Le transport routier est responsable de la production de la majeure partie des oxydes d’azote (NOx) émis dans l’atmosphère. La majorité de cette pollution est donc concentrée dans des zones très urbanisées. L’exposition permanente aux gaz d’échappement a des conséquences graves pour la santé humaine et pour cela, des normes d’émission de plus en plus strictes sont mises en place. Les technologies post-Traitement embarquées dans les pots d’échappement sont de plus en plus complexes et nécessitent un control continu de la composition gazeuse. Les conditions sérères de ce milieu requièrent le développement de capteurs de gaz robustes et de longue durée de vie. Dans ce travail, nous présentons la procédure de fabrication et la caractérisation d’un capteur électrochimique à trois électrodes pouvant satisfaire les exigences d’une application industrielle dans le domaine automobile. La technologie de sérigraphie utilisée a l’avantage d’être facilement transférable dans l’industrie pour une production de masse bas cout.Le principe de fonctionnement du capteur est basé sur la polarisation galvanostatique de l’électrode sensible permettant une détection sélective de NO2 sans interférence avec d’autres gaz comme CO et NO. De plus, afin d’augmenter la stabilité du capteur, de diminuer les temps de réponse et de recouvrement, un nouveau matériau d’électrode composite à base d’or a été développé.Enfin, la réduction électrochimique de l’oxygène sur l’or et sur des électrodes composite a été étudiée, afin de proposer un mécanisme de détection de NO2 / Road transport is one of the main sources of NOx emitted into the atmosphere. The majority of this pollution is concentrated in urbanized areas. The permanent exposure to the exhaust gases has serious consequences for human health and for that, emission standards become more stringent. The modern technologies present in automotive need the continuous control of the exhaust composition. The variations of temperature, composition of exhaust gas, vibrations and other factors require long life robust control systems. In this work, we present the procedure of fabrication and characterization of an electrochemical sensor with three electrodes that can fulfill the demands of industrial applications in automotive industry. Manufacturing by screen-Printing technology allows producing low-Cost sensor with high reproducibility in industrial process.The principle of our sensor is based on galvanostatic polarization of a gold sensing electrode allowing the selective detection of NO2 without interference to other gases such as CO and NO. In order to increase stability, and to decrease the response and recovery time of the sensor, a new Au composite sensitive electrode was developed. The electrochemical reduction of oxygen on gold and gold-Based electrodes was then studied, to propose a detailed mechanism of NO2 detection.

Notre capacité à communiquer et à apprécier la musique repose sur une discrimination de fréquences couvrant une large gamme de fréquences sonores. Cette propriété résulte de cellules mécanosensorielles « ciliées », qui sont réglées pour répondre de façon maximale à une fréquence caractéristique qui varie monotoniquement le long de l’axe de l’organe auditif, la cochlée. Les mécanismes cellulaires et moléculaires qui définissent la fréquence d’une cellule ciliée et régulent sa valeur pour différentes cellules afin de couvrir la gamme auditive demeurent néanmoins inconnus. Notre hypothèse de travail est que cette fréquence est réglée en partie par les propriétés mécaniques passives et actives de la « touffe ciliaire », l’antenne mécanosensorielle de la cellule ciliée. A l’aide d’une préparation excisée de la cochlée du rat, nous avons combiné l’iontophorèse de chélateurs de calcium (BAPTA ou EDTA) pour casser les liens de bout-de-cil qui connectent les stéréocils voisins de la touffe ciliaire, une stimulation grâce à un micro-jet de fluide pour estimer la raideur de la touffe ciliaire et des enregistrements en « patch-clamp » de courants de transduction afin de compter le nombre de liens de bout-de-cil intacts qui contribuent à la réponse. Avec les mouvements évoqués par la rupture des liens de bout-de-cil et avec nos mesures de raideur, nous avons pu estimer la tension dans toute la touffe ciliaire, ainsi que la tension dans un seul lien de bout-de-cil en connaissant le nombre de liens qui contribuent à cette tension. Dans les cellules ciliées externes, qui sont impliquées dans l’amplification du stimulus sonore mais qui n’envoient pas d’information neuronale au cerveau, nous avons observé un gradient de tension et de raideur lorsque la fréquence caractéristique de la cellule ciliée augmente, suggérant que ces paramètres physiques peuvent être impliqués dans le réglage d’une cellule ciliée à sa fréquence caractéristique. Au contraire, pour les cellules ciliées internes, les vraies cellules sensorielles de la cochlée, nos observations ne montrent pas de gradient significatif. De plus, nous avons observé des mouvements de la touffe ciliaire induits par la variation de la concentration en calcium, correspondant à une tension accrue pour des concentrations en calcium plus faibles. Ces mouvements sont similaires à ceux évoqués dans d’autres classes de vertébrés, tels que chez la grenouille ou chez la tortue. Ainsi, nos résultats réconcilient les expériences faites chez les vertébrés inférieurs et chez le mammifère, et montrent l’implication des gradients de la mécanique de la touffe ciliaire pour l’importante sélectivité fréquentielle de la cochlée / Our ability to communicate and appreciate music relies on acute frequency discrimination over a broad range of sound frequencies. This property results from the operation of mechanosensory “hair" cells, which are each tuned to respond maximally to a characteristic frequency that varies monotonically along the axis of the auditory organ, the cochlea. The cellular and molecular mechanisms that set the characteristic frequency of a hair cell and regulate its value among different cells to cover the auditory range have remained elusive. Our working hypothesis is that tuning results in part from passive and active mechanical properties of the “hair" bundle, the mechanosensory antenna of the hair cell.Using an excised preparation from the rat cochlea, we combined iontophoresis of a calcium chelator (BAPTA or EDTA) to break the tip links that interconnect neighbouring stereocilia of the hair-cell bundle, fluid-jet stimulation to estimate hair-bundle stiffness and patch-clamp recordings of transduction currents to count the number of intact transduction channels contributing to the response. From the movements evoked by tip-link breakage and our stiffness measurements, we were able to estimate tension in the whole hair bundle as well as, knowing the number of tip links contributing to this tension, in a single tip link.In outer hair cells, which are involved in sound amplification but do not send neural information to the brain, we observed a gradient of tension and stiffness from the low-frequency to the high-frequency end of the cochlea, suggesting that these physical parameters may help tune the hair cell to its characteristic frequency. Interestingly, with inner hair cells - the true sensors of the cochlea, our observations do not show any significant gradient. Furthermore, we observed calcium-evoked hair-bundle movements corresponding to an increased tension in the tip links at decreased concentrations of calcium. These movements were similar to those evoked in other classes of vertebrates, such as the frog or the turtle. Together, our results reconcile experiments performed in lower vertebrates with those performed in mammals and show the implication of hair-bundle mechanical gradients in the sharp frequency tuning of the cochlea

