Embora a entropia do universo evolua para um máximo, localmente, sistemas podem se odernar às custas do maior desordenamento de suas vizinhanças. Assim, a formação espontânea de padrões temporais e espaciais tem sido observada em diferentes sistemas, incluindo os eletroquímicos. Neste trabalho foram estudadas as dinâmicas oscilatórias temporais de potencial desenvolvidas durante a eletro-oxidação galvanostática de metanol e etanol em meio ácido sobre eletrodos de platina. Como a técnica galvanostática informa apenas sobre a totalidade dos processos a ocorrer na interface eletrodo/solução técnicas auxiliares devem ser empregadas em conjunto para obter informações a respeito de processos individuais. Desta forma as técnicas de espectroscopia de infravermelho in situ, em configuração de reflexão interna, e de espectrometria de massas on line foram utilizadas e permitiram alcançar as seguintes conclusões. Para a eletro-oxidação oscilatória de metanol os resultados mostraram que (i) em média, o grau de recobrimento de monóxido de carbono linearmente adsorvido (θCOL) decai continuamente ao longo do experimento oscilatório, sugerindo que um acúmulo de espécies oxigenadas adsorvidas desenvolve-se ao longo das oscilações de potencial e é o responsável pela deriva que age sobre o sistema; (ii) a variação negativa da posição da banda de COL com o aumento do potencial durante o período de indução sugere que não há formação de padrões ou ilhas de COads previamente à observação de oscilações. Já os resultados da eletro-oxidação oscilatória de etanol mostraram (i) também uma queda contínua, em média, em θCOL ao longo do tempo bem como um crescimento, em média, da população de acetato adsorvido; (ii) para a condição oscilatória estudada a produção de CO2 seguiu a mesma dinâmica temporal das oscilações de potencial, já a corrente iônica associada à produção de acetaldeído permaneceu estacionária dentro do regime oscilatório. / Although the entropy of the universe evolves to a maximum, locally systems can become ordered at the expense of greater disordering of their neighborhoods. Thus, the spontaneous formation of temporal and spatial patterns have been observed in different systems, including electrochemical ones. In this thesis, the temporal dynamics of potential oscillations developed during the galvanostatic electro-oxidation of methanol and ethanol in acid medium on platinum electrodes were studied. As the galvanostatic technique informs just about all the processes occurring at the interface electrode/solution auxiliary techniques should be employed together to obtain information about individual processes. Thus the techniques of in situ infrared spectroscopy, in configuration of internal reflection, and online mass spectrometry were used and allowed to reach at the following conclusions. For the oscillatory electro-oxidation of methanol the results showed that (i) on average, the coverage degree of linearly adsorbed carbon monoxide (θCOL) decays continuously throughout the oscillatory experiment, suggesting that an accumulation of adsorbed oxygen species develops along the oscillations and causes the drift in the system, (ii) the negative change in the band position of COL with potential increasing during the induction period suggests that there is no tendency to pattern formation or islands formation of COads prior to the observation of oscillations. Concerning the oscillatory electro-oxidation of ethanol the results showed that (i) there is also a continuous drop on average in θCOL over time as well as an increase on average in the population of adsorbed acetate, (ii) for the oscillatory condition studied the production of CO2 followed the same temporal dynamics of the oscillations of potential, while the ionic current associated with the production of acetaldehyde remained stationary inside the oscillatory regime.

