Carbide-derived carbon Monoliths (CDC-Ms) containing a multimodal arrangement with high volumes of micro- meso- and macropores are prepared by direct nanocasting of silica monoliths with polycarbosilane precursors. CDC-Ms show well-defined pore structures along with specific surface areas of more than 2600 m2 g−1 and overall pore volumes as high as 3.14 cm3 g−1. They exhibit advanced gas filtration properties compared to purely microporous materials due to enhanced storage capacities and kinetics as demonstrated by thermal response measurements based on InfraSORP technology.

京都大学 / 新制・課程博士 / 博士(医学) / 甲第23065号 / 医博第4692号 / 新制||医||1049(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 村川 泰裕, 教授 平井 豊博, 教授 小川 誠司 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

The scope of this work was to design a bootloader for Kinetis K60, an ARM Cortex-M4 microcontroller. The bootloader should simplify the process of loading user applications to the flash memory of the microcontroller on the Minerva development kit. Based on a quick research of existing bootloader solutions, new bootloader was designed together with communication protocol that would suit the needs for transfer of both the file data and configuration information through all the supported communication interfaces - USB, SDHC, Ethernet and RS-232. On the PC side, development of bootloader’s application library and two supporting utilities with graphical and command line interfaces was made. The system can be used out of the box as well as it can be further extended in the future.

The chemical element carbon plays a key role in the 21st century. “The new carbon age” is associated with the global warming due to increasing carbon dioxide emissions. The latter are a major consequence of the continued combustion of fossil fuels for energy generation. However, carbon is also one key component to overcome these problems. Especially porous carbon materials are highly attractive for many environmentally relevant applications. These materials provide high specific surface area, high pore volume, thermal/chemical stability, and high electrical conductivity. They are promising candidates for the removal of carbon dioxide or other environmentally relevant gases from exhaust gas mixtures. Furthermore, porous carbons are used in electrochemical energy storage devices (e.g. batteries or electrochemical capacitors). The performance of the materials in these applications depends on their pore structure. Hence, precise control over the pore size and the pore geometry is important to achieve. Besides a high specific surface area (SSA) and a well-defined pore size, pore accessibility must be ensured because the surface must be completely available. If the porous carbons exhibit ink-bottle pores, the high surface area is useless because the guest species do not reach the pore interior. Therefore, carbon materials with hierarchical pore structure are attractive. They combine at least two different pore systems of different size which contribute with their individual advantages. While smaller pores provide large specific surface area, larger pores ensure efficient mass transport. Numerous methods for the targeted synthesis of carbide-derived carbon materials (CDCs) with hierarchical pore architectures were developed within this thesis (Figure 1). CDCs are produced by the extraction of metal- or semi-metal atoms from carbide precursors leading to the formation of a microporous carbon network with high specific surface area. PolyHIPE-CDCs with porosity on three hierarchy levels and total pore volumes as high as 8.5 cm3/g were prepared by a high internal phase emulsion technique. CO2 activation increases the SSA to values above 3100 m2/g. These materials are promising for the filtration of non-polar organic compounds from gas mixtures. CDC nanospheres with diameters below 200 nm were obtained from polycarbosilane-based miniemulsions. They show high capacitance of up to 175 F/g in symmetrical EDLCs in 1 M H2SO4 aqueous electrolyte. Besides such emulsion techniques, the hard-templating concept (also referred to as nanocasting) was presented as an efficient approach for the synthesis of CDC mesofoam powders and meso-macroporous CDC monoliths starting from silica templates and polycarbosilane precursors. As a wide range of pore sizes is approachable, the resulting materials are highly versatile in terms of application. Due to their high nanopore volume, well-defined mesopores and large SSA, they show outstanding properties as electrode materials in EDLCs or in Li-S batteries as well as high and rapid uptake in gas adsorption processes. CDC aerogels were produced by pyrolysis and high-temperature chlorine treatment of cross-linked polycarbosilane aerogels. These materials can be tailored for efficient CO2 adsorption and show outstanding performance in EDLC electrodes at high current densities of up to 100 A/g due to the very short electron diffusion pathways within the aerogel-type pore system. It was further shown that CDCs can be combined with mesopores by the sacrificial template method starting from PMMA particles as the pore-forming material. The use of highly toxic hydrofluoric acid for template removal and large amounts of organic solvents as typical for hard- and soft-templating approaches can be overcome. SSAs and total pore volumes of 2434 m2/g and 2.64 cm3/g are achieved ensuring good performance of PMMA-CDCs in Li-S batteries cathodes. Besides the characterization of CDCs in real energy storage devices and adsorption processes, their use as model substances in energy- and environmentally relevant applications was part of this thesis. The questions “How does it work?” and “What do we need?” must be clearly answered before any material can be tailored under the consideration of economic and ecological perspectives. The high potential of CDCs for this purpose was shown in this thesis. These carbons were used as model substances in combination with nuclear magnetic resonance (NMR) techniques to get a detailed understanding of the adsorption processes on porous carbon surfaces. However, such investigations require the use of model substances with a tailored and well-defined pore structure to clearly differentiate physical states of adsorbed species and to understand fundamental mechanisms. The characterization of the interaction of electrolyte molecules with the carbon surface was performed with solid-state NMR experiments. The materials were also studied in the high-pressure adsorption of 129Xe using an in-situ NMR technique. Both NMR studies enable the analysis of ions or gas atoms adsorbed on the carbon surface on an atomic level and experimentally demonstrate different strength of interaction with pores of variable size and connectivity. In addition, the novel InfraSORP technology was used for the investigation of the thermal response of CDCs and templated carbon and carbide materials during n-butane adsorption. These model systems lead to a more profound understanding of this technique for the rapid characterization of porous materials. The Kroll-Carbon (KC) concept is a highly attractive alternative for the synthesis of well-defined carbons on the large scale. In this technique, the porous materials are produced by the reductive carbochlorination reaction between oxidic nanoparticles and a surrounding carbon matrix. First KC materials were produced with high SSA close to 2000 m2/g and total pore volumes exceeding 3 cm3/g. This method was established with template particles of various dimensions as well as by using various types of oxides (silica, alumina, titania). Hence, porous carbon materials with various textural parameters are approachable. The first generation of KCs is promising for the use in Li-S battery cathodes and as electrode materials in EDLCs.

