens dos blocos básicos à reversibilidade de autômatos celulares unidimensionais e apresentam-se algumas demonstrações decsuas propriedades gerais. Observações empíricas aqui realizadas sugerem que um autômato celular unidimensional é conservativo e reversível se, e somente se, sua função local de transição de estados é uma composição das funções locais de transição de estado dos autômatos celulares conservativos e reversíveis de vizinhança de comprimento n=2; tal observação foi constatada para vizinhanças de comprimento n∈{2, 3, 4, 5, 6} e quantidade de estados q=2; n∈{2, 3} e q=3; n∈{2, 3} e q=4. Uma demonstração para tal conjectura permitiria estabelecer uma enumeração entre os comprimentos das vizinhanças e a quantidade de autômatos celulares unidimensionais conservativos e reversíveis no espaço correspondente, os quais podem ser facilmente identificados através do cálculo das composições das funções locais de transição de estados com n=2. Por fim, apresentam-se relações entre as classes dos ACs conservativos, reversíveis, lineares e não-lineares, suas dinâmicas espaçotemporais e campos de bacias de atração.

A proposta deste trabalho é apresentar resultados para o estudo sistemático de sistemas dinâmicos reversíveis-equivariantes, ou seja, em presença simultânea de simetrias e antisimetrias. Este é o caso em que o domínio e as equações que regem o sistema são invariantes pela ação de um grupo de Lie compacto Γ formado pelas simetrias e anti-simetrias do problema. Apresentamos métodos de teoria de Singularidades e teoria de invariantes para classificar bifurcações a um parâmetro de pontos de equilíbrio destes sistemas. Para isso, separamos o estudo de aplicações Γ-reversíveis-equivariantes em dois casos: auto-dual e não auto-dual. No primeiro caso, a existência de um isomorfismo linear Γ-reversível-equivariante estabelece uma correspondência entre a classificação de problemas Γ-reversíveis-equivariantes e a classificação de problemas Γ-equivariantes associados, para os quais todos os elementos de Γ agem como simetria. Os resultados obtidos para o caso não auto-dual se baseiam em teoria de invariantes e envolvem técnicas algébricas que reduzem a análise ao caso polinomial invariante. Dois algoritmos simbólicos são estabelecidos para o cálculo de geradores para o módulo das funções anti-invariantes e para o módulo das aplicações reversíveis-equivariantes. / The purpose of this work is to present results for the sistematic study of reversible-equivariant dynamical systems, namely in simultaneous presence of symmetries and reversing simmetries. This is the case when the domain and the equations modeling the system are invariant under the action of a compact Lie group Γ formed by the symmetries and reversing symmetries of the problem. We present methods in Singularities and Invariant theory to classify oneparameter steady-state bifurcations of these systems. For that, we split the study of the ¡¡reversible-equivariant mapping into two cases: self-dual and non self-dual. In the first case, the existence of a Γ-reversible-equivariant linear isomorphism establishes a one-toone correspondence between the classification of Γ-reversible-equivariant problems and the classification of the associated Γ-equivariant problems, for which all elements in Γ act as symmetries. The results obtained for the non self-dual case are based on Invariant theory and involve algebraic techniques that reduce the analysis to the invariant polynomial case. Two symbolic algorithms are established for the computation of generators for the module of anti-invariant functions and for the module of reversible-equivariant mappings.

