As reações químicas genericamente referidas como reações de Belousov-Zhabotinsky (BZ) têm sido bastante utilizadas como paradigmas de complexidade em sistemas químicos homogêneos. Apesar dos avanços consideráveis realizados no estudo de tais sistemas, aspectos como o papel do fluxo de reagentes e da temperatura na dinâmica oscilatória ainda são pouco entendidos. O presente trabalho consiste na investigação experimental do efeito destes dois parâmetros em duas variantes da reação de BZ. Após alguns testes iniciais com o sistema bromato/hipofosfito-acetona/manganês-ferroína, a maioria dos experimentos foi feita com o sistema bromato/ácido oxálico-acetona/cério. A evolução temporal do sistema foi estudada a diferentes temperaturas e em condições de batelada e de fluxo por meio do monitoramento simultâneo do potencial de um eletrodo de platina e espectrofotometricamente na região do UV-vis. A discussão foi baseada na energia de ativação em regime oscilatório, Eω. Para o sistema com dois catalisadores não foram observadas oscilações nas condições de fluxo. Para o sistema com cério, em batelada, com Ce4+ é observado que Eω aumenta conforme o sistema evolui para o estado de equilíbrio termodinâmico. Com Ce3+, em batelada, Eω manteve-se praticamente constante e em fluxo, o valor de Eω foi menor do que o valor observado para o sistema em batelada. / The chemical reactions usually referred to as the Belousov-Zhabotinsky (BZ) reactions have been extensively employed as paradigms of complexity in homogeneous chemical systems. In spite of the considerable advance in the study of such systems, aspects such as the role played by the flux of reactants and temperature on the oscillatory dynamics are still poorly understood. The present work consists of the experimental investigation of the effect of these two parameters on two variants of the BZ reaction. After some initial tests with the bromate/hipophosphite-acetone/manganese-ferroin, most of the experiments were carried with the bromate/oxalic acid-acetone/cerium system. The time-evolution of the system was followed at different temperatures and under batch and flow conditions by means of potentiometric and spectrophotometric (UV-vis region) approaches. The discussion was based on the activation energy under oscillatory regime, Eω. For the two-catalyst system, no oscillations were observed under flow conditions. For the cerium-catalyzed system operated in batch, when Ce4+ is used, it is observed that Eω increases as the system evolves to the thermodynamic equilibrium. With Ce3+, the Eω under batch conditions remained virtually constant and in flow, the value of Eω was lower than the value observed for the batch system.

As reações químicas genericamente referidas como reações de Belousov-Zhabotinsky (BZ) têm sido bastante utilizadas como paradigmas de complexidade em sistemas químicos homogêneos. Apesar dos avanços consideráveis realizados no estudo de tais sistemas, aspectos como o papel do fluxo de reagentes e da temperatura na dinâmica oscilatória ainda são pouco entendidos. O presente trabalho consiste na investigação experimental do efeito destes dois parâmetros em duas variantes da reação de BZ. Após alguns testes iniciais com o sistema bromato/hipofosfito-acetona/manganês-ferroína, a maioria dos experimentos foi feita com o sistema bromato/ácido oxálico-acetona/cério. A evolução temporal do sistema foi estudada a diferentes temperaturas e em condições de batelada e de fluxo por meio do monitoramento simultâneo do potencial de um eletrodo de platina e espectrofotometricamente na região do UV-vis. A discussão foi baseada na energia de ativação em regime oscilatório, Eω. Para o sistema com dois catalisadores não foram observadas oscilações nas condições de fluxo. Para o sistema com cério, em batelada, com Ce4+ é observado que Eω aumenta conforme o sistema evolui para o estado de equilíbrio termodinâmico. Com Ce3+, em batelada, Eω manteve-se praticamente constante e em fluxo, o valor de Eω foi menor do que o valor observado para o sistema em batelada. / The chemical reactions usually referred to as the Belousov-Zhabotinsky (BZ) reactions have been extensively employed as paradigms of complexity in homogeneous chemical systems. In spite of the considerable advance in the study of such systems, aspects such as the role played by the flux of reactants and temperature on the oscillatory dynamics are still poorly understood. The present work consists of the experimental investigation of the effect of these two parameters on two variants of the BZ reaction. After some initial tests with the bromate/hipophosphite-acetone/manganese-ferroin, most of the experiments were carried with the bromate/oxalic acid-acetone/cerium system. The time-evolution of the system was followed at different temperatures and under batch and flow conditions by means of potentiometric and spectrophotometric (UV-vis region) approaches. The discussion was based on the activation energy under oscillatory regime, Eω. For the two-catalyst system, no oscillations were observed under flow conditions. For the cerium-catalyzed system operated in batch, when Ce4+ is used, it is observed that Eω increases as the system evolves to the thermodynamic equilibrium. With Ce3+, the Eω under batch conditions remained virtually constant and in flow, the value of Eω was lower than the value observed for the batch system.

