Detritylation of tri-O-trityl-penta-O-acetyl sucrose with catalytic bydrogenolysis or graded hydrolysis with aqueous acetic acid gave in yields up to 60% a new crystal line penta-O-acetyl sucrose derivative. Methylation of the pentaacetate with the Purdie reagents, followed by deacetylation and chromatographic purification gave a sirupy tri-O-methyl sucrose which was shown to be 1’, 4, 6' -tri-O-methyl sucrose by periodate oxidation and by hydrolysis to equal parts of 4-O-methyl-D-glucose and 1, 6-di-O-methyl-D-fructose. The glucose derivative was identified by paper chromatography, specific rotation and by conversion to the known, crystalline osazone, and the structure of the new sirupy 1, 6-di-O-raethyl-D-fruetose was established by analysis, periodate oxidation, paper chromatographic behavior and the specific rotation. Deacetylation of tri-0-trityl-penta-O-acetyl sucrose gave an amorphous tri-O-trityl sucrose and methylation of this compound with the Purdie reagents, followed by detritylation with aqueous acetic acid gave a sirupy penta-O-methyl sucrose derivative, which was identified as 2, 3, 3', 4, 4’ -penta-O-methyl sucrose by hydrolysis to equal parts of the known 2, 3, k -tri-O-methyl-D-glueose and 3, 4 -di-O-methyl-D-fructose. It was therefore established that the trityl groups in the original tri-O-trityl-penta-O-acetyl sucrose occupied the three primary positions (1’, 6 and 6’) in the sucrose molecule and that acetyl migration from C4 to C6 in the glucose moiety had occurred during the synthesis of the tri-O-methyl sucrose. Vinylation of 1: 2-3: 4-di-O-isopropylidene-D-galactose with vinyl acetate after the method of Adelraan gave after catalytic hydrogenation followed by removal of the acetone groups a 0.7% yield of sirupy 6-O-ethyl-D-galactose. The new galactose derivative was identified by comparison with an authentic sample synthesized by direct ethylation of 1; 2 -3: 4 -di-O-iaopropylidene-D-galactose. Preliminary studies of the vinylation of the new crystalline penta-O-acetyl sucrose are reported. The action of Dowex I on several acetates of non-reducing carbohydrates was found to result in deacetylation in nearly quantitative yields. / Science, Faculty of / Chemistry, Department of / Graduate