abstract: The maximum theoretical efficiency of a terrestrial non-concentrated silicon solar cell is 29.4%, as obtained from detailed balance analysis. Over 90% of the current silicon photovoltaics market is based on solar cells with diffused junctions (Al-BSF, PERC, PERL, etc.), which are limited in performance by increased non-radiative recombination in the doped regions. This limitation can be overcome through the use of passivating contacts, which prevent recombination at the absorber interfaces while providing the selectivity to efficiently separate the charge carriers generated in the absorber. This thesis aims at developing an understanding of how the material properties of the contact affect device performance through simulations.The partial specific contact resistance framework developed by Onno et al. aims to link material behavior to device performance specifically at open circuit. In this thesis, the framework is expanded to other operating points of a device, leading to a model for calculating the partial contact resistances at any current flow. The error in calculating these resistances is irrelevant to device performance resulting in an error in calculating fill factor from resistances below 0.1% when the fill factors of the cell are above 70%, i.e., for cells with good passivation and selectivity. Further, silicon heterojunction (SHJ) and tunnel-oxide based solar cells are simulated in 1D finite-difference modeling package AFORS-HET. The effects of material property changes on device performance are investigated using novel contact materials like Al0.8Ga0.2As (hole contact for SHJ) and ITO (electron contact for tunnel-oxide cells). While changing the bandgap and electron affinity of the contact affect the height of the Schottky barrier and hence contact resistivity, increasing the doping of the contact will increase its selectivity. In the case of ITO, the contact needs to have a work function below 4.2 eV to be electron selective, which suggests that other low work function TCOs (like AZO) will be more applicable as alternative dopant-free electron contacts. The AFORS-HET model also shows that buried doped regions arising from boron diffusion in the absorber can damage passivation and decrease the open circuit voltage of the device. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2020

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22455号 / 工博第4716号 / 新制||工||1737(附属図書館) / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 中尾 佳亮, 教授 松原 誠二郎, 教授 杉野目 道紀 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Acylation of cyclohexene can provide number of reaction products. Cyclohexene, 1-methylcyclohexene and 3-methylcyclohexene were acylated with propionic anhydride over diferent zeolite structures and molecular sieves. Cyclohexene acylation led to propionylcyclohexene. The major acylation products of 1-methylcyclohexene is 2-methyl-3-propionylcyclohexene. Reaction product of 3-methylcyclohexene acylation is 4-methyl-3-propionylcyklohexene and 3-methyl-2-propionylcyclohexene. The aim of acylation biphenyl with carboxylic acid anhydrides and chlorides was to prove reaction with the highest conversion of substrate. The highest biphenyl conversion was obtained with octanoyl chloride and hexanoic anhydride over zeolite USY (15). The highest selectivity to 4-acylbiphenyl was observed.