Cette thèse tente d’initier un dialogue entre la philosophie de Maurice Merleau-Ponty et l’oeuvre théorique du cinéaste Jean Epstein. Située à la frontière poreuse entre la phénoménologie et l’esthétique du cinéma, elle souligne la profondeur de l’approche proposée et permise par la pensée de Merleau-Ponty, en particulier à travers les pistes ouvertes par ses notes préparatoires du cours Le monde sensible et le monde de l’expression (1953), publiées en 2011. Cette recherche adopte donc une perspective réflexive et interrogative sur la posture du phénoménologue. La première partie met en avant l’importance du rapport ambigu de la phénoménologie merleau-pontienne au langage verbal et les difficultés qu’elle rencontre pour se penser elle même en tant que fait linguistique. Cette ambiguïté se trouve à la racine d’un « besoin » virtuel d’image,mais également de certaines « résistances » à la participation active du cinéma dans la constitution du savoir.Les deuxième et troisième parties de la recherche mettent directement en place la confrontation avec la pensée de Jean Epstein. Elles se concentrent respectivement sur la notion de réversibilité, à la fois comme concept et comme procédé cinématographique; puis sur l’idée du cinéma comme « pensée » artificielle,autonome et expressive. En retraçant l’évolution de la « parole du cinéma » dans l’oeuvre d’Epstein, on découvre certaines problématiques partagées avec l’ontologie de la Chair de Merleau-Ponty. La dernière partie de la thèse reprend une série de propositions critiques de cette ontologie fondées sur des concepts émanant de l’image en mouvement. Au final, cette recherche propose de voir dans les crises internes de l’appareil conceptuel de Merleau-Ponty, une possibilité de pratiquer une philosophie du cinéma. / This thesis attempts to initiate a dialogue between Maurice Merleau-Ponty’s philosophy and the theoretical works of director Jean Epstein. Situated at the porous borders of phenomenology and visualstudies, it underlines the depth offered by Merleau-Ponty’s approach. It gives a specific attention to the newleads opened by the preparatory notes to his lessons « Le monde sensible et le monde de l’expression »(1953), published in 2011. This research adopts a reflexive and interrogative perspective towards thephenomenological « posture ». The first part insists on the importance of the ambiguous attitude of Merleau-Ponty’s phenomenology towards verbal language, and on the difficulties it encounters to conceive itself as alinguistic fact. This ambiguity gives its roots to a virtual « need » for images, but also to several« resistances » against the active participation of cinema in the constitution of knowledge. The second andthird part of the research directly instigate the confrontation with Jean Epstein’s thinking. They focus respectively on the notion of « reversibility », both as concept and as a cinematographic effect; then on thenotion of cinema as an artificial, autonomous and expressive form of thought. By tracing the evolution of the« cinematic speech » in Epstein’s works, several problematics appear to be shared with Merleau-Ponty’sontology of Flesh. The fourth and last part of the thesis presents a series of critical propositions based on the concepts emanating from the moving picture. In the end, this research suggest the possibility to practice a« cinematic » philosophy within the internal crisis of Merleau-Ponty’s conceptual structure.

The thesis deals with analysis of conceptual-methodological issues examined in the framework of post-keynesian economics. The author´s goal is to supply a solution to the problem of a definition of determinism/non-determinism for both deterministic and stochastic systems and also to the problem of the prevailing confusion which surrounds the notion of reversibility/irreversibility in both path-dependent and traditional-equilibrist systems. The author regards the determinism/non-determinism problem as essentially linked to the problem of a definition of fundamental uncertainty. The key issues are being identified in the "problem of a generator of endogenous shocks" and the "selection - creation problem". Finding solutions to these enables us to take a stand on the validity/invalidity of the classical dichotomy, in the eyes of the author. Davidson´s interpretation of ergodicity and O´Donnell´s critique of this are being presented and, drawing on the latter, along with Álvarez-Ehnts´ critique, the author rejects a simplifying pattern of Davidson´s, according to which neoclassical economics is based on the ergodic axiom. The author suggests a solution to the "selection - creation problem" consisting in distinguishing epistemological determinism from ontological determinism on the one hand, and epistemological determinism from epistemological non-determinism on the other hand. While selection is a characteristic feature of epistemological determinism and, in effect, the realm of "fundamental certainty", creation is referred to by the author as a characteristic feature of epistemological non-determinism, i. e., in effect, the realm of fundamental uncertainty. The author regards the "problem of a generator of endogenous shocks" a self-contradictory notion, based on the principle of causality and the law of non-contradiction, and suggests a solution to the problem consisting in rejection of the concept of shock endogeneity. At the same time, the author rejects Davidson´s "fundamental neoclassical article of faith" rhetoric, based on the first cause argument implied by the principle of causality. In opposition to Davidson, the author regards fundamental uncertainty being of a basically epistemological nature, consisting in our ignorance of the "ultimate law of change", the "Devine formula". Unlike O´Donnell, however, who puts stress on the element of epistemological uncertainty in his epistemological approach to uncertainty, the author also puts stress on the element of ontological certainty, consisting in our knowledge of the existence of the "Devine formula", apart from our epistemological uncertainty.

