Artificial photosynthesis is often considered to have great potential to provide alternative, renewable fuels by harvesting, conversion and storage of solar energy. One promising approach is the development of modular molecular photocatalysts inspired by natural photosynthetic enzymes. The first part of this thesis deals with artificial mimics of the water oxidizing photosystem II composed of a chromophore and an electron relay as synthetic counterpart of the P680-TyrZ/His190 ensemble of photosystem II. Three ruthenium polypyridyl - imidazole - phenol complexes with varying position of a methyl group on the phenol ring (Ru-xMe) were synthesized and characterized by electrochemical and photophysical methods. As an improvement compared to earlier complexes the increased redox potential (~0.9 V vs. Ferrocene) of the phenol groups makes their function as an electron relay in a photocatalytic system for water oxidation thermodynamically possible. Time-resolved absorption studies revealed fast intramolecular electron transfer (<5-10 µs in aprotic solvent and <100 ns in water) despite the low driving force and the importance of the hydrogen bond between the phenol and the imidazole group was put in evidence. Slight differences between the three Ru-xMe complexes and investigation of the effect of external bases allowed to derive a mechanistic picture in which the imidazole is involved in a "proton domino" reaction. Accepting the phenolic proton upon ligand oxidation (within the H-bond) renders its second nitrogen site more acidic and only deprotonation of this site pulls the overall equilibrium completely towards oxidation of the ligand. Another part of this thesis comprises a chromophore-tryptophan construct synthesized using a click chemistry approach. Light-induced oxidation of Trp in this Ru-tryptophan complex was shown to follow ETPT mechanism. Depending on the pH conditions tryptophan radicals, either Trp* or TrpH*⁺ were detected and spectral measurement at different time showed the transition between the two forms. Deprotonation of the radical was dependent on the concentration of water as proton acceptor. Later part of the thesis deals with efforts to covalently bind a catalytic unit to the previously characterized chromophore-electron relay module. The click chemistry approach was not successful to obtain the final photocatalytic assembly. Therefore bimolecular activation of a Mn salen catalyst was performed and formation of Mn(IV) species was observed. As a step towards utilization of these types of photocatalysts in a photoelectrochemical cell a [Ru(bpy)₃]²⁺ chromophore with phosphonate anchoring groups (Ru-Phosphonate) was synthesized and grafted on the surface of a TiO₂ mesoporous semiconductor surface anode to perform photocurrent measurements.

While signatures of attention can be observed in widespread areas within and outside of cortex, the control of attention is thought to be regulated by higher cognitive brain areas, such as the prefrontal cortex. In their recent study on mice Kim et al. could show that successful allocation of attention is characterized by increased spiking of a specific type of inhibitory interneurons, the parvalbumin neurons, and higher oscillatory activity in the gamma band in the local prefrontal network. It was recently demonstrated that encoding of working memory in prefrontal areas is linked to bursts of gamma oscillations, a discontinuous network process characterized by short periods of intense power in the gamma band. The relationship between attention and working memory is unclear, and it is possible that these two cognitive processes share encoding principles. To address this gap, the electrophysiological data collected in the Carlén Lab have been analyzed with advanced spatio-temporal approaches. In particular, we have analyzed bursting gamma activity in medial prefrontal cortex during attentional processing and investigated the similarities to gamma bursting observed during working memory. Gamma-band bursts during attention were reliably detected with several methods. We have characterized several features of the bursts, including the occurrence, duration and amplitude. The neuronal firing rates during and outside of bursts have also been computed. We investigated the correlation between different criteria characterizing the gamma burst and successful vs failed allocation of attention. Control data were generated to discuss the obtained results. The aim of the study was to explore the hypothesis that the medial prefrontal cortex encodes attention trough gamma bursts, which could reveal some similarities and differences in coding of central cognitive processes. No clear difference was found in the characterization between successful and failed allocation of attention. In addition, results were very similar in control set and original data. No underlying mechanism could be identified from this analysis. Therefore, as the bursts occurring in the gamma band in the prefrontal cortex (PFC) were not discriminative with respect to the different tested conditions, they do not seem to encode information related to attention. / Även fast flera olika hjärnområdens aktivitet kan korreleras med uppmärksamhet, anses kontrollen av uppmärksamhet regleras av högre kognitiva hjärnområden, såsom främre hjärnbarken. I en nyligen publicerad artikel studerade Kim et al. hjärnaktiviteten hos möss och kunde visa att en framgångsrik uppmärksamhet kännetecknas av en ökad aktivitet av en specifik typ av inhiberande nervceller, parvalbumin celler, och högre oscillerande aktivitet i gammafrekvens