Im Rahmen dieser Arbeit werden Untersuchungen der Spinrelaxation in epitaktischen GaN-Schichten mit unterschiedlichen Donatorkonzentrationen und Versetzungsdichten mit Hilfe spin- und zeitaufgelöster differentieller Reflektanzspektroskopie präsentiert. Dabei wurden die optischen Anregungsbedingungen sehr sorgfältig gewählt. Neben der genauen Abstimmung der Anregungsenergie, unterstützt durch die Modellierung der differentiellen Reflektanz, wurden insbesondere spektral schmale Laserpulse verwendet. Diese erlauben eine selektive Anregung der untersuchten Übergänge. Es wurden Spinlebensdauern von 30 bis 170~ps bei tiefen Temperaturen für das freie A-Exziton bestimmt. In der Nähe des Metall-Isolator-Übergangs ließ sich eine langsamere Spinrelaxation als für schwächer dotierte Proben nachweisen. Die längsten beobachteten Spinrelaxationszeiten zeigen freistehende GaN-Schichten hoher Materialqualität mit sehr geringen Versetzungsdichten. In der Literatur besteht eine kategorische Unterteilung der Ergebnisse in lange elektronische Spinlebensdauern bis in den Nanosekundenbereich, erhalten mit Kerr-Messungen, und extrem kurze exzitonische Spinrelaxation in Reflektanz-Experimenten im (Sub-)Pikosenkundenbereich. Dieses Bild wird hier nicht bestätigt. Die beobachteten Spinrelaxationszeiten liegen eineinhalb bis zweieinhalb Größenordnungen über Ergebnissen, von denen bisher mit der hier verwendeten Methode berichtet wurde. Es wird gezeigt, dass die Beobachtungen extrem kurzer Spinrelaxationszeiten an anderer Stelle eine Folge der optischen Anregungsbedingungen sind. Die Verwendung sehr kurzer und damit spektral breiter Laserpulse, die eine selektive Exziton-Anregung verbieten, führt zu einem deutlich anderen zeitlichen Verhalten und stark verfälschten Ergebnissen. Diese Beobachtung löst den scheinbaren Widerspruch zwischen den beiden Ergebnisgruppen in der Literatur auf und bildet die Grundlage für weiterführende Untersuchungen. / In this work, an investigation of spin relaxation in GaN epitaxial layers with different doping concentrations and dislocation densities is presented. The measurements were carried out by the means of spin- and time-resolved differential reflectance spectroscopy. The conditions of optical excitation were chosen with special care. In particular, spectrally narrow laser pulses were used to achieve selective excitation of the examined transitions in addition to the precise adjustment of the excitation energy, supported by the modeling of the differential reflectance. The spin relaxation times obtained for the free A exciton at low temperatures are in the range of 30 to 170 ps. In the proximity of the metal insulator transition, a slower spin relaxation was observed than for lower doping concentrations. The longest spin relaxation times were found in high quality, free-standing GaN layers with very low dislocation densities. Existing results in the literature can be strictly grouped into long electronic spin lifetimes of up to a few nanoseconds, obtained with Kerr rotation, and extremely short spin relaxation in the (sub)picosecond range, measured with reflectance experiments. This picture cannot be confirmed here. The spin relaxation times observed here lie 1.5 to 2.5 orders of magnitude above the values previously reported using the same experimental method. It is shown that the instances of extremely fast spin relaxation are caused by the properties of the optical excitation. The use of ultra-short and thus spectrally broad laser pulses, which prohibits the selective excitation of excitons, leads to a significantly different temporal behavior and strongly distorted results. This finding elucidates the apparent conflict between the two groups of results and forms the basis for further investigations.

