La complexation de l'arénophile à un ligand naphtalène substitué sur un seul noyau par un ou deux groupe triméthylsilyléthynyle conduit à la formation des deux régio-isomères A (arénophile coordiné au cycle substitué) et B (arénophile lié au cycle libre). L'isomère A est le produit cinétique et l'isomère B le produit thermodynamique de la réaction. La substitution du groupe trimétylsilyle par le fragment organométallique électro-actif permet d'étudier l'isomérisation A B . La migration haptotropique électro-induite, réalisée à 20 °C, est quasi quantitative . Elle résulte de l'activation de la liaison Ru provoquée par l'oxydation mono-électronique du centre redox organofer en présence d'un solvant coordinant . La synthèse du complexe ortho disubstitué, stériquement très encombré, et de ses dérivés mono- et di-oxydés a été effectuée avec succès. L'espèce mono-oxydée qui possède un couplage électronique fort est un dérivé à valence mixte de classe II B, à la limite entre les classes II et III. Les complexes tétranucléaires ont également été synthétisés et caractérisés par différentes techniques incluant notamment la radiocristallographie. Ces composés présentent des interactions électroniques à la fois en ortho, meta et para, générant de nouvelles propriétés qui pourraient s'avérer totalement inédites dans le domaine de l'électronique moléculaire. Finalement, une nouvelle famille de composés hybrides organiques inorganiques trans- a aussi été préparée (TTF = tétrathiafulvalène; n = 0-3). Le dérivé mono-oxydé est un composé à valence mixte de classe II. Le transfert d'électron intramoléculaire peut se faire selon un mécanisme par effet tunnel et par un mécanisme multi-étape par sauts entre les centres redox inorganiques et organiques. / The complexation of the arenophile to a naphthalene ligand bearing one or two trimethylsilylethynyle group gives the two regioisomers A (arenophile coordinated to the substituted ring) and B (arenophile coordinated to the free cycle). Isomer A is the kinetic product and isomer B is the thermodynamic product of the reaction. The substitution of the trimethylsilyl group by the electroactive organometallic fragment allows to control the isomerization from A to B. The electro induced haptotropic migration, performed at 20 ° C, is almost quantitative, and results from the activation of the Ru bond induced by the one-electron oxidation of the organoiron redox center in the presence of a coordinating solvent. The synthesis of the sterically constraint ortho disubstituted complex, and its mono and di-oxidized forms were successfully achieved. The mono-oxidized species that shows a strong electronic coupling is a Class-II B mixed valence compound. The tetranuclear complexes were also prepared and characterized by various methods including X-ray crystallography. These compounds exhibit electronic interactions in the ortho, meta and para positions, generating new properties that could be of great interest in the field of molecular electronics. Finally, a new family of organic-inorganic hybrids trans- has also been prepared (TTF = tetrathiafulvalene; n = 0-3). The mono-oxidized complex (n = 1) is a Class-II mixed-valence compound in which the spin density varies with the respective orientation of the metal termini. Intramolecular electron transfer occurs through single-step tunneling and multiple-step hopping mechanisms.