i främre hjärnbarkens lokala nätverk. Det har nyligen visats att kodning av arbetsminne i främre hjärnbarken är kopplat till utbrott av gamma-oscillationer, en diskontinuerlig nätverksprocess som kännetecknas av korta perioder av intensiva oscillationer av det lokala nätverket i gammafrekvens . Relationen mellan uppmärksamhet och arbetsminne är oklar, och det är möjligt att dessa två kognitiva processer delar kodningsprinciper. För att minska detta gap av kunskap har den elektrofysiologiska datan som samlats in i Carlén Lab analyserats med avancerade spatio-temporala tillvägagångssätt. I synnerhet har vi analyserat utbrott i gammaaktivitet i främre hjärnbarken under uppmärksamhet och undersökt likheterna med gamma- utbrott observerade under arbetsminne. Gamma-bandutbrott under uppmärksamhet påvisades på ett tillförlitligt sätt med flera metoder. Vi har karaktäriserat flera funktioner hos utbrotten, inklusive förekomsten, varaktigheten och amplituden. De enskilda cellernas aktivitet undersöktes även under och utanför utprotten av gamma-oscillationer. Vi undersökte sambandet mellan de olika kriterier som karakteriserar gamma-utbrott under framgångsrik mot misslyckad allokering av uppmärksamhet. Kontrolldata genererades för att diskutera de erhållna resultaten. Syftet med studien var att utforska hypotesen att den främre hjärnbarken kodar uppmärksamhet genom gamma-utbrott, vilket kan avslöja vissa likheter och skillnader i kodning av centrala kognitiva processer. Ingen klar skillnad hittades i karaktäriseringen mellan framgångsrik och misslyckad allokering av uppmärksamhet. Dessutom var resultaten mycket likartade i kontrolluppsättningen och den ursprungliga datan. Ingen underliggande mekanism kunde identifieras ur denna analys. Eftersom de utbrott som uppstod i gamma-bandet i främre hjärnbarken inte var unika med hänsyn till de olika testade förhållandena, tycks de därför inte koda information relaterad till uppmärksamhet.

La photosynthèse artificielle est considérée comme étant un atout capable de fournir des carburants alternatifs et renouvelables par conversion et stockage de l'énergie solaire. Une approche prometteuse consiste en un développement de photo-catalyseurs moléculaires inspirés par des enzymes photosynthétiques naturelles. La première partie de cette thèse concerne les modèles artificiels du photosystème II (qui catalyse l'oxydation d'eau), composé d'un chromophore et d’un relais d’électrons comme équivalent synthétique correspondant à l'ensemble P680-TyrZ/His190 du photosystème II. Trois complexes ruthénium polypyridyl - imidazole - phénol avec un groupe méthylique à différentes positions sur l'anneau phénolique (Ru-xMe) ont été synthétisés et caractérisés par des méthodes électrochimiques et photophysiques. L’augmentation, comparée aux complexes précédents, du potentiel redox des groupes phénols (0.20 V->0.9 V par rapport à l’électrode de ferrocène) rend leur fonction de relais d’électron dans un système photocatalytique pour l'oxydation d'eau thermodynamiquement possible. Des études d’absorption transitoire ont révélé que le transfert d’électron intramoléculaire est rapide (5-10 µs dans solvant aprotique et < 100 ns dans l'eau) malgré la faible force motrice, mettant en evidence l'importance de la liaison hydrogène entre le phénol et le groupe imidazole. Les légères différences entre les trois complexes Ru-xMe ainsi que l’étude de l'effet de bases externes nous ont permis d’établir un mécanisme dans laquelle l'imidazole est impliqué dans une réaction de transfert de proton en cascade. L'acceptation du proton phénolique durant l'oxydation du ligand rend son deuxième site azote plus acide et seulement la déprotonation de ce dernier bascule l’équilibre réactionnel complétement vers l'oxydation du ligand. La deuxième partie de cette thèse consiste en la synthèse d’un complexe chromophore-tryptophane en utilisant une approche de chimie dite « click ». On a montré que l'oxydation, induite par la lumière, du Trp au sein du complexe Ru-tryptophane suit un mécanisme ETPT. Selon le pH, les radicaux du tryptophane (Trp• ou TrpH•⁺) ont été détectés et les mesures spectrales à différents temps ont montrés la transition entre les deux formes radicalaires. La déprotonation du radical dépend de la concentration d'eau assurant la fonction d’accepteur de proton. La dernière partie de la thèse concerne nos efforts à lier, par une liaison covalente, une unité catalytique au module de chromophore- relais électronique caractérisé précédemment. L'approche de chimie « click » n’était pas efficace pour l’obtention de l’assemblage photocatalytique final. Donc, l'activation biomoléculaire d'un catalyseur Mn salen a été effectuée et la formation de l’espèce Mn(IV) a été observée. Etant une étape vers l'utilisation de ces types de photocatalyseurs dans une cellule photoélectrochimique, un chromophore [Ru(bpy)₃]²⁺ avec des groupes d’ancrage phosphonate a été synthétisé (Ru-phosphonate) et greffé sur la surface méso-poreuses d'un semi-conducteur de TiO₂ pour effectuer des mesures du photocourant. / Artificial photosynthesis is often considered to have great potential to provide alternative, renewable fuels by harvesting, conversion and storage of solar energy. One promising approach is the development of modular molecular photocatalysts inspired by natural photosynthetic enzymes. The first part of this thesis deals with artificial mimics of the water oxidizing photosystem II composed of a chromophore and an electron relay as synthetic counterpart of the P680-TyrZ/His190 ensemble of photosystem II. Three ruthenium