<p>To estimate the propagation of light in tissue-like optical phantoms (fat emulsions), this thesis utilized the diffuse reflectance spectroscopy in combination with Monte Carlo simulations. A method for determining the two-parametric Gegenbauer-kernal phase function was utilized in order to accurately describe the diffuse reflectance from poly-dispersive scattering optical phantoms with small source-detector separations. The method includes the spectral collimated transmission, spatially resolved diffuse reflectance spectra (SRDR) and the inverse technique of matching spectra from Monte Carlo simulations to those measured. An absolute calibration method using polystyrene micro-spheres was utilized to estimate the relation between simulated and measured SRDR intensities. The phase function parameters were comparable with previous studies and were able to model measured spectra with good accuracy. Significant differences between the phase functions for homogenized milk and the nutritive fat emulsions were found.</p><p> </p>

To estimate the propagation of light in tissue-like optical phantoms (fat emulsions), this thesis utilized the diffuse reflectance spectroscopy in combination with Monte Carlo simulations. A method for determining the two-parametric Gegenbauer-kernal phase function was utilized in order to accurately describe the diffuse reflectance from poly-dispersive scattering optical phantoms with small source-detector separations. The method includes the spectral collimated transmission, spatially resolved diffuse reflectance spectra (SRDR) and the inverse technique of matching spectra from Monte Carlo simulations to those measured. An absolute calibration method using polystyrene micro-spheres was utilized to estimate the relation between simulated and measured SRDR intensities. The phase function parameters were comparable with previous studies and were able to model measured spectra with good accuracy. Significant differences between the phase functions for homogenized milk and the nutritive fat emulsions were found.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Submitted by VITOR HUGO MARQUES LUIZ null (vitorhmluiz@hotmail.com) on 2016-03-14T14:35:25Z No. of bitstreams: 1 tese Vitor Hugo repositório.pdf: 12742690 bytes, checksum: 808cc9757cd523a743880c2238379bc1 (MD5) / Approved for entry into archive by Sandra Manzano de Almeida (smanzano@marilia.unesp.br) on 2016-03-14T17:09:34Z (GMT) No. of bitstreams: 1 luiz_vhm_dr_araiq_par.pdf: 1804257 bytes, checksum: 83b423fb984c5b0c70d305405ab840c2 (MD5) / Made available in DSpace on 2016-03-14T17:09:34Z (GMT). No. of bitstreams: 1 luiz_vhm_dr_araiq_par.pdf: 1804257 bytes, checksum: 83b423fb984c5b0c70d305405ab840c2 (MD5) Previous issue date: 2016-02-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Este trabalho descreve o desenvolvimento de métodos analíticos para a determinação quantitativa de furosemida e bumetanida em amostras de urina utilizando espectroscopia por reflectância difusa (para a furosemida) e por imagem por scanner com quantificação através do histograma de cores utilizando o padrão RGB (para ambas). Envolve também o desenvolvimento de um método quantitativo para a detecção de chumbo em resíduos de armas de fogo (GSR) nas mãos de atiradores utilizando membranas de celulose bacteriana como substrato de coleta, visando o descobrimento do tempo de disparo. Também foi realizada a quantificação de chumbo em amostras de tintura para cabelos utilizando método previamente desenvolvido, visando detecção da adulteração destes produtos e controle de qualidade. Estuda também a potencialidade do uso das membranas de celulose bacteriana para a coleta de impressões digitais. Os métodos desenvolvidos consistem na reação da furosemida (FUR) com o regente cromogênico paradimetilaminocinamaldeído (p-DAC) 0,70% e ácido clorídrico (HCl) 1,72 mol L-1 em papel de filtro qualitativo com barreiras hidrofóbicas, com detecção espectrofotométrica e por histograma de cores; na reação do íon chumbo(II) (Pb2+) com rodizonato de sódio (ROD) 0,16% em meio micelar de dodecil sulfato de sódio (SDS) 5 mmol L-1 em membranas de celulose bacterianas, com detecção espectrofotométrica e por microscopia eletrônica de varredura (MEV); na reação de bumetanida (BMT) com o reagente p-DAC 0,6% e HCl 0,26 mol L-1 em papel de filtro qualitativo com barreiras hidrofóbicas, com detecção por histograma de cores e na coleta de impressões digitais utilizando membrana de celulose bacteriana impregnadas com ninidrina, nitrato de prata ou óxido de zinco, dos quais o nitrato de prata e a ninidrina atuaram como agentes de coleta