Abstract Developments in information technology have had a big impact in healthcare, producing vast amounts of data and increasing demands associated with their secure transfer, storage and analysis. To serve them, biomedical data need to carry patient information and records or even extra biomedical images or signals required for multimodal applications. The proposed solution is to host this information in data using data hiding algorithms through the introduction of imperceptible modifications achieving two main purposes: increasing data management efficiency and enhancing the security aspects of confidentiality, reliability and availability. Data hiding achieve this by embedding the payload in objects, including components such as authentication tags, without requirements in extra space or modifications in repositories. The proposed methods satisfy two research problems. The first is the hospital-centric problem of providing efficient and secure management of data in hospital networks. This includes combinations of multimodal data in single objects. The host data were biomedical images and sequences intended for diagnoses meaning that even non-visible modifications can cause errors. Thus, a determining restriction was reversibility. Reversible data hiding methods remove the introduced modifications upon extraction of the payload. Embedding capacity was another priority that determined the proposed algorithms. To meet those demands, the algorithms were based on the Least Significant Bit Substitution and Histogram Shifting approaches. The second was the patient-centric problem, including user authentication and issues of secure and efficient data transfer in eHealth systems. Two novel solutions were proposed. The first method uses data hiding to increase the robustness of face biometrics in photos, where due to the high robustness requirements, a periodic pattern embedding approach was used. The second method protects sensitive user data collected by smartphones. In this case, to meet the low computational cost requirements, the method was based on Least Significant Bit Substitution. Concluding, the proposed algorithms introduced novel data hiding applications and demonstrated competitive embedding properties in existing applications. / Tiivistelmä Modernit terveydenhuoltojärjestelmät tuottavat suuria määriä tietoa, mikä korostaa tiedon turvalliseen siirtämiseen, tallentamiseen ja analysointiin liittyviä vaatimuksia. Täyttääkseen nämä vaatimukset, biolääketieteellisen tiedon täytyy sisältää potilastietoja ja -kertomusta, jopa biolääketieteellisiä lisäkuvia ja -signaaleja, joita tarvitaan multimodaalisissa sovelluksissa. Esitetty ratkaisu on upottaa tämä informaatio tietoon käyttäen tiedonpiilotusmenetelmiä, joissa näkymättömiä muutoksia tehden saavutetaan kaksi päämäärää: tiedonhallinnan tehokkuuden nostaminen ja luottamuksellisuuteen, luotettavuuteen ja saatavuuteen liittyvien turvallisuusnäkökulmien parantaminen. Tiedonpiilotus saavuttaa tämän upottamalla hyötykuorman, sisältäen komponentteja, kuten todentamismerkinnät, ilman lisätilavaatimuksia tai muutoksia tietokantoihin. Esitetyt menetelmät ratkaisevat kaksi tutkimusongelmaa. Ensimmäinen on sairaalakeskeinen ongelma tehokkaan ja turvallisen tiedonhallinnan tarjoamiseen sairaaloiden verkoissa. Tämä sisältää multimodaalisen tiedon yhdistämisen yhdeksi kokonaisuudeksi. Tiedon kantajana olivat biolääketieteelliset kuvat ja sekvenssit, jotka on tarkoitettu diagnosointiin, missä jopa näkymättömät muutokset voivat aiheuttaa virheitä. Siispä määrittävin rajoite oli palautettavuus. Palauttavat tiedonpiilotus-menetelmät poistavat lisätyt muutokset, kun hyötykuorma irrotetaan. Upotuskapasiteetti oli toinen tavoite, joka määritteli esitettyjä algoritmeja. Saavuttaakseen nämä vaatimukset, algoritmit perustuivat vähiten merkitsevän bitin korvaamiseen ja histogrammin siirtämiseen. Toisena oli potilaskeskeinen ongelma, joka sisältää käyttäjän henkilöllisyyden todentamisen sekä turvalliseen ja tehokkaaseen tiedonsiirtoon liittyvät haasteet eHealth-järjestelmissä. Työssä ehdotettiin kahta uutta ratkaisua. Ensimmäinen niistä käyttää tiedonpiilotusta parantamaan kasvojen biometriikan kestävyyttä valokuvissa. Korkeasta kestävyysvaatimuksesta johtuen käytettiin periodisen kuvion upottamismenetelmää. Toinen menetelmä suojelee älypuhelimien keräämää arkaluontoista käyttäjätietoa. Tässä tapauksessa, jotta matala laskennallinen kustannus saavutetaan, menetelmä perustui vähiten merkitsevän bitin korvaamiseen. Yhteenvetona ehdotetut algoritmit esittelivät uusia tiedonpiilotussovelluksia ja osoittivat kilpailukykyisiä upotusominaisuuksia olemassa olevissa sovelluksissa.