Les composés à transition de spin forment une classe spécifique de matériaux pour lesquels la commutation de l’état de spin du centre métallique peut être pilotée par divers stimuli (T, P, irradiation lumineuse, …) et s’accompagne de changements remarquables des propriétés physiques (magnétiques, optiques, structurales ou encore vibrationnelles). Ils se distinguent des autres matériaux commutables par l’observation, pour un certain nombre d’entre eux, de processus coopératifs à l’état solide, donnant lieu à l’ouverture d’une hystérèse thermique (bistabilité) particulièrement intéressante pour le stockage de l’information. Un des challenges technologiques actuels est de réduire la taille des matériaux susceptibles d’application et de les mettre en forme au sein de dispositifs sans altérer pour autant leurs propriétés. Les objectifs de la thèse ont été d’élaborer des micro- et nanoparticules à conversion de spin à partir de composés moléculaires présentant une transition de spin du premier ordre à l’état massif, puis d’étudier et analyser l’influence de la taille et de la matrice dispersante sur les processus de transition de spin. Après un premier chapitre introductif portant sur les matériaux à transition de spin, les méthodes de nanochimie et de mise en forme, le deuxième chapitre décrit l’élaboration de particules des composés FeII(phen)2(NCX)2 (X = S, Se) et [FeIII(3-OMeSalRen)2]PF6 (R = Me, Et). Comme la technique de précipitation rapide convient pour des composés ioniques, son application à FeII(phen)2(NCX)2 composé neutre, a nécessité la mise au point d’une synthèse indirecte de particules, basée sur l’extraction de ligand de précurseurs solubles, et le contrôle via des paramètres expérimentaux, des étapes de nucléation-croissance. De nouvelles particules de composés ioniques de Fe(III) [FeIII(3-OMeSalRen)2]PF6 (R = Me, Et) et des films minces contenant ces particules dispersées dans un polymère (PVP) ont été préparées. Les études magnétique et optique de ces films montrent que la matrice et la mise en forme modifient toujours les caractéristiques de la transition de spin des particules.La deuxième partie des travaux a été consacrée à l’étude des effets d’environnement. L’interaction entre des microparticules de Fe(phen)2(NCS)2 et des matrices vitreuses (Tg > T1/2; T1/2, étant la température de transition) peut conduire à l’ouverture d’un large cycle d’hystérésis, déplacé vers les plus basses températures. Cette zone de bistabilité a été examinée à l’aide de la méthode FORC (First-Order Reversal Curves). L’analyse a permis d’établir l’existence de composantes réversibles attribuées aux interactions élastiques à l’interface matrice/particule et au changement de volume de la particule à transition de spin.L’étude des effets de matrice et de taille a été poursuivie avec des micro- et nanocristaux de [FeIII(3-OMeSalEen2]PF6 dispersés dans des polymères ou des liquides moléculaires formant des verres à basse température. L’encapsulation dans des verres rigides de particules haut-spin (T1/2 < Tg) ou bas-spin (T1/2 > Tg) donnent lieu à des conversions de spin déplacées respectivement vers les plus basses ou plus hautes températures, éventuellement des processus coopératifs avec hystérésis. Le renforcement de la coopérativité et la bistabilité observées dans le second cas ont été interprétés comme résultant des contraintes mécaniques vis-à-vis du changement de volume BS-HS de la particule. Enfin, le changement d’état de la matrice induit par des étapes de trempe (ou recuit) en-dessous (au-dessus) de la température de transition vitreuse, a été exploité pour moduler ces effets. Dans la perspective d’une application, de nouvelles études de composites ont été engagées avec des complexes présentant une transition de spin proche de la température ambiante. Le choix de la matrice dispersante selon certains critères (nature chimique, température de transition vitreuse) a permis de retrouver certains effets. / Spin-transition compounds are a class of materials for which the spin-state switching of the metal center can be controlled by various stimuli (T, P, light irradiation,...) and produces dramatic changes of physical properties (magnetic, optical, structural or vibrational). With respect to the set of switchable materials, a number of spin-transition compounds exhibit at solid-state cooperative processes and thermal hysteresis loops (bistability), particularly suitable for information storage. One of the current technological challenges is to integrate in