polypyridyl – imidazole - phenol complexes with varying position of a methyl group on the phenol ring (Ru-xMe) were synthesized and characterized by electrochemical and photophysical methods. As an improvement compared to earlier complexes the increased redox potential (~0.9 V vs. Ferrocene) of the phenol groups makes their function as an electron relay in a photocatalytic system for water oxidation thermodynamically possible. Time-resolved absorption studies revealed fast intramolecular electron transfer (<5-10 µs in aprotic solvent and <100 ns in water) despite the low driving force and the importance of the hydrogen bond between the phenol and the imidazole group was put in evidence. Slight differences between the three Ru-xMe complexes and investigation of the effect of external bases allowed to derive a mechanistic picture in which the imidazole is involved in a “proton domino” reaction. Accepting the phenolic proton upon ligand oxidation (within the H-bond) renders its second nitrogen site more acidic and only deprotonation of this site pulls the overall equilibrium completely towards oxidation of the ligand. Another part of this thesis comprises a chromophore-tryptophan construct synthesized using a click chemistry approach. Light-induced oxidation of Trp in this Ru-tryptophan complex was shown to follow ETPT mechanism. Depending on the pH conditions tryptophan radicals, either Trp• or TrpH•⁺ were detected and spectral measurement at different time showed the transition between the two forms. Deprotonation of the radical was dependent on the concentration of water as proton acceptor. Later part of the thesis deals with efforts to covalently bind a catalytic unit to the previously characterized chromophore-electron relay module. The click chemistry approach was not successful to obtain the final photocatalytic assembly. Therefore bimolecular activation of a Mn salen catalyst was performed and formation of Mn(IV) species was observed. As a step towards utilization of these types of photocatalysts in a photoelectrochemical cell a [Ru(bpy)₃]²⁺ chromophore with phosphonate anchoring groups (Ru-Phosphonate) was synthesized and grafted on the surface of a TiO₂ mesoporous semiconductor surface anode to perform photocurrent measurements.

Signals recorded from the brain often show rhythmic patterns at different frequencies, which are tightly coupled to the external stimuli as well as the internal state of the subject. These signals also have transient structures related to spiking or sudden onset of a stimulus, which have a duration not exceeding tens of milliseconds. Further, brain signals are highly non-stationary because both behavioral state and external stimuli can change over a short time scale. It is therefore essential to study brain signals using techniques that can represent both rhythmic and transient components of the signal. In Chapter 2, we describe a multi-scale decomposition technique based on an over-complete dictionary called matching pursuit (MP), and show that it is able to capture both sharp stimulus-onset transient and sustained gamma rhythm in local field potential recorded from the primary visual cortex. Gamma rhythm (30 to 80 Hz), often associated with high-level cortical functions, has been proposed to provide a temporal reference frame (“clock”) for spiking activity, for which it should have least center frequency variation and consistent phase for extended durations. However, recent studies have proposed that gamma occurs in short bursts and it cannot act as a reference. In Chapter 3, we propose another gamma duration estimator based on matching pursuit (MP) algorithm, which is tested with synthetic brain signals and found to be estimating the gamma duration efficiently. Applying this algorithm to real data from awake monkeys, we show that the median gamma duration is more than 330 ms, which could be long enough to support some cortical computations.

While task-based functional magnetic resonance imaging (fMRI) has helped us understand the functional role of many regions in the human brain, many diseases and complex behaviors defy explanation. Alternatively, if no task is performed, the fMRI signal between distant, anatomically connected, brain regions is similar over time. These correlations in “resting state” fMRI have been strongly linked to behavior and disease. Previous work primarily calculated correlation in entire fMRI runs of six minutes or more, making understanding the neural underpinnings of these fluctuations difficult. Recently, coordinated dynamic activity on shorter time scales has been observed in resting state fMRI: correlation calculated in comparatively short sliding windows and quasi-periodic (periodic but not constantly active) spatiotemporal patterns. However, little relevance to behavior or underlying neural activity has been demonstrated. This dissertation addresses this problem, first by using 12.3 second windows to demonstrate a behavior-fMRI relationship previously only observed in entire fMRI runs. Second, simultaneous recording of fMRI and electrical signals from the brains of anesthetized rats is used to demonstrate that both types of dynamic activity have strong correlates in electrophysiology. Very slow neural signals correspond to the quasi-periodic patterns, supporting the idea that low-frequency activity organizes large scale information transfer in the brain. This work both validates the use of dynamic analysis of resting state fMRI, and provides a starting point for the investigation of the systemic basis of many neuropsychiatric diseases.