Parkinson’s disease is an age-related neurodegenerative disorder. The major symptoms of Parkinson’s disease are closely linked to the pathology of the disease. The main pathology of Parkinson’s disease consists of the degeneration of neurons of the substantia nigra pars compacta (SNpc), which leads to reduced amounts of dopamine in the brain. One of the treatment strategies in Parkinson’s disease is to conserve dopamine by inhibiting the enzymes responsible for its catabolism. The monoamine oxidase (MAO) B isoform catalyses the oxidation of dopamine in the central nervous system and is therefore an important target for Parkinson’s disease treatment. Inhibition of MAO-B provides symptomatic relief for Parkinson’s disease patients by increasing endogenous dopamine levels as well as enhancing the levels of dopamine after administration of levodopa (L-dopa), the metabolic precursor of dopamine. Recent studies have shown that phthalide can be used as a scaffold for the design of reversible MAO inhibitors. Although phthalide is a weak MAO-B inhibitor, substitution on the C5 position of phthalide yields highly potent reversible MAO-B inhibitors. In the present study, sesamol and benzodioxane were used as scaffolds for the design of MAO inhibitors. The structures of sesamol and benzodioxane closely resemble that of phthalide, which suggests that these moieties may be useful for the design of MAO inhibitors. This study may be viewed as an exploratory study to discover new scaffolds for MAO inhibition. Since substitution at C5 of phthalide with a benzyloxy side chain yielded particularly potent MAO inhibitors, the sesamol and benzodioxane derivatives possessed the benzyloxy substituent in the analogous positions to C5 of phthalide. These were the C5 and C6 positions of sesamol and benzodioxane, respectively. The sesamol and benzodioxane derivatives were synthesised by reacting sesamol and 6- hydroxy-1,4-benzodioxane, respectively, with an appropriate alkyl bromide in the presence of potassium carbonate (K2CO3) in N,N-dimethylformamide (DMF). 6-Hydroxy-1,4- benzodioxane, in turn, was synthesised from 1,4-benzodioxan-6-carboxaldehyde. The structures of the compounds were verified with nuclear magnetic resonance (NMR) and mass spectrometry (MS) analyses, while the purities were estimated by high-pressure liquid chromatography (HPLC). Sixteen sesamol and benzodioxane derivatives were synthesised. To determine the inhibition potencies of the synthesised compounds the recombinant human MAO-A and MAO-B enzymes were used. The inhibition potencies were expressed as the corresponding IC50 values. The results showed that the sesamol and benzodioxane derivatives are highly potent and selective inhibitors of MAO-B and to a lesser extent MAOA. The most potent MAO-B inhibitor was 6-(3-bromobenzyloxy)-1,4-benzodioxane with an IC50 value of 0.045 μM. All compounds examined displayed selectivity for the MAO-B isoform over MAO-A. Generally the benzodioxane derivatives were found to be more potent inhibitors of human MAO-A and MAO-B than the sesamol derivatives. The reversibility and mode of MAO-B inhibition of a representative derivative, 6-(3- bromobenzyloxy)-1,4-benzodioxane, was examined by measuring the degree to which the enzyme activity recovers after dialysis of enzyme-inhibitor complexes, while Lineweaver- Burk plots were constructed to determine whether the mode of inhibition is competitive. Since MAO-B activity is completely recovered after dialysis of enzyme-inhibitor mixtures, it was concluded that 6-(3-bromobenzyloxy)-1,4-benzodioxane binds reversibly to the MAO-B enzyme. The Lineweaver-Burk plots constructed were linear and intersected on the y-axis. Therefore it may be concluded that 6-(3-bromobenzyloxy)-1,4-benzodioxane is a competitive MAO-B inhibitor. To conclude, the C6-substituted benzodioxane derivatives are potent, selective, reversible and competitive inhibitors of human MAO-B. These compounds are therefore promising leads for the future development of therapy for Parkinson’s disease. / MSc (Pharmaceutical Chemistry), North-West University, Potchefstroom Campus, 2015