devices such potentially interesting materials without altering their properties. The goal of the research, recently developed by several teams, is to determine the smaller size of object in which an information can be stored, and thus to understand the effect of downsizing on cooperativity and bistability. Therefore, the objectives of the Ph-D thesis were (i) to synthesize spin-crossover nano- and microparticles from molecular materials that in the form of bulk undergo a first-order phase transition; (ii), to investigate the importance of particles size and matrix effects on the spin-transition process.After a first chapter in which the spin crossover materials are introduced, the second chapter describes the synthesis of particles of FeII(phen)2(NCX)2 (X = S, Se) and [FeIII(3-OMeSalRen)2]PF6 (R = Me, E) compounds. As the fast precipitation technique essentially suits for ionic compounds, its application to neutral ones like FeII(phen)2(NCX)2, has been made possible by an indirect syntheses based on the ligand extraction from soluble precursors and the control of nucleation and growth processes of neutral products via experimental parameters. New particles of [FeIII(3-OMeSalEen)2]PF6 and thin films containing them after their dispersion in a polymeric matrix (PVP) have been prepared. The study of these films with UV-vis and magnetic measurements has raised the issue of the impact of the polymeric matrix and processing on the spin transition properties of these particles.The second part of the manuscript focuses on the interaction between the spin-crossover particles and the dispersing medium. This interaction between microparticles of Fe(phen)2(NCS)2 and glassy matrices (Tg > T1/2, T1/2, being the transition temperature) may result in the observation of large hysteresis loops shifted towards lower temperatures. This bistability has been examined with the FORC (First-Order Reversal Curves) method, magnetic measurements and a theoretical model. This analysis has shown the existence of reversible components associated to the particles/matrix interactions and the change of volume of spin-crossover particles.In a third part, the study of matrix and size effect has been pursued with micro- and nanocrystals of [FeIII(3-OMeSalEen2]PF6 encapsulated in polymeric or molecular liquids which form glasses at sufficiently low temperature. The encapsulation in rigid glasses of high spin (T1/2 < Tg) or low spin (T1/2 > Tg) particles give rise to transitions shifted towards lower or higher temperature respectively, possibly with cooperativity and hysteresis. The reinforcement of cooperativity and the bistability observed in the second case have been accounted for by the effect of the mechanical stress exerted by the glassy matrix on the particle volume. In addition, it has been shown that a thermal treatment of matrices (quenching or annealing steps below or above the glass transition) results in the modulation of the matrix effects. Finally, in the last chapter, a few composites including compounds undergoing a spin transition close to room temperature have been shortly investigated in presence of dispersing matrices. The choice of the matrices characteristics (chemical nature, glass transition temperature) has allowed some of these effects to be observed.

HTLV-I is the first discovered human retrovirus and a causative agent of both adult T-cell leukemia (ATL) and HTLV-I-associated myelopathy (or tropical spastic paraparesis) (HAM/TSP). Previous models have been successful in providing insight into the progression of HTLV-I infection. The relative simplicity of HTLV as well as its similarities to HIV and other diseases allow HTLV-I research to have diverse applications. The development of HAM/TSP is precipitated by a CTL immune response. Previous models for CTL response to HTLV-I infection have had relatively simple behaviours. A novel sigmoidal CTL response function results in complex behaviours previously unobserved. We establish the existence of bistability between solutions corresponding to carrier and endemic states. In addition, both super- and sub-critical Hopf bifurcations as well as the resulting stable and unstable periodic solutions are observed. Analytical and numerical results are discussed, as well as the biological consequences of the aforementioned behaviours. / Applied Mathematics