An investigation was conducted to determine and compare the effect of cell current pulsing and "self-oxidation" in increasing the CO tolerance of a PEM fuel cell. The most effective pulsing parameter values were also determined. Current pulsing involves periodically demanding positive current pulses from the fuel cell to create an anode over-potential, while "self-oxidation" or sustained potential oscillations is achieved when the anode catalyst becomes so saturated with CO that the anode over-potential increases to a value at which CO is oxidized from the catalyst surface. The CO tolerance of a fuel cell system with a Pt-Ru anode was tested using 50 and 496 ppm CO in the anode fuel. The performance of the system declined with an increase in CO concentration. Current pulses of various amplitude, frequency, and duty cycle were applied to the cell while CO was present in the anode fuel. With 50 ppm CO in the anode fuel, the most effective pulse in increasing CO tolerance while maintaining normal cell operation was 1.0 A/cm2, 0.25 Hz, and a 5% duty cycle. A pulse (120 Hz, 50% duty cycle) similar to the ripple current often generated when converting DC to single-phase 60 Hz AC had a positive effect on the CO tolerance of the system, but at frequencies that high, the pulse duration was not long enough to completely oxidize the CO from the catalyst surface. With 496 ppm CO in the anode fuel, a pulse of 1.0 A/cm2, 0.5 Hz, and a 20% duty cycle proved most effective. When the cell was exposed to 496 ppm CO, without employing pulsing, "self-oxidation" occurred and CO was periodically oxidized from the catalyst surface. However, pulsing allowed the cell to operate at the desired voltage and power a higher percentage of the time than "self-oxidation"; hence, pulsing was more effective.

Embora a entropia do universo evolua para um máximo, localmente, sistemas podem se odernar às custas do maior desordenamento de suas vizinhanças. Assim, a formação espontânea de padrões temporais e espaciais tem sido observada em diferentes sistemas, incluindo os eletroquímicos. Neste trabalho foram estudadas as dinâmicas oscilatórias temporais de potencial desenvolvidas durante a eletro-oxidação galvanostática de metanol e etanol em meio ácido sobre eletrodos de platina. Como a técnica galvanostática informa apenas sobre a totalidade dos processos a ocorrer na interface eletrodo/solução técnicas auxiliares devem ser empregadas em conjunto para obter informações a respeito de processos individuais. Desta forma as técnicas de espectroscopia de infravermelho in situ, em configuração de reflexão interna, e de espectrometria de massas on line foram utilizadas e permitiram alcançar as seguintes conclusões. Para a eletro-oxidação oscilatória de metanol os resultados mostraram que (i) em média, o grau de recobrimento de monóxido de carbono linearmente adsorvido (θCOL) decai continuamente ao longo do experimento oscilatório, sugerindo que um acúmulo de espécies oxigenadas adsorvidas desenvolve-se ao longo das oscilações de potencial e é o responsável pela deriva que age sobre o sistema; (ii) a variação negativa da posição da banda de COL com o aumento do potencial durante o período de indução sugere que não há formação de padrões ou ilhas de COads previamente à observação de oscilações. Já os resultados da eletro-oxidação oscilatória de etanol mostraram (i) também uma queda contínua, em média, em θCOL ao longo do tempo bem como um crescimento, em média, da população de acetato adsorvido; (ii) para a condição oscilatória estudada a produção de CO2 seguiu a mesma dinâmica temporal das oscilações de potencial, já a corrente iônica associada à produção de acetaldeído permaneceu estacionária dentro do regime oscilatório. / Although the entropy of the universe evolves to a maximum, locally systems can become ordered at the expense of greater disordering of their neighborhoods. Thus, the spontaneous formation of temporal and spatial patterns have been observed in different systems, including electrochemical ones. In this thesis, the temporal dynamics of potential oscillations developed during the galvanostatic electro-oxidation of methanol and ethanol in acid medium on platinum electrodes were studied. As the galvanostatic technique informs just about all the processes occurring at the interface electrode/solution auxiliary techniques should be employed together to obtain information about individual processes. Thus the techniques of in situ infrared spectroscopy, in configuration of internal reflection, and online mass spectrometry were used and allowed to reach at the following conclusions. For the oscillatory electro-oxidation of methanol the results showed that (i) on average, the coverage degree of linearly adsorbed carbon monoxide (θCOL) decays continuously throughout the oscillatory experiment, suggesting that an accumulation of adsorbed oxygen species develops along the oscillations and causes the drift in the system, (ii) the negative change in the band position of COL with potential increasing during the induction period suggests that there is no tendency to pattern formation or islands formation of COads prior to the observation of oscillations. Concerning the oscillatory electro-oxidation of ethanol the results showed that (i) there is also a continuous drop on average in θCOL over time as well as an increase on average in the population of adsorbed acetate, (ii) for the oscillatory condition studied the production of CO2 followed the same temporal dynamics of the oscillations of potential, while the ionic current associated with the production of acetaldehyde remained stationary inside the oscillatory regime.