Parkinson’s disease is an age-related neurodegenerative disorder. The major symptoms of Parkinson’s disease are closely linked to the pathology of the disease. The main pathology of Parkinson’s disease consists of the degeneration of neurons of the substantia nigra pars compacta (SNpc), which leads to reduced amounts of dopamine in the brain. One of the treatment strategies in Parkinson’s disease is to conserve dopamine by inhibiting the enzymes responsible for its catabolism. The monoamine oxidase (MAO) B isoform catalyses the oxidation of dopamine in the central nervous system and is therefore an important target for Parkinson’s disease treatment. Inhibition of MAO-B provides symptomatic relief for Parkinson’s disease patients by increasing endogenous dopamine levels as well as enhancing the levels of dopamine after administration of levodopa (L-dopa), the metabolic precursor of dopamine. Recent studies have shown that phthalide can be used as a scaffold for the design of reversible MAO inhibitors. Although phthalide is a weak MAO-B inhibitor, substitution on the C5 position of phthalide yields highly potent reversible MAO-B inhibitors. In the present study, sesamol and benzodioxane were used as scaffolds for the design of MAO inhibitors. The structures of sesamol and benzodioxane closely resemble that of phthalide, which suggests that these moieties may be useful for the design of MAO inhibitors. This study may be viewed as an exploratory study to discover new scaffolds for MAO inhibition. Since substitution at C5 of phthalide with a benzyloxy side chain yielded particularly potent MAO inhibitors, the sesamol and benzodioxane derivatives possessed the benzyloxy substituent in the analogous positions to C5 of phthalide. These were the C5 and C6 positions of sesamol and benzodioxane, respectively. The sesamol and benzodioxane derivatives were synthesised by reacting sesamol and 6- hydroxy-1,4-benzodioxane, respectively, with an appropriate alkyl bromide in the presence of potassium carbonate (K2CO3) in N,N-dimethylformamide (DMF). 6-Hydroxy-1,4- benzodioxane, in turn, was synthesised from 1,4-benzodioxan-6-carboxaldehyde. The structures of the compounds were verified with nuclear magnetic resonance (NMR) and mass spectrometry (MS) analyses, while the purities were estimated by high-pressure liquid chromatography (HPLC). Sixteen sesamol and benzodioxane derivatives were synthesised. To determine the inhibition potencies of the synthesised compounds the recombinant human MAO-A and MAO-B enzymes were used. The inhibition potencies were expressed as the corresponding IC50 values. The results showed that the sesamol and benzodioxane derivatives are highly potent and selective inhibitors of MAO-B and to a lesser extent MAOA. The most potent MAO-B inhibitor was 6-(3-bromobenzyloxy)-1,4-benzodioxane with an IC50 value of 0.045 μM. All compounds examined displayed selectivity for the MAO-B isoform over MAO-A. Generally the benzodioxane derivatives were found to be more potent inhibitors of human MAO-A and MAO-B than the sesamol derivatives. The reversibility and mode of MAO-B inhibition of a representative derivative, 6-(3- bromobenzyloxy)-1,4-benzodioxane, was examined by measuring the degree to which the enzyme activity recovers after dialysis of enzyme-inhibitor complexes, while Lineweaver- Burk plots were constructed to determine whether the mode of inhibition is competitive. Since MAO-B activity is completely recovered after dialysis of enzyme-inhibitor mixtures, it was concluded that 6-(3-bromobenzyloxy)-1,4-benzodioxane binds reversibly to the MAO-B enzyme. The Lineweaver-Burk plots constructed were linear and intersected on the y-axis. Therefore it may be concluded that 6-(3-bromobenzyloxy)-1,4-benzodioxane is a competitive MAO-B inhibitor. To conclude, the C6-substituted benzodioxane derivatives are potent, selective, reversible and competitive inhibitors of human MAO-B. These compounds are therefore promising leads for the future development of therapy for Parkinson’s disease. / MSc (Pharmaceutical Chemistry), North-West University, Potchefstroom Campus, 2015