razoáveis. Todas as concentrações foram otimizadas por planejamentos quimiométricos. As reações foram realizadas na forma de spot test, envolvendo a formação de um produto colorido em 545 nm para o chumbo, em 585 nm para a furosemida e 520 nm para a bumetanida. As curvas analíticas foram contruídas a partir de soluções padrões dos respectivos analitos. Os métodos desenvolvidos para a bumetanida e para a furosemida foram aplicados em amostras de urina sintética e natural fortificadas e os resultados obtidos foram comparados estatisticamente com métodos comparativos. A validação dos métodos foi realizada por adição de padrão e recuperação e por comparação de métodos, no caso da FUR e da BMT, obtendo-se recuperações entre 98,0 e 115,3% para os métodos de quantificação da furosemida e entre 93,0 e 102,0% para o método de quantificação da bumetanida. O método de coleta de GSR é baseado na utilização de membranas finas de celulose bacteriana desenvolvidas pelo Grupo de Materiais Fotônicos do IQ-UNESP.Para os GSR foram realizadas 40 coletas totais em tempos de coleta após o disparo (diferentes e conhecidos), sendo sua comparação realizada através das curvas analíticas, mostrando ser possível a detecção do tempo de disparo com uma margem de erro de aproximadamente 5 minutos. Os resultados foram comparados estatisticamente e os valores obtidos a partir de testes estatísticos mostraram que os métodos podem ser usados para análises de rotina em laboratórios forenses. / This work describes the development of analytical methods for the quantitative determination of furosemide and bumetanide in urine samples using diffuse reflectance spectroscopy (for furosemide) and scanning imaging with quantification by color histogram using RGB color pattern (for both). It involves also the development of a quantitative method for the detection of lead in gunshot residues (GSR) in the hands of the shooters using bacterial cellulose membranes as substrate collection, aiming the discovery of shooting time. It is also done the quantification of lead in progressive hair lotions samples using a previously developed method, aiming the detection of products adulterations and quality control. It also studies the potentiality of the usage of bacterial cellulose membranes for the collection of fingerprints. The developed methods are consisted in the reaction of furosemide (FUR) with the cromogenic reagent p-dimethylamino cinnamaldehyde (p-DAC) 0.70% and hydrochloric acid (HCl) 1.72 mol L-1 in qualitative filter papers with hydrophobic barrier, with spectrophotometric detection and by color histogram; in the reaction of lead(II) ion (Pb2+) with sodium rhodizonate (ROD) 0.16% in micellar medium of sodium dodecyl sulfate (SDS) 5 mmol L-1 in bacterial cellulose membranes with spectrophotometric detection and by scanning electron microscopy; in the reaction of bumetanide (BMT) with the reagent p-dimethylamino cinnamaldehyde (p-DAC) 0.6% and hydrochloric acid (HCl) 0.27 mol L-1 in qualitative filter papers with hydrophobic barrier with color histogram detection an in the collect of fingerprints using bacterial cellulose membranes impregnated with ninhydrine, silver nitrate or zinc oxide, of which the silver nitrate and ninhydrin acted as reasonable collection agents. All concentrations were optimized through chemometrics designs. The reactions were carried out as spot test, involving the formation of a colored product at 545 nm for lead, in 585 nm for furosemide and in 520 nm for bumetanide. Analytical curves were built from standard solutions of the respective analytes. The methods developed for furosemide and bumetanide were applied in fortified synthetic and natural urine samples and the results obtained were compared statistically with comparative methods. The validation of the methods were performed by standard addition and recovery and by comparison of methods, for FUR and BMT, yielding recoveries between 98.0 and 115.3% for furosemide quantification methods and between 93.0 and 102.0% for the quantification method for bumetanide. GSR collection method is based on the use of thin membranes of bacterial cellulose developed by Photonic Materials Group IQ-UNESP. For GSR, 40 total collections were carried out in known and different times of collection after shooting times and their comparison through analytical curves were done, showing the possibility of the detection of the shooting time with an error of 5 minutes, approximately. The results were statistically compared and the values obtained from statistical tests showed that the methods can be used for routine analysis in forensic laboratories.