Deep brain stimulation (DBS) of the subthalamic nucleus (STN) and DBS of the pedunculopontine nucleus (PPN) have been shown to be effective surgical therapies for Parkinson’s disease (PD). To better understand the PPN and STN as DBS targets for PD, this research compares the anatomy, electrophysiology, and motor control roles of these nuclei. PPN and STN connections were examined in vivo in human subjects and in the non-human primate using probabilistic diffusion tractography. Both the PPN and STN were connected with each other and with the motor cortex (M1) and basal ganglia. After studying these anatomical connections in primates, their functional significance was further explored in an anesthetized rat model of PD. Examination of the electrophysiological relationship between the PPN and basal ganglia in the presence of slow cortical oscillatory activity suggested that excitatory input from the STN may normally modulate PPN spike timing but that inhibitory oscillatory input from the basal ganglia output nuclei has a greater effect on PPN spike timing in the parkinsonian brain. To examine transmission and modulation of oscillatory activity between these structures at higher frequencies, LFP activity was recorded from the PPN and STN in PD patients performing simple voluntary movements. Movement-related modulation of oscillatory activity predominantly occurred in the α (8-12 Hz) and low β (12-20 Hz) frequencies in the STN but in the high β (20-35 Hz) frequencies in the PPN, supporting observations from rodent studies suggesting that oscillatory activity is not directly transmitted from the STN to the PPN in PD. Finally, to better understand the roles of the STN and PPN in large-scale movement, the effects of STN and PPN DBS on gait abnormalities in PD patients were studied. DBS of the STN appeared to improve gait by optimising executive gait control while DBS of the PPN appeared to restore autonomic gait control. These results have several implications for DBS patient selection, surgical targeting, and for understanding the mechanisms underlying DBS efficacy.

Les mécanismes cellulaires et moléculaires qui sous-tendent la mémoire et l’apprentissage chez les mammifères sont incomplètement compris. Le rythme thêta de l’hippocampe constitue l’état « en ligne » de cette structure qui est cruciale pour la mémoire déclarative. Dans la région CA1 de l’hippocampe, les interneurones inhibiteurs LM/RAD démontrent des oscillations de potentiel membranaire (OPM) intrinsèques qui pourraient se révéler importantes pour la génération du rythme thêta. Des travaux préliminaires ont suggéré que le courant K+ I(A) pourrait être impliqué dans la génération de ces oscillations. Néanmoins, peu de choses sont connues au sujet de l’identité des sous-unités protéiques principales et auxiliaires qui soutiennent le courant I(A) ainsi que l’ampleur de la contribution fonctionnelle de ce courant K+ dans les interneurones. Ainsi, cette thèse de doctorat démontre que le courant I(A) soutient la génération des OPM dans les interneurones LM/RAD et que des protéines Kv4.3 forment des canaux qui contribuent à ce courant. De plus, elle approfondit les connaissances sur les mécanismes qui régissent les interactions entre les sous-unités principales de canaux Kv4.3 et les protéines accessoires KChIP1. Finalement, elle révèle que la protéine KChIP1 module le courant I(A)-Kv4.3 natif et la fréquence de décharge des potentiels d’action dans les interneurones. Nos travaux contribuent à l’avancement des connaissances dans le domaine de la modulation de l’excitabilité des interneurones inhibiteurs de l’hippocampe et permettent ainsi de mieux saisir les mécanismes qui soutiennent la fonction de l’hippocampe et possiblement la mémoire chez les mammifères. / Cellular and molecular mechanisms underlying learning and memory in mammals are incompletely understood. The theta rhythm in the hippocampus constitutes the « on-line » state of this structure which is crucial for declarative memory. In the CA1 hippocampal area, LM/RAD inhibitory interneurons exhibit intrinsic membrane