Le sujet général de cette thèse est l’étude de la fonctionnalisation covalente des nanotubes de carbone (CNT) et son application en électronique. Premièrement, une introduction au sujet est présentée. Elle discute des propriétés des CNT, des différentes sortes de fonctionnalisation covalente ainsi que des principales techniques de caractérisation utilisées au cours de la thèse. Deuxièmement, les répercussions de la fonctionnalisation covalente sur les propriétés des nanotubes de carbone monoparoi (SWNT) sont étudiées. Deux types de fonctionnalisation sont regardés, soit le greffage de groupements phényles et le greffage de groupements dichlorométhylènes. Une diminution de l’absorption optique des SWNT dans le domaine du visible-proche infrarouge est observée ainsi qu’une modification de leur spectre Raman. De plus, pour les dérivés phényles, une importante diminution de la conductance des nanotubes est enregistrée. Troisièmement, la réversibilité de ces deux fonctionnalisations est examinée. Il est montré qu’un recuit permet de résorber les modifications structurales et retrouver, en majorité, les propriétés originales des SWNT. La température de défonctionnalisation varie selon le type de greffons, mais ne semble pas affectée par le diamètre des nanotubes (diamètre examinés : dérivés phényles, Ømoyen= 0,81 nm, 0,93 nm et 1,3 nm; dérivés dichlorométhylènes, Ømoyen = 0,81 nm et 0,93 nm). Quatrièmement, la polyvalence et la réversibilité de la fonctionnalisation covalente par des unités phényles sont exploitées afin de développer une méthode d’assemblage de réseaux de SWNT. Celle-ci, basée sur l’établissement de forces électrostatiques entre les greffons des SWNT et le substrat, est à la fois efficace et sélective quant à l’emplacement des SWNT sur le substrat. Son application à la fabrication de dispositifs électroniques est réalisée. Finalement, la fonctionnalisation covalente par des groupements phényles est appliquée aux nanotubes de carbone à double paroi (DWNT). Une étude spectroscopique montre que cette dernière s’effectue exclusivement sur la paroi externe. De plus, il est démontré que la signature électrique des DWNT avant et après la fonctionnalisation par des groupements phényles est caractéristique de l’agencement nanotube interne@ nanotube externe. / The general subject of this thesis is the covalent functionalization of carbon nanotubes and its applications in electronics. First, the properties of the carbon nanotubes, their functionalization, and the principal techniques used to characterize them are presented. Second, the repercussions of the grafting of phenyl addends and dichloromethylene addends on the properties of single-wall carbon nanotubes (SWNT) are investigated. A decrease of light absorption and a modification of the Raman spectra of the nanotubes are observed as well as, for the phenyl derivatives, an important loss of their electrical conductivity. Third, the reversibility of the functionalization is examined. The study shows that the addends are detached from the sidewall upon annealing, leading to the reconstruction of the graphene structure. Most of the original properties of the SWNT are then recovered. In addition, it is observed that the temperature of defunctionalization depends on the nature of the addends, but it is not influenced by the diameter of the SWNT (Range studied: phenyl derivatives, Ømoyen= 0,81 nm, 0,93 nm et 1,3 nm; dichlorométhylènes derivatives, Ømoyen = 0,81 nm et 0,93 nm). Fourth, a new method to reliably self-assemble networks of dense SWNT onto patterned substrates is presented. The method is based on covalent functionalization and electrostatic interactions. Its suitability for making electronic devices is demonstrated. Last, this thesis investigated the covalent functionalization of double-wall carbon nanotubes (DWNT). A spectroscopic study revealed that the grafting of the phenyl addends occurs exclusively on the outer wall. Furthermore, the identification of the metallic or semiconductor character of each wall of the DWNT is realized using electrical measurements taken before and after the functionalization.