L'objectif de cette thèse concerne l'association de deux techniques de mesure dans le cadre de la caractérisation in vivo de la peau. La première, nommée Spectroscopie de Réflectance Diffuse (DRS), permet la caractérisation des paramètres optiques de la peau analysée et quantifie les phénomènes d'absorption et de diffusion de la lumière. La deuxième est la microspectroscopie Raman. Elle fournit une identification chimique des composés analysés sans marquage. L'objet de cette thèse est d'évaluer l'effet de l'interaction lumière-matière sur les capacités de localisation et de quantification de la microspectroscopie Raman, lesquelles sont dégradées dans un milieu diffusant tel que la peau. Une approche in vivo bimodale (DRS et Raman) est proposée pour la caractérisation biochimique quantitative des tissus cutanés avec l'idée d'établir un protocole de correction des spectres Raman acquis, en exploitant les propriétés optiques fournies par la DRS. Elle est décomposée en trois axes de travail complémentaires : le développement d'une instrumentation DRS permettant la mesure des spectres de réflectance diffuse et le calcul des propriétés optiques dans la zone sondée par la spectroscopie Raman ; le développement de fantômes optiques permettant une compréhension expérimentale des phénomènes d'absorption, de diffusion élastique et de diffusion Raman; le développement d'un protocole de correction des spectres Raman à partir des propriétés optiques obtenues par DRS. / This thesis relates to the combination of two in vivo skin characterization techniques. On the one hand, Diffuse Reflectance Spectroscopy (DRS) enables skin optical properties characterization by quantifying light absorption and light elastic scattering. On the other hand, Raman microspectroscopy provides information on molecular compositions of tissues with no need of labeling. Localization and quantification functions of Raman microspectroscopy are both distorted in scattering media such as skin. Therefore, the aim of this thesis was to assess the effect of light-matter interactions on these functions. A bimodal method is proposed to achieve quantitative biochemical characterization of cutaneous tissues in vivo. The main idea is to develop a procedure of Raman spectra correction based on the quantified optical properties provided by DRS. This work was divided in three complementary approaches: the development of a system enabling diffuse reflectance and optical properties measurements in the same zone as Raman microspectroscopy; the fabrication of optical phantoms improving our knowledge on absorption, elastic scattering and Raman scattering phenomena; and the development of a Raman spectra correction model as function of the skin optical properties given by DRS measurements.

Le développement de variétés performantes de blé dur (Triticum turgidum durum) doit prendre en compte la corrélation négative entre rendement et teneur en protéines (GPC). Une meilleure compréhension de ce phénomène nécessite une connaissance de l'élaboration des composantes de ces variables. Au cours de cette thèse nous nous sommes focalisés sur l'étude du déterminisme de paramètres foliaires pendant le remplissage du grain (morphologie, résorption d'azote/senescence) ainsi que leurs relations avec les caractéristiques post-récolte (rendement, GPC). La population d'étude est constituée de 282 lignées recombinantes issues d'un croisement demi-diallèle entre quatre lignées élites. Les données proviennent d'expérimentations menées en milieu contrôlé (3 expérimentations) et en plein champ (2 essais).En milieu contrôlé, plusieurs variables (teneur en azote, masse surfacique) ont été prédites par spectrométrie infrarouge à raison de mesures régulières au cours de la période d'intérêt. La résorption d'azote de la dernière feuille a été modélisée pour chaque génotype dont les paramètres ont été analysés. Un lien négatif fort a été établi entre la date d'initiation de la résorption (t0) en temps thermique post-floraison et sa durée et un lien positif entre cette date clé et le poids individuel des grains. A l'échelle de la parcelle, le suivi dynamique de la senescence par la mesure d'évolution d'un indice de végétation, le NDVI (Normalized Difference Vegetation Index) a montré une relation forte entre vitesse d'évolution de la senescence et son ordonnée à l'origine, suggérant que la fin de la senescence était un phénomène très contraint dans les conditions environnementales de plein champ.En absence de stress azoté, l'analyse des 4 géniteurs a montré que des combinaisons linéaires de paramètres foliaires permettaient d'expliquer environ 2/3 des variations de la production en grains d'un épi et de la GPC. En considérant l'ensemble de la population, les effets antagonistes d'une résorption tardive sur la production de grains et la teneur en protéines ont été établis. Une carence en azote appliquée post-floraison provoque une résorption précoce et longue, ce qui semble d'avantage affecter la GPC que le rendement. Une carence en azote appliqué pré-floraison réduit la quantité d'azote disponible dans les feuilles drapeau (et par conséquent leur potentiel photosynthétique) ainsi