potential oscillations (MPOs) that could be important for the generation of theta rhythm. Preliminary work suggested that K+ current I(A) could be involved in the generation of these oscillations. Nevertheless, little is known about the identity of the principal and auxiliary protein subunits underlying I(A) current and the extent of the functional contribution of this K+ current in hippocampal interneurons. Thus, this Ph.D. thesis shows that I(A) current underlies MPO generation in LM/RAD interneurons and that Kv4.3 proteins form channels that contribute to this current. Also, it deepens the knowledge on the mechanism controlling the interactions between Kv4.3 channel-forming principal subunits and KChIP1 auxiliary proteins. Finally, it reveals that KChIP1 modulates native I(A)-Kv4.3 current and the action potential discharge frequency in interneurons. Our work takes part in advancing the knowledge on the field of modulation of excitability in hippocampal inhibitory interneurons and allows a better understanding of the mechanisms underlying the function of the hippocampus and possibly memory in mammals.

Rhythmische neuronale Aktivität spielt vermutlich eine wichtige Rolle in der Informationsverarbeitung im zentralen Nervensystem. Oszillationen neuronaler Netze sind heterogen, von der Hirnregion und ihrer Funktion abhängig und werden entsprechend ihrer Frequenz eingeteilt. Für ihre Entstehung sind über die Verschaltung der Neuronen und der synaptischen Übertragung hinaus insbesondere die Erregbarkeit und Oszillationseigenschaften einzelner Neurone von Bedeutung. Bestimmte Zellen der hippokampalen Formation wie zum Beispiel Sternzellen (SC) der Schicht II des Entorhinalkortex zeigen oszillatorische Aktivität und antworten verstärkt auf Stimuli einer bestimmten Frequenz – sie sind resonant. Beide Phänomene werden auf spezifische spannungsabhängige Leitfähigkeiten in der Membran zurückgeführt. Es stellte sich heraus, dass die Resonanzfrequenz von SCs durch das Muster der vorhandenen Leitfähigkeiten bestimmt wird und von der Position der Zelle entlang der dorso-ventralen Achse abhängt. Dieser Gradient ist bereits in frühen Entwicklungsstadien nachweisbar. Im Zuge der weiteren Entwicklung werden SCs weniger erregbar und der Bereich der Resonanzfrequenz dehnt sich nach dorsal aus. Pharmakologische Experimente ergaben, dass die Resonanz von SCs von HCN-Kanälen abhängt und von Kv7-Kanälen moduliert wird. Außerdem konnten zwei, bisher unbekannte Klassen von oszillatorischen Interneuronen beschrieben werden, deren Resonanz ebenfalls im Theta-Bereich liegt und auf ähnliche Leitfähigkeiten zurückgeführt werden kann. Weitere, auch CA1-Pyramidenzellen einschließende Experimente ergaben, dass HCN-Kanäle die allgemeine Voraussetzung für Resonanz zu sein scheinen während Kv7-Kanäle potente Modulatoren darstellen. Die pharmakologische Blockade dieser Kanäle unterbrach Netzwerkoszillation im Hippokampus. Dies unterstützt die These, dass bestimmte Leitfähigkeiten Neuronen Resonanzeigeschaften verleihen und somit wiederum Netzwerkoszillationen unterstützen. / Rhythmic neuronal activity is thought to be crucial for information processing in the brain. Neuronal network oscillations are heterogeneous, vary with brain region and type of information processed. They are classified according to their frequency content. Their generation relies on network circuitry, synaptic transmission and neuronal properties. Oscillatory behavior of individual cells has been particularly implicated. Different cell types within the hippocampal formation such as layer II stellate cells (SC) of the medial entorhinal cortex display oscillatory activity and are resonant, i.e., respond preferentially to stimuli of a given frequency. Voltage dependent ionic conductances have been suggested to give rise to these phenomena. It was found that resonance of SCs is defined by the composition of voltage-dependent channels embedded in their membrane and changes with their position along the dorsal-ventral axis. This gradient of SC properties develops during early postnatal life. During the