Le but de cette thèse est de présenter une analyse statique générique pour des programmes multitâche écrits en Java.<br />Les programmes multitâche exécutent plusieurs tâches en parallèle. Ces tâches communiquent implicitement par le biais de la mémoire partagée et elles se synchonisent sur des moniteurs (les primitives wait-notify, etc..). Il y a quelques années, les architectures avec double processeurs ont commencé à être disponibles sur le marché à petit prix. Aujourd'hui, presque tous les ordinateurs ont au moins deux noyaux, la tendance actuelle du marché étant de mettre de plus en plus de processeurs par puce. Cette révolution amène également de nouveaux défis en matière de programmation, car elle demande aux développeurs d'implanter des programmes multitâche. Le multitâche est supporté en natif par la plupart des langages de programmation courants, comme Java et C#.<br />Le but de l'analyse statique est de calculer des informations sur le comportement d'un programme, de manière conservative et automatique. Une application de l'analyse statique est le développement d'outils qui aident au débogage des programmes. Plusieurs méthodes d'analyse statique ont été proposées. Nous suivrons le cadre de l'interprétation abstraite, une théorie mathématique permettant de définir des approximations correctes de sémantiques de programmes. Cette méthode a déjà été utilisée pour un large spectre de langages de programmation.<br />L'idée fondamentale des analyseurs statiques génériques est de développer un outils qui puissent être interfacé avec différents domaines numériques et différentes propriétés. Pendant ces dernières années, beaucoup de travaux se sont attaqués à cet enjeu, et ils ont été appliqué avec succès pour déboguer des logiciels industriels. La force de ces analyseurs réside dans le fait qu'une grande partie de l'analyse peut être réutilisée pour vérifier plusieurs propriétés. L'utilisation de différents domaines numériques permet le développement d'analyses plus rapides mais moins précises, ou plus lentes mais plus précises.<br /><br />Dans cette thèse, nous présentons la conception d'un analyseur générique pour des programmes multitâche. Avant tout, nous définissons le modèle mémoire, appelé happens-before memory model. Puis, nous approximons ce modéle mémoire en une semantique calculable. Les modéles mémoire définissent les comportements autorisés pendant l'exé-cution d'un programme multitâche. Commençant par la définition (informelle) de ce modèle mémoire particulier, nous définissons une sémantique qui construit toutes les exécutions finies selon ce modèle mémoire. Une exécution d'un programme multitâche est décrite par une function qui associe les tâches à des séquences (ou traces) d'états. Nous montrons comment concevoir une sémantique abstraite calculable, et nous montrons formellement la correction des résultat de cette analyse.<br />Ensuite, nous définissons et approximons une nouvelle propriété qui porte sur les comportements non-déterministes causés par le multitâche, c'est à dire aux entrelacements arbitraires pendant l'exécution de differentes instructions de lecture. Avant tout, le non déterminisme d'un programme multitâche se définit par une différence entre plusieurs exécutions. Si deux exécutions engendrent des comportements différents dus au valeurs qui sont lues ou écrites en mémoire partagée, alors le programme est non déterministe. Nous approximons cette propriété en deux étapes: dans un premier temps, nous regroupons, pour chaque tâche, la valeur (abstraite) qui peut être écrite dans la mémoire partagée à un point de programme donné. Dans un deuxième temps, nous résumons toutes les valeurs pouvant être écrites en parallèle, tout en nous rapellant l'ensemble des tâches qui pourraient les avoir écrites. à un premier niveau d'approximation, nous introduisons un nouveau concept de déterminisme faible. Nous proposons par ailleurs d'autres manière affaiblir la propriété de déterminisme, par exemple par projection des traces et des états, puis nous définissons une hierarchie globale de ces affaiblissements. Nous étudions aussi comment la présence de conflit sur les accès des données peut affecter le déterminisme du programme.<br />Nous appliquons ce cadre de travail théorique à Java. En particulier, nous définissons une sémantique du language objet de Java, selon sa spécification. Ensuite, nous approximons cette sémantique afin de garder uniquement l'information qui est nécessaire pour l'analyse des programmes multitâche. Le cœur de cette abstraction est une analyse d'alias qui approxime les références afin d'identifier les tâches, de vérifier les accès en mémoire partagée, et de détecter quand deux tâches ont un moniteur commun afin d'en déduire quelles parties du code ne peuvent pas être éxécutées en parallèle.<br />L'analyseur générique qui est décrit ci-dessus a été entierement implanté, dans un outils appelé Checkmate. Checkmate est ainsi le premier analyseur générique pour des programmes multitâche écrits en Java. Des résultats expérimentaux sont donnés et analysés en détails. En particulier, nous étudions la précision de l'analyse lorsqu'elle est appliquée à des schémas courants de la programmation concurrente, ainsi qu'à d'autres exemples. Nous observons également les performances de l'analyse lorsqu'elle est appliquée à une application incrémentale, ainsi qu'à des exemples de références bien connus.<br />Une autre contribution de cette thèse est l'extension d'un analyseur générique existant qui s'appelle Clousot et qui permet de vérifier le non débordement des mémoires tampons. Il s'avère que cette analyse passe à l'échelle des programmes industriels et qu'elle est précise. En résumé, nous présentons une application d'un analyseur statique générique industriel existant pour détecter et prouver une propriété présentant un intérêt pratique, ce qui montre la puissance de cette approche dans le développement d'outils qui soient utiles pour les développeurs.

The basic philosophy of Functional Data Analysis (FDA) is to think of the observed data functions as elements of a possibly infinite-dimensional function space. Most of the current research topics on FDA focus on advancing theoretical tools and extending existing multivariate techniques to accommodate the infinite-dimensional nature of data. This dissertation reports contributions on both fronts, where a unifying inverse regression theory for both the multivariate setting (Li 1991) and functional data from a Reproducing Kernel Hilbert Space (RKHS) prospective is developed. We proposed a functional multiple-index model which models a real response variable as a function of a few predictor variables called indices. These indices are random elements of the Hilbert space spanned by a second order stochastic process and they constitute the so-called Effective Dimensional Reduction Space (EDRS). To conduct inference on the EDRS, we discovered a fundamental result which reveals the geometrical association between the EDRS and the RKHS of the process. Two inverse regression procedures, a “slicing” approach and a kernel approach, were introduced to estimate the counterpart of the EDRS in the RKHS. Further the estimate of the EDRS was achieved via the transformation from the RKHS to the original Hilbert space. To construct an asymptotic theory, we introduced an isometric mapping from the empirical RKHS to the theoretical RKHS, which can be used to measure the distance between the estimator and the target. Some general computational issues of FDA were discussed, which led to the smoothed versions of the functional inverse regression methods. Simulation studies were performed to evaluate the performance of the inference procedures and applications to biological and chemometrical data analysis were illustrated.

The S shaped log log drawdown time curve typical of pumping tests in unconfined aquifers is reinvestigated via numerical experiments. We examine the temporal and spatial evolution of the rate of change in storage in an unconfined aquifer during pumping. This evolution is related to the transition of water release mechanisms from the expansion of water and compaction of the porous medium to the drainage of water from the unsaturated zone above the initial water table and initially saturated pores as the water table falls during the pumping of the aquifer. We conclude that the transition of the water release mechanisms and vertical flow are the cause of the S shaped drawdown time. Cross-correlation analysis is then employed to examine the relationship between hydraulic properties of an unconfined aquifer and pressure observations. The analysis reveals that head observed in the saturated zone at late times along a streamline is positively correlated with the conductivity (K(s)) of the region upstream of the observation location, and negatively correlated with the K(s) of the region downstream of the observation location along the same streamline. Besides, head observations in the saturated zone at the early time are positively correlated with specific storage (S(s)) in a narrow region between the observation and pumping locations. At intermediate and late times, the head positively correlates with the heterogeneity of α (pore-size distribution parameter) in a thin disk-shaped unsaturated region above the pumping and observation locations. Saturated water content θ(s) in the vadose zone directly above the pumping and monitoring locations is found positively correlated with the head observations during the intermediate times and late times.In the end, a stochastic inverse estimation is conducted to jointly interpret a sequential pumping test in a three dimensional unconfined aquifer. K(s), S(s), θ(s) and α are estimated at the same time. The estimated results capture the pattern of the heterogeneous parameters as well as the details with a smooth distribution. The estimated heterogeneous parameter fields produce better head predictions than the traditional homogeneous method.