Modelling of interactions of proteins and peptides with metal ions Ondrej Gutten - Diploma thesis Keywords: Metalloproteins, metal ion selectivity, in silico prediction Abstract: An approach for in silico prediction and estimation of selectivity properties of metal-binding peptides is suggested. An in-depth analysis is performed to disclose the justifiability and limitations of this approach. The study is divided into three parts. First part investigates the soundness of two quantum chemical methods (MP2 and DFT) for their use in the set-up quest. The testing includes comparison with CCSD(T), effect of basis selection, performance of the two methods in geometry optimizations and effect of implicit solvent model. Second part foreshadows the approach of searching for a metal selective peptide by thoroughly investigating the ability of simple representative systems, derived from their metalloprotein templates, to retain the property of interest. Final part describes the initial step of extensive combinatorial approach towards examination of vast number of simple systems that represent metal-binding sites, and which are to be used for prediction of metal-selectivity through exploitation of the described approach and, ultimately, to the de novo design of metalloproteins with desired properties.

A highly selective eggshell Fischer-Tropsch catalyst has been fabricated via interaction of hydrophobic and hydrophilic molecules on thermally treated silica gel. The physical interactions of the mesoporous silica support and the effect of catalyst preparation conditions on the performance of the cobalt/SiO2 were explored. It was found that dispersion and performance of the FT cobalt/SiO2 catalyst were significantly affected by the preparation technique used. In this study we focus on two key variables: the solvent used during the precursor loading and the calcination atmosphere. Silanol groups on the silica surface and near-surface regions can alter morphology and dispersion of the supported active metals. Solvents used for precursor such as water or alcohol attach to these silanol sites in specific configurations and compete with metal salts during ion exchange and adsorption. By fine tuning the solvent attachments on heat treated silica we have fabricated a cobalt/silica catalyst with high dispersion and low metal loads. Additionally, since silica has affinity for both polar and non-polar molecule depending on the surface conditions; this property has been exploited in preparing an engineered eggshell profile. This together with simultaneous calcination/ reduction in a dynamic hydrogen environment has been shown to further enhance dispersion and reducibility. Characterization techniques including BET, XPS, XRD, H-chemisorption and FTIR were employed. Catalyst activity, product selectivity, distribution and conversion were studied using a bench scale fixed bed reactor fitted with a GC/MS instrument.

Metal ions are a tempting tool for organisms thanks to the diversity of func- tions they have to offer, if they can be distinguished properly. Examining metal-ion selectivity computationally is challenging mainly due to complex- ity of electronic structure and solvation effects. A DFT-based protocol for predicting metal-ion selectivity of metal-binding systems was developed. The most essential part of the thesis is discussion of the magnitudes and sources of inherent errors, both for metal-ion complexes and small peptides. The thesis connects the work of four original papers. It includes computational and ex- perimental benchmarks, a case-study validating the computational protocol for obtaining energetic and structural insights, and attempts applying the protocol to peptidic systems. ii

<p>The primary visual cortex (V1) is a center in the visual pathway that receives the converging information and sends diverging information to multiple visual areas. It is essential for the normal functioning of the visual system. While processing the input from the outside world, it is also continually modified by the sensory experience. This thesis is dedicated to studying the plasticity in the visual cortex that is associated with experience and brain damage recovery. In this thesis, we discovered that the visual experience induces 5 Hz oscillations that recruit inhibition in V1, sharpening the feature selectivity. We have also demonstrated that gene therapy to convert astrocytes into neurons induces neuronal circuit plasticity and functional recovery in mouse V1 following ischemia.</p>

The neuronal substrates underlying aspects of comorbidity in brain disease states may be described over psychiatric and neurologic conditions that include affective disorders, cognitive disorders, schizophrenia, obsessive-compulsive disorder, substance abuse disorders as well as the neurodegenerative disorders. Regional and circuitry analyses of biogenic amine systems that are implicated in neural and behavioural pathologies are elucidated using neuroimaging, electrophysiological, neurochemical, neuropharmacological and neurobehavioural methods that present demonstrations of the neuropathological phenomena, such as behavioural sensitisation, cognitive impairments, maladaptive reactions to environmental stress and serious motor deficits. Considerations of neuronal alterations that may or may not be associated with behavioural abnormalities examine differentially the implications of discrete areas within brains that have been assigned functional significance; in the case of the frontal lobes, differential deficits of ventromedial and dorsolateral prefrontal cortex may be associated with different aspects of cognition, affect, remission or response to medication thereby imparting a varying aspect to any investigation of comorbidity.