que le nombre de grains alors que les apports tardifs en azote réalisés dans ce traitement vont retarder la résorption donc augmenter le poids individuel des grains et la GPC. L'analyse génétique en modèle mixte a permis de prendre en compte un apparentement entre lignées, calculé grâce aux pedigrees ou aux marqueurs. Ces deux estimateurs de l'apparentement sont très fortement corrélés ; l'ordonnée à l'origine de la relation (0.3) pouvant être interprétée comme une mesure de l'identité par état de la population de base à partir de laquelle les géniteurs sont issus. Par conséquent, les variances additives issues d'un apparentement marqueurs sont systématiquement supérieures à celles d'un apparentement pedigree. Les valeurs d'héritabilité des variables étudiées caractérisant la morphologie de la feuille drapeau à floraison et des paramètres de résorption d'azote sont du même ordre de grandeur que celles du rendement d'un épi et de la teneur en protéines des grains.En conclusion, nous discutons des stratégies de sélection autour de la corrélation négative rendement/GPC en lien avec la résorption d'azote et la senescence, de l'intérêt de l'utilisation du modèle dit « animal » pour les analyses génétiques et la recherche de QTL. / Performing cultivar development of durum wheat (Triticum turgidum durum) have to take in consideration the negative correlation existing between yield and grain protein content (GPC). A best comprehension of this phenomenon needs the knowledge of these variables elaboration. During this thesis, we focused on the study of foliar parameters determinism during the grain filling (morphology, nitrogen resorption/senescence) and their relations with post-harvest parameters (yield, GPC). The population was formed of 282 recombinant lines coming from a half-diallel cross between 4 elite lines. Data are from experimentations on controlled environment (3 experimentations) and on field (2 experimentations).In controlled environment, various variables (nitrogen content, mass area) were predicted using near-infrared spectroscopy and performing regular measures during the period of interest. Nitrogen resorptions of the last leaf were modeled for each genotype and parameters were analyzed. A strong negative correlation was established between the resorption initiation date (t0) in thermal time post-flowering and its duration and a positive correlation was established between t0 and the grain individual weight. At the plot scale, the dynamic monitoring of senescence through measures of NDVI (Normalized Difference Vegetation Index) evolution showed a strong relation between the senescence evolution rate and its intercept, suggesting the senescence end was a very constraint phenomenon in field.Without nitrogen stress, the analysis of the 4 genitors indicated that linear combinations of foliar parameters could explain around 2/3 of one-spike grain production and GPC variations. Considering the entire population, the antagonist effects of a late resorption on grain production and on the GPC were established. A post-flowering nitrogen stress causes an early and long resorption which seems to affect more GPC than yield. A pre-flowering nitrogen stress reduces nitrogen quantity available in flag leaves (and consequently their photosynthetic potential) and the grain number whereas late nitrogen inputs of this environment delay resorption and raise grain individual weight and GPC.The genetic analysis in mixed model allowed taking into account relatedness among lines, calculated with pedigrees or markers. Those 2 relatedness estimators are strongly correlated; the regression intercept (0.3) can be interpreted as an identity-by-state measure of the base population from which genitors are derived. Consequently, additive variances from a marker-relatedness model are always superior to additive variances form a pedigree-relatedness model. Heritability values of the study variables (flag leaf morphology and nitrogen resorption parameters) have the same order of magnitude than those of one-spike yield and GPC.Field experimentations allowed highlighting the flag leaf weight as a contributor organ to yield and GPC. Nitrogen balance showed a link between post-flowering nitrogen fluxes and nitrogen available at flowering. Genotype-phenotype association's research was realized through a simple-marker analysis for all the experimentations and a Composite Interval Mapping analysis only for data obtained in greenhouses. A stable QTL was detected on the 3 controlled environments for t0. QTL comparison on controlled environment QTL and field QTL highlighted various area containing QTL on certain chromosomes: an area of foliar nitrogen content at flowering QTL on the 1A, an area of GPC QTL, Thousand Kernel Weight (TKW) QTL and grain number QTL on the 2A, an area of foliar morphology QTL on the 2B, an area of TKW QTL on the 3B and an area of senescence variables QTL on the 7B.In conclusion, we discuss about breeding strategies around the negative correlation yield/GPC in relations with nitrogen resorption and senescence and about the interest to use the “animal” model for genetic analysis and QTL research.