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Submitted by Murilo Oliveira (murilo.oliveira@df.ufscar.br) on 2018-05-28T14:03:10Z No. of bitstreams: 1 MuriloOliveira_dissertacao.pdf: 3213764 bytes, checksum: eaf61f839f12dceed4b235ef7970e674 (MD5) / Rejected by Ronildo Prado (ri.bco@ufscar.br), reason: Oi Murilo, Faltou enviar a Carta comprovante assinada pelo orientador. Solicite o modelo em sua Secretaria de Pós-graduação, preencha e colete a assinatura com o orientador e acesse novamente o sistema para fazer o Upload. Fico no aguardo para finalizarmos o processo. Abraços Ronildo on 2018-06-04T17:58:14Z (GMT) / Submitted by Murilo Oliveira (murilo.oliveira@df.ufscar.br) on 2018-06-04T18:39:43Z No. of bitstreams: 2 MuriloOliveira_dissertacao.pdf: 3213764 bytes, checksum: eaf61f839f12dceed4b235ef7970e674 (MD5) IMG_20180604_0001.pdf: 522878 bytes, checksum: b7fa478fbcdf1b45955f8a02f8403af0 (MD5) / Approved for entry into archive by Ronildo Prado (ri.bco@ufscar.br) on 2018-06-06T17:29:19Z (GMT) No. of bitstreams: 2 MuriloOliveira_dissertacao.pdf: 3213764 bytes, checksum: eaf61f839f12dceed4b235ef7970e674 (MD5) IMG_20180604_0001.pdf: 522878 bytes, checksum: b7fa478fbcdf1b45955f8a02f8403af0 (MD5) / Approved for entry into archive by Ronildo Prado (ri.bco@ufscar.br) on 2018-06-06T17:32:09Z (GMT) No. of bitstreams: 2 MuriloOliveira_dissertacao.pdf: 3213764 bytes, checksum: eaf61f839f12dceed4b235ef7970e674 (MD5) IMG_20180604_0001.pdf: 522878 bytes, checksum: b7fa478fbcdf1b45955f8a02f8403af0 (MD5) / Made available in DSpace on 2018-06-06T17:32:18Z (GMT). No. of bitstreams: 2 MuriloOliveira_dissertacao.pdf: 3213764 bytes, checksum: eaf61f839f12dceed4b235ef7970e674 (MD5) IMG_20180604_0001.pdf: 522878 bytes, checksum: b7fa478fbcdf1b45955f8a02f8403af0 (MD5) Previous issue date: 2018-02-28 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / The aim of this work is to study the electromagnetically induced transparency (EIT) and the coherent population trapping (CPT) phenomena in three-level systems, such as atoms and quantum dot molecules (QDM). The present work can be basically divided into two parts. The first one focus on comparing and explaining the differences between the optical reponses of systems composed by atoms and QDM and on proposing a possible application in cavity linewidth narrowing. In the second part, we turn our attention to the study of controlable optical bistability in three-level systems in the regime of CPT, bringing new perspectives to the study of these bistable systems and some practical applications as well. / O presente trabalho de mestrado tem como objetivo estudar o fenômeno da transparência eletromagneticamente induzida (EIT) e do aprisionamento coerente de populações (CPT) em sistemas de três níveis, como átomos e moléculas de ponto quântico (QDM). Essa dissertação pode ser dividida basicamente em duas partes. A primeira se encarrega de comparar e explicar a origem das diferenças observadas na resposta óptica de sistemas compostos por átomos e sistemas compostos por QDM, bem como propor uma possível aplicação para o sistema de QDM no estreitamento da largura de linha de cavidades. Já a segunda parte consiste de um estudo da biestabilidade óptica controlável em sistemas de 3 de níveis no regime de CPT, trazendo novas perspectivas de estudo desses sistemas biestáveis e aplicações como sensores de pequenas flutuações de frequência ou de amplitudes de campos eletromagnéticos. / CNPq: 131392/2016-6

Made available in DSpace on 2016-06-02T20:15:28Z (GMT). No. of bitstreams: 1 5145.pdf: 3696466 bytes, checksum: a50814528dfffc17767d4ca059a77ac6 (MD5) Previous issue date: 2013-03-27 / Universidade Federal de Minas Gerais / We investigate in this thesis the control of absorptive optical bistability in a standing wave optical cavity filled with a collection of two and three-level noninteracting atoms weakly coupled to a single electromagnetic mode of a optical resonator. The observed control for the three-level configuration happens under cavity coherent population trapping conditions, it is sensitive to the induced atomic coherence in the system and it can be manipulated through different parameters. We propose some applications presenting a new effect, named by ourselves as complementary optical bistability. It is very interesting to exploit bistability phenomenon to perform bistable cascade devices, such as an optical transistor. We also study the all-optical control of the quantum fuctuations of a beam via a combination of single-atom cavity quantum electrodynamics (CQED) and electromagnetically induced transparency (EIT). Specifically, the EIT control field is used to tune the CQED transition frequencies