This project is a comparative case study of five Community Development Corporations (CDCs) that emerged in the seven central neighborhoods of Inner North/Northeast Portland, Oregon in the late 1980s. Of the five organizations that began at that time, only two exist currently. Analyzing how and why these organizations rose and fell, merged and failed, struggled and survived in a compressed time frame and geographic area will elucidate the different paths that each organization chose in a neighborhood that changed from derelict to gentrified. Drawing on the overlapping bodies of literature that cover low-income and affordable housing development, CDC structure and evolution, and neighborhood revitalization, this study will highlight issues of local government participation in the expansion of CDCs and a changing community context. The choices that organizations made, or were compelled to make, in response to these particularly local conditions contribute either to their fortitude or their demise. This case study is intended to fill in gaps in the existing CDC and gentrification literature and to contribute an understanding of survival strategies for CDCs in an intensely competitive environment.

<p> The object of this work was to evaluate the Supernova ninicomputer as a process simulation tool. To accomplish this obje c tive the GEMCS ste2dy-state simulation system wa.s programmed for the Supernova. This system was programmed to run in five different modes, BASIC , two modes which require that al.L progra1ns are written in Assembly Language, and two modes in which programs may be called from the disk. Of these latter two modes, one requires all programs to be written in Assembly Language; the other mode allows programs to be written in Assembly Language or FORTRAN IV. </p> <p> Two case studies which had previously been run on the CDC 6400 were run on the Supernova to test and evaluate f our of the modes in which GEMCS was proerammed for the Supernova. </p> <p> The studies have also provided an a ssessment of the hardware and softws.re facilities of the Supernova and the results of thjs assessment were documented. In addition the opera tion of the various strategies used to impl ement GEMCS have provided an indication of the feasibility of the impl ementation of the dynamic system simulation program, DYNSYS. </p> / Thesis / Doctor of Philosophy (PhD)