This dissertation investigates the self assembly and automatic oscillation of intelligent poly (N-isopropylacrylamide) [PNIPAM] microgel particles. The equilibrium phase diagram as a function of temperature and concentration was constructed for the charged PNIPAM spheres. The PNIPAM microgel particles display rhythmic size oscillations when covalently coupled to a nonlinear chemical reaction, the Belousov-Zhabotinsky (BZ) reaction. The nonequilibrium dynamics of PNIPAM microgels in the presence of BZ reaction was studied by the systematic variation of substrate concentrations and temperature. In addition, the BZ chemical reaction was modeled to reveal the existence of upper temperature limits for nonlinear chemical systems. The experiments employ environment sensitive PNIPAM particles that are sensitive to temperature, pH, and ionic strength. The PNIPAM particles have been demonstrated here to behave as hard spheres at low pH values and soft spheres at high pH. This is done by measuring the freezing and melting boundary of fluid-crystal coexistence region with a new technique which is simpler and quicker compared to the traditional sedimentation method. A novel method was developed to achieve size uniformity of PNIPAM gel particles with covalently-bound tris(bipyridyl)ruthenium(II) via the coordination chemistry between a ruthenium complex and the monodispersed PNIPAM gel particles bearing bipyridine ligands. The correlation between the dynamic behavior of BZ reaction induced mechanical oscillations of PNIPAM particles and substrate concentrations was presented in a ternary phase diagram. In particular, the dependence of oscillation frequency and induction time on the substrate concentrations was studied. The temperature dependency of the induction time and oscillatory frequency of the BZ reaction in this polymerimmobilized catalyst system were compared to the bulk BZ reaction with the catalyst in the solution phase. Prolonged induction times were observed for the immobilized catalyst, compared with free catalyst, while little difference was observed on the oscillation frequency. A theoretical improvement has been achieved by incorporating the temperature dependence in the BZ Oregonator model. Bifurcation has been calculated in the phase space spanned by initial reagents concentration ratio, stoichiometric factor and temperature. The existence of upper temperature limits has been demonstrated.

Self-oscillating reactions have been widely observed and studied since the last century because they exhibit unique behaviors different from the traditional chemical reactions. Self-oscillating systems, such as the Belousov-Zhabotinsky (BZ) reaction, oxidation reaction of CO on single crystal Pt, and calcium waves in the heart tissue, are of great interest in a variety of scientific areas. This thesis contributes to the understanding of wave transition in BZ reaction, and to possible applications of non-equilibrium behaviors of polymer systems. In BZ reaction, two types of wave patterns, target and spiral, are frequently observed. The transition from one to another is not fully understood. Hence, a systematic investigation has been performed here to investigate the mechanism by which heterogeneity affects the formation of wave patterns. A BZ reaction catalyst was immobilized in ion exchange polystyrene beads to form active beads. Then active and inactive beads with no catalyst loading were mixed together with various ratios to achieve various levels of heterogeneity. In the same reaction environment, different wave patterns were displayed for the bead mixtures. We observed a transition from target patterns to spiral patterns as the percentage of the active beads in the beads mixture decreased. The increase of the heterogeneity led to wave pattern transition. Heterogeneity hindered the propagation of target waves and broke them into wavelets that generated spiral waves. In an effort to develop practical applications based on non-equilibrium phenomena, we have established a novel drug delivery system. A proton generator Zirconium Phosphate (ZrP) was imbedded inside a pH sensitive polymer matrix, poly acrylic acid (PAA). Through the ion exchange with sodium cation (Na+), ZrP generates protons to control the swelling/shrinking behaviors of PAA. The drug encapsulated in the matrix can be released in a controlled manner by adjusting the supply of Na+. This system might be developed into vehicles to deliver drugs to specific targets and release at a proper time. This new delivery technique will be convenient and significantly increase the efficiency of medicines.