in and out of resonance with the probe light. In this way, single-photon and two-photon blockade and anti-blockade effects are employed to produce sub-Poissonian and super-Poissonian light fields, respectively. The achievable quantum control paves the way towards the realization of a prototype of a quantum transistor which amplifies or attenuates the noise. Its feasibility is demonstrated by calculations using realistic parameters from recent experiments. / Nesta tese estudamos o controle da biestabilidade óptica absortiva em uma cavidade linear contendo uma coleção de átomos de dois e três níveis não interagentes fracamente acoplados a um único modo do campo. Mostramos que o controle para a configuração atômica de três níveis ocorre apenas nas condições de aprisionamento coerente de população e que o mesmo é sensível à coerência atômica induzida no sistema podendo ser manipulado através de diferentes parâmetros. Propomos algumas aplicações apresentando um efeito novo, o qual denominamos de biestabilidade óptica complementar, muito interessante para explorar dispositivos ópticos biestáveis com funções de cascatabilidade, como um transistor óptico. Estudamos também o controle óptico das flutuações do campo de prova pela combinação do fenômeno de transparência eletromagneticamente induzida para um único átomo no regime de acoplamento forte em eletrodinâmica quântica de cavidades. Especificamente, o campo de controle é utilizado para ajustar as frequências de transição dos estados vestidos ressonantemente ou quase ressonantemente com o campo de prova do sistema. Desta forma, efeitos de bloqueio de um e dois fótons e anti-bloqueio são observados produzindo campos sub- e super-Poissonianos, respectivamente. O controle quântico obtido pode ser promissor para a realização de um protótipo de um transistor quântico que amplifica e atenua flutuações quânticas do campo transmitido pelo sistema. A viabilidade desse dispositivo é demonstrada através de cálculos utilizando parâmetros de experimentos recentes.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Grades de Bragg nÃo-lineares tÃm sido consideradas desde o final do sÃculo passado para aplicaÃÃes em sistemas de comunicaÃÃes Ãpticas e sensoriamento. O estudo de pulsos ultra-curtos em grades de Bragg lineares, entretanto, sà tem sido considerado nos Ãltimos anos, devido ao desenvolvimento de tÃcnicas numÃricas especÃficas para se resolver o problema. Neste trabalho, foi realizado um estudo analÃtico-numÃrico das caracterÃsticas de transmissÃo e reflexÃo das grades de Bragg nÃo-lineares. Pela primeira vez, foram consideradas variaÃÃes periÃdicas da nÃo-linearidade no dispositivo operando no regime de onda continua, levando a uma nova classe de grades nÃo-uniformes. CaracterÃsticas dos estados bi- e multi-estÃveis foram extensamente investigados nas grades de Bragg nÃo-lineares. TambÃm, pela primeira vez, foi realizado o estudo numÃrico de pulsos ultracurtos ($sim$1 ps) incidindo em grades nÃo-lineares. O enfoque foi dado para a dependÃncia da intensidade de um pulso ultracurto ao passar por tal grade. Foram estudadas, ainda, as dependÃncias na forma temporal da profundidade de modulaÃÃo da grade e do Ãndice nÃo-linear. Grades apodizadas foram consideradas, jà que estas sÃo de importÃncia fundamental nos sitemas de comunicaÃÃes modernos. / Nonlinear fiber Bragg gratings has been considered since the end of last century for applications in optical communications and sensor techniques. The investigation of ultrashort pulses in linear Bragg gratings, however has been considered in the last few years due the development of specifical numerical techniques to solve this problem. In the present work an analytical and numerical study of the reflection and transmission characteristics of nonlinear Bragg gratings was done. For the first time, it has been considered periodic variations of the nonlinearity in that devices operating in the continuous wave regime, leading to a new class of nonuniform gratings. It was extensively investigated the bi- and multistable characteristics in these nonlinear fiber Bragg gratings. Also, for the first time, the numerical study of ultrahsort pulses ($sim$1 ps) incident in nonlinear gratings was done. The focus was the input pulse intensity dependence on that gratings. Also, the depedences in the time shapes of grating index modulation depth and nonlinear index were studied. Apodized gratings were considered since they are of fundamental importance in modern communications systems.