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L’objectif principal de cette thèse était d’examiner dans quelle mesure il est possible d’étendre l’approche de la courbe maîtresse à des composants complexes afin de déterminer des conditions de déverminage et de réaliser une prédiction de durée de vie en fonction de ces conditions de déverminage. Nous avons considéré la stabilité d’un réseau dit élémentaire (réseau carré, à pas constant et droit) puis le problème de la stabilité (selon des critères spécifiques) des composants complexes: les CDC et les monofiltres GFF. Cette thèse a permis de décrire de façon rigoureuse, puis d'utiliser le cadre de travail VAREPA pour résoudre des problèmes issus de l'industrie de télécoms. A cet effet, des séries d’études de vieillissement accéléré sur des réseaux simples et complexes ont été menées. Un protocole de mesure permettant de déterminer les incertitudes de mesure a été mis au point afin de déterminer de façon fiable des intervalles de confiance sur les prédictions de durée de vie.Nous avons étudié les cinétiques de croissance des réseaux inscrits dans une fibre dédiée à l’inscription des CDC (Coreactive). Cette étude nous a permis de montrer que la réaction prédominante à l’origine des changements d’indice de réfraction est activée par une absorption à 1 photon. D’autre part, nous avons étendu le cadre de travail utilisé pour prédire l’effacement des réseaux (VAREPA) afin de rendre compte de leurs cinétiques d’inscription. Puis nous avons cherché à déterminer les conditions de passivation et à prédire la durée de vie des réseaux déverminés en présence d’hydrogène résiduelle (procédé industriel actuel). Pour cela, nous avons établi la courbe maîtresse de réseaux photoinscrits non déverminés puis nous avons validé les conditions de déverminage et les prédictions de durée de vie en construisant une nouvelle courbe maîtresse sur des réseaux déverminés.Nous avons étudié la stabilité thermique des réseaux inscrits dans une fibre hydrogénée dédiée aux futurs monofiltres GFF dans des conditions d’inscription similaires à celles de ces composants. Nous avons utilisé les courbes maîtresses établies à partir des réseaux élémentaires (mais apodisés) simplement dégazés « à froid » (ici 2jours à 50°C puis 2 jours à 110°C). Puis, nous avons fait vieillir le profil d’indice (cœur et gaine) d’un monofiltre GFF. Puis, nous avons recalculé la réponse spectrale de ce filtre vieilli (e.g. 30jours à 200°C) et nous l’avons comparé à des mesures expérimentales. Cette approche reste générale et permet de changer les conditions de déverminage au besoin. Cette étude nous a permis de mettre en évidence que la stabilité des variations d’indice photo-induites dans le cœur dépend peu de l’amplitude initiale de la modulation pour des valeurs comprises entre quelques 10-5 et 10-3. Du fait de la présence d’une gaine optique fortement photosensible (car fortement dopée en Ge), nous avons établi les courbes maîtresses des variations d’indice photo-inscrites dans le cœur et la gaine optique pour des valeurs allant jusque 10-3 dans le cœur et 3.10-3 dans la gaine. Nous avons ainsi obtenu des courbes maîtresses présentant le même k0 (fréquence d'essai, i.e facteur pré exponentiel) mais dont la forme est légèrement différente. La stabilité des variations d’indice est meilleure dans le cœur (moins dopé en Ge) que dans la gaine photosensible. Dans un second temps, nous avons cherché à déterminer les conditions de passivation et à prédire la durée de vie des réseaux déverminés à partir des réseaux de Bragg qualifiés d’élémentaires. Pour la première fois à notre connaissance, nous avons validé de façon fiable les conditions de passivation et les prédictions de durée de vie en construisant une nouvelle courbe maîtresse sur des monofiltres GFF préalablement déverminés. Conformément à la théorie, cette courbe maîtresse présente le même k0 et une forme similaire à celle établie au moyen de réseaux non déverminés, ce qui valide la fiabilité de nos prédictions. / The main objective of this thesis was to investigate how it is possible to extend the master curveapproach to complex components, in order to calculate annealing conditions and giving a life timeprediction according those annealing conditions. We studied the stability of a simple Bragg grating (noapodisation, constant pitch, no tilt). Then, we have been able to study the problem of the stability(according to specific criteria) of complex components: CDC and GFF monofilters. This thesis allowed toshow precisely what is the VAREPA framework and how to apply it to optical telecommunicationsproblems. To give an answer to the question of the possibility of extending the master curve approach tocomplex components, series of accelerate aging studies have been carried out. For this purpose, ameasurement protocol including the determination of the measurement uncertainty was developed. Thisprotocol allow, to determine confidence intervals on the life time prediction.We studied the kinetics of photo induced index growth in the optical fiber dedicated forfabrication of CDC (Coreactive). This study allowed us to demonstrate that the predominant reaction atthe origin of changes in refractive index is activated by a one photon absorption. On the other hand wehave extended the VEREPA framework used to predict the Bragg gratings erasure to take into account thegrowing kinetics. In a second step we tried to calculate annealing conditions in the presence of residualmolecular hydrogen and associated Bragg grating life time prediction. For that purpose we established themaster curve of photo-induced Bragg gratings without annealing, then we validated the annealingconditions and lifetime predictions by building a new master curve from aging of annealed Bragg gratings(in presence of residual hydrogen).We studied the thermal stability of hydrogenated fiber Bragg gratings dedicated to futuremonofiltres GFF in similar conditions to those components. We used master curves from basic Bragggratings (ie no apodisation, constant pitch, no tilt) simply out-gazed at "cold" temperature (here 2 days at50 ° C and 2 days at 110 ° C). Then the aging of the index profile of a GFF monofilter have beensimulated (index profile of the core and of the cladding, each of them having a different master curve).For that purpose the profile have been separated into 35 "basic" filters. Then the spectral response of thisaged monofilter (e.g. 30 days at 200°C) have been calculated and compared with experimentalmeasurements. The advantage of this approach is that it is general and allow to change the annealingconditions if needed. Firstly, this study allowed to highlight that the stability of photo-induced indexchanges in the core depend little on the initial amplitude modulation for values between several 10-5 and10-3. Secondly, due to the presence of a highly sensitive optical cladding (and therefore highly Ge doped),Master curves, of photo-induced index change in the core and the cladding have been established forvalues ranging up to 10-3 in the core and 3.10-3 in the cladding. Master Curves with the same k0 havebeen obtained but the elbow and the slopes are different. Stability of index variations in the core is better(less Ge doped) than in the photosensitive cladding. In a second step, from the basic Bragg gratings, theannealing conditions and the lifetime have been determined. For the first time to our knowledge, thereliably of the annealing conditions and the life time predictions have been validated by building a newmaster curve on annealed GFF monofilters. According to the theory, this master curve show the same k0as the one determined using non-annealed gratings. More beyond the elbow, the two curves are same,which validates the reliability of our predictions.