transition to adulthood cells become less excitable and the range of resonance frequencies expands in the dorsal direction. Pharmacological experiments reveal the resonance of SCs to depend strongly on HCN-channels and to be modulated by Kv7-channels. Also, two previously unknown classes of oscillating interneurons were identified in the stratum radiatum of the CA1 region. These are targeted by neurons from the dentate gyrus, display frequency preferences in the theta range which relies on similar membrane conductances. Further experiments including CA1 pyramidal cells suggested HCN-channels to be the primary global requirement for resonance whereas Kv7-channels appear to be effective modulators. Pharmacological blockade of these channels disrupted ongoing network oscillations in the hippocampus. This supports the notion that specific ion channels support rhythmic activity of individual cells and in turn of entire networks.

<p>Self-oscillating behaviour in alkaline Cu(II)-lactate and -tartrate systems has been investigated by in-situ pH and confocal Raman spectroscopy measurements. Formation of Cu(II)-lactate and -tartrate complexes is a key factor underlying the self-oscillations. Dynamic processes in the diffusion layer have been probed to give a better understanding of the self-oscillating process.</p><p>The self-oscillating behaviour is found to be an effect of pH variations in the diffusion layer. Mainly copper is deposited at lower pH values and potentials; at the same time, the pH increases. This is an effect of the dissociation of the Cu(II)-complex during electrochemical reduction. The absence of a buffer within a given pH region is crucial to the fast and sudden pH increase and thereby to the positive potential shift, where cuprous oxide is deposited. A precipitation reaction probably decreases the pH again, leading to a negative potential shift, and copper again begins to deposit. The concentration and strength of the buffer in the electrolyte affect the appearance of the oscillation pattern. The pH and temperature of the bulk electrolyte also influence the self-oscillations. The deposit consists of copper and cuprous oxide, where the composition of the phases deposited is a function of the working-electrode potential. Cuprous oxide is deposited at the higher potentials and mainly copper at the lower potentials.</p><p>Finally, two-dimensional arrays of Cu/Cu₂O microcylinders have been deposited using the Cu(II)-lactate system through the application of a template method.</p>

Self-oscillating behaviour in alkaline Cu(II)-lactate and -tartrate systems has been investigated by in-situ pH and confocal Raman spectroscopy measurements. Formation of Cu(II)-lactate and -tartrate complexes is a key factor underlying the self-oscillations. Dynamic processes in the diffusion layer have been probed to give a better understanding of the self-oscillating process. The self-oscillating behaviour is found to be an effect of pH variations in the diffusion layer. Mainly copper is deposited at lower pH values and potentials; at the same time, the pH increases. This is an effect of the dissociation of the Cu(II)-complex during electrochemical reduction. The absence of a buffer within a given pH region is crucial to the fast and sudden pH increase and thereby to the positive potential shift, where cuprous oxide is deposited. A precipitation reaction probably decreases the pH again, leading to a negative potential shift, and copper again begins to deposit. The concentration and strength of the buffer in the electrolyte affect the appearance of the oscillation pattern. The pH and temperature of the bulk electrolyte also influence the self-oscillations. The deposit consists of copper and cuprous oxide, where the composition of the phases deposited is a function of the working-electrode potential. Cuprous oxide is deposited at the higher potentials and mainly copper at the lower potentials. Finally, two-dimensional arrays of Cu/Cu2O microcylinders have been deposited using the Cu(II)-lactate system through the application of a template method.