Formal mentoring programs rely on mentors to build supportive relationships with youth with the intention of providing positive developmental opportunities for the youth. This dissertation, which includes three studies, explores the experiences of mentors, focusing on factors that contribute to mentors committing to and sustaining mentoring relationships, and how mentors approach building a supportive relationship. Study 1 develops and tests a conceptual model of mentor retention integrating concepts from the volunteerism and interpersonal relationship literatures to predict mentor retention. Participants were 51 college student-mentors. Path analysis showed support for the conceptual model. Mentor retention was predicted by their commitment but not by role identity. Role identity was positively related to mentor commitment. Role identity was predicted by relationship satisfaction, available alternatives and investment; only satisfaction predicted commitment. Study 2 examined how program practices influence mentor commitment utilizing secondary data from 551 mentors from mentoring programs involved in a large, randomized controlled trial evaluating an intervention to improve mentoring program quality. Path analysis demonstrated that how well the mentor felt the program set expectations and whether they were matched with a youth based on their preferences were associated with the mentor’s commitment. The relationships between commitment and program practices were partially mediated by the mentor’s relationship satisfaction and available alternatives. Study 3 explores how mentors approach building their mentoring relationship, whether different approaches contribute to supports offered to the youth, and if there are differences by gender or whether the mentor has previous experience mentoring. Thematic analysis of 16 mentoring relationships did not identify any specific approach as best. Instead, what mattered was the fit of the approach with the specific circumstances of the match. Mentors whose approach fit well or who were able to adapt their approach had the longest matches and provided the most support. Males were more often described to have an approach that was a good fit and to have provided more support. Whether previous mentoring experience helped a mentor build the relationship and support the youth depended on how the previous relationship went and how it influenced the mentor’s expectations with regard to the current match.

The identification of the physical parameters (mass, stiffness, and damping) of structural, mechanical, and biomechanical systems is a major challenge in many applications, especially when dealing with old systems and biological systems with heavy damping and where environmental noises are presented. This work presents a novel methodology called eigenvector phase correction (EVPHC) to solve for the physical parameters of structural and biomechanical systems even with the existence of a significant amount of noise. The method was first tested on structural/mechanical systems and showed superior results when compared with an iterative method from the literature. EVPHC was then developed and used to identify the physical parameters of supine humans under vertical whole-body vibration. Modal parameters of fifteen human subjects, in the supine position, were first identified in this work using experimentation under vertical whole-body vibration. EVPHC was then used to solve an inverse modal problem for the identification of the stiffness and damping parameters at the cervical and lumbar areas of supine humans. The results showed that the resulting physical parameters were realistically close to those presented in the literature. The proposed human model was able to predict the time histories of the acceleration at the head, chest, pelvis, and legs very closely to those of the experimental measured values. A scaling methodology is also presented in this work, where an average human model was scaled to an individual subject using the body mass properties.

Mass spectrometry-based proteomics excels at high-throughput identification of proteins expressed in complex biological samples. However, the technology struggles to identify low abundance proteins due to large amounts of redundant data acquired for high abundance proteins with little collected for low abundance proteins. To improve the identification sensitivity of these proteins, I designed a machine learning classifier that assesses protein identification confidence on-the-fly, during mass spectrometry analysis. Proteins deemed confidently identified are excluded from further analysis, saving mass spectrometry resources for lower abundance proteins. Simulating data from a HEK293 cell lysate mass spectrometry analysis, our algorithm uses 16.2% - 66.2% fewer mass spectrometry resources with a 2.6% - 39.5% drop in protein identifications. When applied to live mass spectrometry experiments, these saved resources will likely improve the overall protein identification sensitivity of the experiment, particularly for lower abundance proteins, and will therefore provide a better understanding of the cell’s biology.

付記する学位プログラム名: デザイン学大学院連携プログラム / 京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22772号 / 工博第4771号 / 新制||工||1746(附属図書館) / 京都大学大学院工学研究科機械理工学専攻 / (主査)教授 椹木 哲夫, 教授 松原 厚, 教授 小森 雅晴 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

This master’s thesis covers analysis of financial performance of company Jessgrove Central Europe s.r.o through analysis of time lines. Theoritical part is focused on definition of basic terms relating to analysis of time lines and regression analysis. In practical part, current situation of the Company is analysed. The conclusion brings own suggestions to improve current financial situation of the Company.