Le sujet général de cette thèse est l’étude de la fonctionnalisation covalente des nanotubes de carbone (CNT) et son application en électronique. Premièrement, une introduction au sujet est présentée. Elle discute des propriétés des CNT, des différentes sortes de fonctionnalisation covalente ainsi que des principales techniques de caractérisation utilisées au cours de la thèse. Deuxièmement, les répercussions de la fonctionnalisation covalente sur les propriétés des nanotubes de carbone monoparoi (SWNT) sont étudiées. Deux types de fonctionnalisation sont regardés, soit le greffage de groupements phényles et le greffage de groupements dichlorométhylènes. Une diminution de l’absorption optique des SWNT dans le domaine du visible-proche infrarouge est observée ainsi qu’une modification de leur spectre Raman. De plus, pour les dérivés phényles, une importante diminution de la conductance des nanotubes est enregistrée. Troisièmement, la réversibilité de ces deux fonctionnalisations est examinée. Il est montré qu’un recuit permet de résorber les modifications structurales et retrouver, en majorité, les propriétés originales des SWNT. La température de défonctionnalisation varie selon le type de greffons, mais ne semble pas affectée par le diamètre des nanotubes (diamètre examinés : dérivés phényles, Ømoyen= 0,81 nm, 0,93 nm et 1,3 nm; dérivés dichlorométhylènes, Ømoyen = 0,81 nm et 0,93 nm). Quatrièmement, la polyvalence et la réversibilité de la fonctionnalisation covalente par des unités phényles sont exploitées afin de développer une méthode d’assemblage de réseaux de SWNT. Celle-ci, basée sur l’établissement de forces électrostatiques entre les greffons des SWNT et le substrat, est à la fois efficace et sélective quant à l’emplacement des SWNT sur le substrat. Son application à la fabrication de dispositifs électroniques est réalisée. Finalement, la fonctionnalisation covalente par des groupements phényles est appliquée aux nanotubes de carbone à double paroi (DWNT). Une étude spectroscopique montre que cette dernière s’effectue exclusivement sur la paroi externe. De plus, il est démontré que la signature électrique des DWNT avant et après la fonctionnalisation par des groupements phényles est caractéristique de l’agencement nanotube interne@ nanotube externe. / The general subject of this thesis is the covalent functionalization of carbon nanotubes and its applications in electronics. First, the properties of the carbon nanotubes, their functionalization, and the principal techniques used to characterize them are presented. Second, the repercussions of the grafting of phenyl addends and dichloromethylene addends on the properties of single-wall carbon nanotubes (SWNT) are investigated. A decrease of light absorption and a modification of the Raman spectra of the nanotubes are observed as well as, for the phenyl derivatives, an important loss of their electrical conductivity. Third, the reversibility of the functionalization is examined. The study shows that the addends are detached from the sidewall upon annealing, leading to the reconstruction of the graphene structure. Most of the original properties of the SWNT are then recovered. In addition, it is observed that the temperature of defunctionalization depends on the nature of the addends, but it is not influenced by the diameter of the SWNT (Range studied: phenyl derivatives, Ømoyen= 0,81 nm, 0,93 nm et 1,3 nm; dichlorométhylènes derivatives, Ømoyen = 0,81 nm et 0,93 nm). Fourth, a new method to reliably self-assemble networks of dense SWNT onto patterned substrates is presented. The method is based on covalent functionalization and electrostatic interactions. Its suitability for making electronic devices is demonstrated. Last, this thesis investigated the covalent functionalization of double-wall carbon nanotubes (DWNT). A spectroscopic study revealed that the grafting of the phenyl addends occurs exclusively on the outer wall. Furthermore, the identification of the metallic or semiconductor character of each wall of the DWNT is realized using electrical measurements taken before and after the functionalization.