No description available.

A eletro-oxidação de ácido fórmico vem sendo discutida por muito tempo na literatura, em particular, a natureza do intermediário ativo no caminho direto tem sido debatida. Recentemente alguns grupos relataram novos aspectos deste processo por meio da análise da oxidação de ácido fórmico e sua dependência com o pH da solução. A maioria dos estudos, no entanto, foi realizado sob condições convencionais, ou seja, próximas ao estado de equilíbrio termodinâmico. Alternativamente, o sistema pode ser estudado longe do equilíbrio pelo controle da corrente, nessas condições a oxidação de moléculas orgânicas pequenas sobre platina pode apresentar a formação de padrões e mostrar comportamentos oscilatórios. Pelas condições drasticamente diferentes se poderia alcançar um melhor entendimento do rede complexo de reação, qual fica escondido em experimentos convencionais. Dessa maneira, a dependência do pH de oxidação de ácido fórmico foi revisitada em voltametria cíclica e estendida a uma ampla região de temperatura e condições oscilatórias. Algumas observações adicionais podem ser obtidas: a) a dependência do pH, como relatada anteriormente, pode ser reproduzida, reforçando a proposição do formiato mais provável como espécie ativa, em lugar do ácido fórmico; b) em meio ácido um terceiro caminho ao lado dos caminhos direito e indireto poderia ser ativo; c) padrões oscilatórios foram encontrados em meio alcalino e evidenciaram o carácter bloqueante de espécies oxigenadas como responsável pela formação de padrões; d) geralmente, todos os processos envolvidos diretamente ou indiretamente, podem ser muito propensos a variações pequenas no pH e temperatura da solução, que a atividade deles pode mudar significativamente e o sistema apresentar resultados diferentes sob condições similares. Adicionalmente, os estudos foram estendidos à oxidação de metanol, qual permitido um visto diferenciado na adsorção de espécies carbonáceas e oxigenadas, as quais principalmente poderiam ter caráter inibitório. Apesar disso, como os resultadas mostraram sob algumas condições, uma interação efetiva de ambas espécies via o mecanismo de Langmuir-Hinshelwood pode ocorrer, que o caminho direito da oxidação pode mostrar uma atividade mais alta e as padrões oscilatórios desaparecem. Observou-se ainda que o ácido fórmico produzido como subproduto parcialmente oxidado poderia ter um papel importante na reação da eletro-oxidação de metanol. Ao fim foi encontrado que não apenas ajustamentos como ligar platina com ouro pode melhorar o desempenho do catalisador pelos efeitos eletrônicos e ligantes, mas também modificações no conteúdo da solução, como a oxidação simultânea do ácido fórmico e metanol poderiam permitir um aumento no desempenho. Em ambos os casos a formação de CO pode ser oprimida, que o processo mais ativo, notadamente a oxidação direta do ácido fórmico é mais pronunciada. / The electro-oxidation of formic acid remained under discussion for a long time in literature, where especially the active intermediate in the direct oxidation pathway was discussed controversially. Recently some groups reported new insight by the analysis of the formic acid oxidation in dependence on the bulk solution pH. Yet, the majority of the studies are carried out under conventional conditions, which are close to the thermodynamic equilibrium. On the other hand the system can be driven far from equilibrium by controlling the current, conditions where the oxidation of small organic molecules over platinum may undergo pattern formation and show oscillatory behaviour. Due to the drastically different conditions one may get a better understanding of the complex reaction network, which remains hidden in conventional experiments. Thus, the pH dependence of formic acid oxidation was revisited under steady state voltammetry and extended to a wide temperature range and oscillating conditions. Here insight could be given in various points: a) the pH dependence, as reported earlier, could be reproduced and strongly suggests formate rather than formic acid as most active species; b) in acidic media a third pathway beside direct and indirect ones may be active; c) newly found oscillation patterns in alkaline media revealed the site blocking character of adsorbed water species as possible origin for pattern formation; and d) generally, all surface