Les mécanismes cellulaires et moléculaires qui sous-tendent la mémoire et l’apprentissage chez les mammifères sont incomplètement compris. Le rythme thêta de l’hippocampe constitue l’état « en ligne » de cette structure qui est cruciale pour la mémoire déclarative. Dans la région CA1 de l’hippocampe, les interneurones inhibiteurs LM/RAD démontrent des oscillations de potentiel membranaire (OPM) intrinsèques qui pourraient se révéler importantes pour la génération du rythme thêta. Des travaux préliminaires ont suggéré que le courant K+ I(A) pourrait être impliqué dans la génération de ces oscillations. Néanmoins, peu de choses sont connues au sujet de l’identité des sous-unités protéiques principales et auxiliaires qui soutiennent le courant I(A) ainsi que l’ampleur de la contribution fonctionnelle de ce courant K+ dans les interneurones. Ainsi, cette thèse de doctorat démontre que le courant I(A) soutient la génération des OPM dans les interneurones LM/RAD et que des protéines Kv4.3 forment des canaux qui contribuent à ce courant. De plus, elle approfondit les connaissances sur les mécanismes qui régissent les interactions entre les sous-unités principales de canaux Kv4.3 et les protéines accessoires KChIP1. Finalement, elle révèle que la protéine KChIP1 module le courant I(A)-Kv4.3 natif et la fréquence de décharge des potentiels d’action dans les interneurones. Nos travaux contribuent à l’avancement des connaissances dans le domaine de la modulation de l’excitabilité des interneurones inhibiteurs de l’hippocampe et permettent ainsi de mieux saisir les mécanismes qui soutiennent la fonction de l’hippocampe et possiblement la mémoire chez les mammifères. / Cellular and molecular mechanisms underlying learning and memory in mammals are incompletely understood. The theta rhythm in the hippocampus constitutes the « on-line » state of this structure which is crucial for declarative memory. In the CA1 hippocampal area, LM/RAD inhibitory interneurons exhibit intrinsic membrane potential oscillations (MPOs) that could be important for the generation of theta rhythm. Preliminary work suggested that K+ current I(A) could be involved in the generation of these oscillations. Nevertheless, little is known about the identity of the principal and auxiliary protein subunits underlying I(A) current and the extent of the functional contribution of this K+ current in hippocampal interneurons. Thus, this Ph.D. thesis shows that I(A) current underlies MPO generation in LM/RAD interneurons and that Kv4.3 proteins form channels that contribute to this current. Also, it deepens the knowledge on the mechanism controlling the interactions between Kv4.3 channel-forming principal subunits and KChIP1 auxiliary proteins. Finally, it reveals that KChIP1 modulates native I(A)-Kv4.3 current and the action potential discharge frequency in interneurons. Our work takes part in advancing the knowledge on the field of modulation of excitability in hippocampal inhibitory interneurons and allows a better understanding of the mechanisms underlying the function of the hippocampus and possibly memory in mammals.

Gamma oscillations of local field potentials (LFP) in the basal ganglia and thalamus had not been studied during saccades. Eleven patients were studied during deep brain stimulation (DBS); 6 were in the subthalamic nucleus (STN); 3 in the globus pallidus interna (GPi); and 2 in the thalamic ventralis intermedius nucleus (Vim). Patients performed horizontal saccades to visual targets while LFPs from DBS electrodes, scalp electroencephalogram (EEG), and electrooculogram (EOG) were recorded. Wavelet spectrograms were generated and saccade onset and event-related gamma synchronizations (ERS) were compared to baseline without eye motion. ERS were recorded at and after saccade onset in the STN, GPi and Vim, EEGs and EOGs; but were absent during target light illumination without saccades. ERS were symmetric in all DBS contacts and appeared identical in DBS LFPs, frontal EEGs and EOGs. These findings indicate their origin from extraocular muscle spike potentials rather than brain neural activity.