Les méthodes de Monte Carlo par chaînes de Markov (MCCM) sont des méthodes servant à échantillonner à partir de distributions de probabilité. Ces techniques se basent sur le parcours de chaînes de Markov ayant pour lois stationnaires les distributions à échantillonner. Étant donné leur facilité d’application, elles constituent une des approches les plus utilisées dans la communauté statistique, et tout particulièrement en analyse bayésienne. Ce sont des outils très populaires pour l’échantillonnage de lois de probabilité complexes et/ou en grandes dimensions. Depuis l’apparition de la première méthode MCCM en 1953 (la méthode de Metropolis, voir [10]), l’intérêt pour ces méthodes, ainsi que l’éventail d’algorithmes disponibles ne cessent de s’accroître d’une année à l’autre. Bien que l’algorithme Metropolis-Hastings (voir [8]) puisse être considéré comme l’un des algorithmes de Monte Carlo par chaînes de Markov les plus généraux, il est aussi l’un des plus simples à comprendre et à expliquer, ce qui en fait un algorithme idéal pour débuter. Il a été sujet de développement par plusieurs chercheurs. L’algorithme Metropolis à essais multiples (MTM), introduit dans la littérature statistique par [9], est considéré comme un développement intéressant dans ce domaine, mais malheureusement son implémentation est très coûteuse (en termes de temps). Récemment, un nouvel algorithme a été développé par [1]. Il s’agit de l’algorithme Metropolis à essais multiples revisité (MTM revisité), qui définit la méthode MTM standard mentionnée précédemment dans le cadre de l’algorithme Metropolis-Hastings sur un espace étendu. L’objectif de ce travail est, en premier lieu, de présenter les méthodes MCCM, et par la suite d’étudier et d’analyser les algorithmes Metropolis-Hastings ainsi que le MTM standard afin de permettre aux lecteurs une meilleure compréhension de l’implémentation de ces méthodes. Un deuxième objectif est d’étudier les perspectives ainsi que les inconvénients de l’algorithme MTM revisité afin de voir s’il répond aux attentes de la communauté statistique. Enfin, nous tentons de combattre le problème de sédentarité de l’algorithme MTM revisité, ce qui donne lieu à un tout nouvel algorithme. Ce nouvel algorithme performe bien lorsque le nombre de candidats générés à chaque itérations est petit, mais sa performance se dégrade à mesure que ce nombre de candidats croît. / Markov Chain Monte Carlo (MCMC) algorithms are methods that are used for sampling from probability distributions. These tools are based on the path of a Markov chain whose stationary distribution is the distribution to be sampled. Given their relative ease of application, they are one of the most popular approaches in the statistical community, especially in Bayesian analysis. These methods are very popular for sampling from complex and/or high dimensional probability distributions. Since the appearance of the first MCMC method in 1953 (the Metropolis algorithm, see [10]), the interest for these methods, as well as the range of algorithms available, continue to increase from one year to another. Although the Metropolis-Hastings algorithm (see [8]) can be considered as one of the most general Markov chain Monte Carlo algorithms, it is also one of the easiest to understand and explain, making it an ideal algorithm for beginners. As such, it has been studied by several researchers. The multiple-try Metropolis (MTM) algorithm , proposed by [9], is considered as one interesting development in this field, but unfortunately its implementation is quite expensive (in terms of time). Recently, a new algorithm was developed by [1]. This method is named the revisited multiple-try Metropolis algorithm (MTM revisited), which is obtained by expressing the MTM method as a Metropolis-Hastings algorithm on an extended space. The objective of this work is to first present MCMC methods, and subsequently study and analyze the Metropolis-Hastings and standard MTM algorithms to allow readers a better perspective on the implementation of these methods. A second objective is to explore the opportunities and disadvantages of the revisited MTM algorithm to see if it meets the expectations of the statistical community. We finally attempt to fight the sedentarity of the revisited MTM algorithm, which leads to a new algorithm. The latter performs efficiently when the number of generated candidates in a given iteration is small, but the performance of this new algorithm then deteriorates as the number of candidates in a given iteration increases.