processes, which are directly or indirectly involved, can be very susceptible to small variations in the bulk solution pH and temperature, that their activity can change significantly and the system emerge different results under similar conditions. Further effort was done to extend the study to methanol oxidation, which allowed a differentiated view on the adsorption of carbonaceous and oxygenated species, which may have mostly inhibiting character. Yet, as the results showed under some conditions, an effective interaction of both species via Langmuir-Hinshelwood mechansim can be realized, that the direct oxidation pathway can undergo higher activity and oscillation patterns may cease. It could also be found, that the produced formic acid as partially oxidized by-product may have a crucial role in the reaction network of the electro-oxidation of methanol. At last it could be found, that not just adjustments like alloying of platinum with gold can enhance the catalyst performance by electronic and ligand effects, but also modifications in the solution content, such as simultaneous oxidation of formic acid and methanol allow an increasing performance. In both ways the formation of CO can be suppressed, that the most active process, namely the direct oxidation of formic acid is more pronounced.

Les sols constituent le premier réservoirterrestre de carbone organique et jouent ainsi un rôleclé pour limiter le réchauffement climatique. Les solsurbains représentent 3% du territoire mondial etl’urbanisation est la première cause de changementd’affectation des sols. L’augmentation rapide dessurfaces artificialisées a entraîné un intérêt croissantquant à la capacité des sols urbains à stocker ducarbone. Les travaux de thèse ont visé à comprendrela contribution des sols urbains au stock global decarbone organique et à proposer une méthodestandardisée pour son suivi. Les recherches ont aussiporté sur l’étude de la stabilité du carbone organiquedes sols urbains et la modélisation de la dynamique dece carbone. Une base de données a été construite àpartir de données disponibles au niveau national, puisde mesures supplémentaires acquises dans trois villes françaises.Le stock de carbone des sols ouverts est similaireentre les villes, et équivalent voire supérieur enprofondeur, à celui des sols forestiers environnants.Ce stock dépend plus particulièrement du mode degestion des espaces verts urbains, et de l’histoire dusite. Ainsi, les sols urbains ouverts sont caractériséspar une forte proportion de matières organiqueslabiles sur 0-44 cm de profondeur. Au contraire, lessols scellés présentent des stocks de carbone trèsfaibles. Ils sont caractérisés par une forte proportionde matières organiques stables dont l’évolution(stockage ou minéralisation) dépend de l’état dedormance microbienne. Un modèle conceptuel de ladynamiq / Soils are the largest terrestrial pool oforganic carbon and thus play a key role in mitigatingclimate change. The urban soils account for 3% of theworld’s territory and urbanization is currently theprimary cause of land use change. The increase ofartificial areas have led to a growing interest in theurban soil ability to store organic carbon. This workaimed to understand the contribution of urban soils tothe global organic carbon stock and to propose astandardized method for its monitoring. The researchalso focused on studying the stability of organic carbonin urban soils and modeling its dynamics. A databasewas built using data available at the French territorylevel as well as using additional measurements acquired in three French cities.The organic carbon stock in urban open soils aresimilar between cities, and equivalent, or even higherin depth, than that of surrounding forest soils. Thestock in open soils is particularly dependent upon themanagement methods of the urban green spaces,and on the specific site history. Thus, open urban soilsare characterized by a high proportion of labileorganic matter at 0-44 cm depth. Conversely, sealedsoils have very low carbon stocks. They arecharacterized by a high proportion of stable organicmatter whose evolution (storage or mineralization)depends on the dormant state of the microbialcommunities. A conceptual model of carbon dynamicsfor these two soil types has been developed. Finally,recommendations for optimizing carbon monitoringand urban soil management have been proposed