Indiana University-Purdue University Indianapolis (IUPUI) / Physical and biological phenomena that involve oscillations on multiple time scales attract attention of mathematicians because resulting equations include a small parameter that allows for decomposing a three- or higher-dimensional dynamical system into fast/slow subsystems of lower dimensionality and analyzing them independently using geometric singular perturbation theory and other techniques. However, in most life sciences applications observed dynamics is extremely complex, no small parameter exists and this approach fails. Nevertheless, it is still desirable to gain insight into behavior of these mathematical models using the only viable alternative – ad hoc computational analysis. Current dissertation is devoted to this latter approach. Neural networks in the region of the brain called basal ganglia (BG) are capable of producing rich activity patterns. For example, burst firing, i.e. a train of action potentials followed by a period of quiescence in neurons of the subthalamic nucleus (STN) in BG was shown to be related to involuntary shaking of limbs in Parkinson’s disease called tremor. The origin of tremor remains unknown; however, a few hypotheses of tremor-generation were proposed recently. The first project of this dissertation examines the BG-thalamo-cortical loop hypothesis for tremor generation by building physiologically-relevant mathematical model of tremor-related circuits with negative delayed feedback. The dynamics of the model is explored under variation of connection strength and delay parameters in the feedback loop using computational methods and data analysis techniques. The model is shown to qualitatively reproduce the transition from irregular physiological activity to pathological synchronous dynamics with varying parameters that are affected in Parkinson’s disease. Thus, the proposed model provides an explanation for the basal ganglia-thalamo-cortical loop mechanism of tremor generation. Besides tremor-related bursting activity BG structures in Parkinson’s disease also show increased synchronized activity in the beta-band (10-30Hz) that ultimately causes other parkinsonian symptoms like slowness of movement, rigidity etc. Suppression of excessively synchronous beta-band oscillatory activity is believed to suppress hypokinetic motor symptoms in Parkinson’s disease. Recently, a lot of interest has been devoted to desynchronizing delayed feedback deep brain stimulation (DBS). This type of synchrony control was shown to destabilize synchronized state in networks of simple model oscillators as well as in networks of coupled model neurons. However, the dynamics of the neural activity in Parkinson’s disease exhibits complex intermittent synchronous patterns, far from the idealized synchronized dynamics used to study the delayed feedback stimulation. The second project of this dissertation explores the action of delayed feedback stimulation on partially synchronous oscillatory dynamics, similar to what one observes experimentally in parkinsonian patients. We employ a computational model of the basal ganglia networks which reproduces the fine temporal structure of the synchronous dynamics observed experimentally. Modeling results suggest that delayed feedback DBS in Parkinson’s disease may boost rather than suppresses synchronization and is therefore unlikely to be clinically successful. Single neuron dynamics may also have important physiological meaning. For instance, bistability – coexistence of two stable solutions observed experimentally in many neurons is thought to be involved in some short-term memory tasks. Bistability that occurs at the depolarization block, i.e. a silent depolarized state a neuron enters with excessive excitatory input was proposed to play a role in improving robustness of oscillations in pacemaker-type neurons. The third project of this dissertation studies what parameters control bistability at the depolarization block in the three-dimensional conductance-based neuronal model by comparing the reduced dopaminergic neuron model to the Hodgkin-Huxley model of the squid giant axon. Bifurcation analysis and parameter variations revealed that bistability is mainly characterized by the inactivation of the Na+ current, while the activation characteristics of the Na+ and the delayed rectifier K+ currents do not account for the difference in bistability in the two models.

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