La génération, propagation et la réception d’informations (bio/chimiques) entre les organismes individuels sont la clé de voûte de nombreux systèmes communicants intelligents et sont omniprésents dans la nature. Les colonies de lucioles synchronisent leurs flashs, et la contraction et l’expansion des muscles cardiaques sont quelques exemples parmi d’autres, où les signaux bio / chimiques générés par des sources synchronisées produisent un comportement coopératif. L’objectif final de cette thèse est de développer une plateforme fiable pour générer des réseaux de communication de liposomes, en encapsulant la réaction de Belousov-Zhabotinsky (BZ) en tant que source d’information ou un signal transmis, et d’étudier la dynamique d’un tel système. Pour atteindre cet objectif, plusieurs questions ont été abordées par une approche “bottom-up” et multi-échelle. Tout d’abord, nous avons étudié l’interaction entre des liposomes de DMPC dopés et non-dopés avec le cholestérol, l’acide myristique, tétradécylsulfate, tétradécylamine, et les espèces impliquées dans la reaction BZ en utilisant la diffusion de rayons X aux petits angles et par spectrophotométrie UV-visible. Des rangées 1D de micro-gouttelettes ont été fabriquées en encapsulant la réaction BZ en microgouttelettes au moyen de la microfluidique et la communication entre les gouttelettes adjacentes a été étudiée. Plus tard, nous avons démontré un système microfluidique facile à monter / démonter avec une conception robuste et une géométrie modulable pour générer des emulsions doubles d’eau dans l’huile dans l’eau (E/ H / O). Enfin, le comportement de ces doubles emulsions générées dans système microfluidique en utilisant des phosphoplipides comme tensioactif et du chloroforme comme phase huileuse, est rapporté. Nous avons montré, avec cette composition de la phase d’huile, que le comportement dynamique des émulsions doubles sous écoulement donne lieu à des phénomènes riches incluant la déformation et du “tip-streaming”. / Generation, propagation and reception of (bio/chemical) information between individual organisms are the keystone of many intelligent communicating systems, and are ubiquitous in Nature. Colonies of fireflies synchronize their flashes, and contraction and expansion of heart muscles are few examples among others, where bio/chemical signals generated by synchronized sources produce a cooperative behaviour. The final objective of this thesis is to develop a reliable platform for generating communicative networks of liposomes, encapsulating the Belousov-Zhabotinsky (BZ) reaction as source of information or transmitted signals, and to study the dynamics of such a system. To reach this goal, several issues were addressed by following bottom-up and multi-scale approaches. First we investigated the interaction between both bulk DMPC liposomes, and liposomes doped with cholesterol, myristic acid, tetradecylsulfate, tetradecylamine, and the species involved in the BZ-reaction by using small angle X-ray scattering (SAXS) and UV-visible spectrophotometry. Than 1D arrays of micro-droplets were fabricated by encapsulating the BZ reaction into microdroplets by means of microfluidics, and the communication between adjacent droplets was studied. Later, we demonstrated an easy to assemble/disassemble and robust design for a microfluidic device with adjustable geometry, for generating monodisperse water-in-oil-in-water (w/o/w) double emulsions. Finally, the behavior of w/o/w double emulsions generated in a microfluidic device, using phospholipids as surfactant and chloroform as the oil phase, was reported. We showed, with this composition of the oil phase, that the dynamic behaviour of the double emulsions under flow gave rise to different phenomena, such as deformation and tip-streaming.

On caractérise les milieux excitables par le fait qu'ils présentent un point d'équilibre linéairement stable et qu'une perturbation finie peut entraîner une longue excursion dans l'espace des phases. Les comportements de tels milieux sont en général bien approchés par des modèles simplifiés de réaction-diffusion a deux variables. Des exemples de milieux excitables sont le coeur, les axones neuronaux et la réaction de Belousov-Zhabotinsky dans les gels. On peut y observer des ondes d'excitation planes et spirales. Ce mémoire est consacré à l'étude numérique de la dynamique des filaments (ondes spirales empilées le long du filament) d'ondes spirales, éventuellement twistés, dans les milieux excitables. Dans un premier temps on calcule les états stationnaires par une méthode de Newton, puis on étudie la stabilité linéaire de ces états vis à vis de perturbations modulées suivant l'axe du filament par une méthode itérative, enfin on détermine les états restabilisés, quand ils existent, à l'aide de simulations numériques directes. L'étude des filaments non twistés met en évidence deux instabilités distinctes. L'une due à la déstabilisation de la branche de méandre (modulation périodique du rayon de rotation de la spirale) aboutit à un état restabilisé que nous caractérisons précisément. Cette instabilité correspond à une bifurcation de Hopf. L'autre correspond à une déstabilisation des modes de translation et aboutit à un état désordonné. L'étude de l'influence du twist sur la dynamique des filaments de spirales montre que le twist induit une déstabilisation des modes de translation à nombre d'onde fini. Cette bifurcation de Hopf correspond à la transformation du twist imposé au filament en Writhe (déformation géométrique). Le filament prend, dans les cas simples, une forme hélicoïdale. Dans des cas plus compliqués il prend une forme invariante dans le temps qui est la somme de plusieurs hélices. Une analogie avec une tige élastique soumise à la torsion est présentée.