La morphine demeure l'antalgique de référence pour le traitement de la douleur (nociception), mais elle est également responsable d‘effets secondaires importants. Des études ont montré que les animaux privés de canaux potassiques TREK-1 (TWIK-related K+channels) étaient plus sensibles à la douleur. Plus récemment, il a été démontré que le canal potassique TREK-1 joue un rôle crucial dans l'analgésie induite par la morphine chez les souris, alors qu'il n'est pas impliqué dans les effets secondaires (constipation, dépression respiratoire et dépendance). Ces résultats suggèrent que les canaux TREK-1 constituent des cibles d‘intérêt pour la conception de nouveaux antalgiques sans effets indésirables liés aux opioïdes. Des études antérieures au sein de notre laboratoire ont permis l'identification de quatre structures chefs de file, activatrices des canaux TREK-1, présentant une activité antalgique in vivo. La structure 3D du canal TREK-1 n‘étant pas élucidée au moment de nos travaux, nous avons décidé d'effectuer une optimisation basée sur une étude de relation structure-activité (RSA). Trente-six analogues ont été synthétisés par condensation de Knoevenagel et évalués pour leur effet antalgique (test de l‘acide acétique, test de la plaque chaude) et leur capacité à activer le canal TREK-1 (électrophysiologie). La capacité des substituants du noyau aromatique à établir des interactions de type liaison hydrogène ainsi que le volume de ces substituants ont une influence déterminante sur l'activité. Des résultats prometteurs ont émergé de cette étude RSA: 5 molécules présentent une très bonne activité antalgique (> 50% d'inhibition de la douleur, test de la plaque chaude) ainsi que d'une bonne activation de TREK-1 canaux (R ≥ 2 à 10 μM ou R ≥ 4 au-dessus de 20 μM). / Morphine remains the analgesic of reference for the treatment of pain (nociception), but it is also responsible for serious adverse effects. Research studies have shown that animals deprived of potassium channels TREK-1 (TWIK-related K+ channels) were over-sensitive to pain. More recently, it has been demonstrated that the TREK-1 potassium channel is a crucial contributor of morphine-induced analgesia in mice, while it is not involved in morphine-induced constipation, respiratory depression and dependence. These results suggest that the TREK-1 channels constitute targets of interest for the design of novel analgesics without opioid-like adverse effects. Previous studies within our consortium led to the identification of four lead structures as TREK-1 activators exhibiting analgesic activity in vivo.Since the 3D structure of TREK-1 was not available at the time, we decided to perform hit optimization by conventional structure-activity relationship (SAR) studies. Thirty six analogs were synthesized via Knoevenagel condensation and evaluated for their analgesic effect (writhing test, hot plate assay) and their ability to activate TREK-1 channel (electrophysiology). It turned out that the possibility to form hydrogen bonding interaction (aryl moiety) and the volume of substituents of the amide or ester has a crucial influence on activity. Promising results emerged from this SAR study: 5 molecules display a very good analgesic activity (> 50% inhibition of pain, hot plate assay) as well as a good activation of TREK-1 channels (R ≥ 2 at 10μM or R ≥ 4 above 20μM).