Ruthenium(III) acetylacetonate was employed for the first time as homogeneous catalyst in the hydrolysis of sodium borohydride. Ruthenium(III) acetylacetonate was not reduced by sodium borohydride under the experimental conditions and remains unchanged after the catalysis, as shown by FT-IR and UV-Vis spectroscopic characterization. Poisoning experiments with mercury, carbon disulfide or trimethylphosphite provide compelling evidence that ruthenium(III) acetylacetonate is indeed a homogenous catalyst in the hydrolysis of sodium borohydride. Kinetics of the ruthenium(III) acetylacetonate catalyzed hydrolysis of sodium borohydride was studied depending on the catalyst concentration, substrate concentration and temperature. The hydrogen generation was found to be first order with respect to both the substrate concentration and catalyst concentration. The activation parameters of this reaction were also determined from the evaluation of the kinetic data: activation energy / Ea = 25.6 &amp / #61617 / &amp / #61472 / 1.3 kJ.mol-1, the enthalpy of activation / &amp / #8710 / H# = 24.6 &plusmn / 1.2 kJ.mol-1 and the entropy of activation &amp / #8710 / S# = -170 &plusmn / 5 J&amp / #61655 / mol-1&amp / #61655 / K-1. Ruthenium(III) acetylacetonate provides the lowest activation energy ever found for the hydrolysis of sodium borohydride. Ruthenium(III) acetylacetonate was found to be highly active catalyst providing 1183 total turnovers in the hydrolysis of sodium borohydride over 180 min before they are deactivated. The recorded turnover frequency (TOF) is 6.55 min-1.

In this thesis we develop a theoretical framework for the identification of situations where the equal frequency (EF) or equal variance (EV) subclassification may produce lower bias and/or variance of the estimator. We conduct simulation studies to examine the EF and EV approaches under different types of model misspecification. We apply two weighting schemes in our simulations: equal weights (EW) and inverse variance (IV) weights. Our simulation results indicate that under the quadratic term misspecification, the EF-IV estimator provides the lowest bias and root mean square error as compared to the ordinary least square estimator and other propensity score estimators. Our theorem development demonstrates that if higher variation occurs with larger bias for within subclass treatment effect estimates then the EF-IV estimator has a smaller overall bias than the EF-EW estimator. We show that the EF-IV estimator always has a smaller variance than the EF-EW estimator. We also propose a novel method of subclassification that focuses on creating homogeneous propensity score subclasses to produce an estimator with reduced biased in some circumstances. We feel our research contributes to the field of propensity score adjustments by providing new theorems to compare the overall bias and variance between different propensity score estimators. / Graduation date: 2012

本研究的研究目的是提供英文老師如何在課堂上有效運用合作教 學，並提供老師在處理合作學習分組上一些適當、 有用的建議。本研究以一班台北市高職二年級學生為對象，以四種合作教學法應用在他們英文課上，並將實驗劃分為兩階段—同質學習能力小組及異質學習能力小組。藉此探討不同學習能力的學生對不同能力分組方式，有何感受及差異。此外，本論文亦深入探討合作學習在學生情意領域上的影響， 比照他們在不同分組階段後的感受及成效。 資料蒐集方式包括兩份主要問卷調查，分別於不同分組階段後實施，及學生週誌、課堂觀察、及訪談。資料分析方式為量化的描述性統計及質化內容分析法。研究結果摘要如下： 一. 高成就學生偏好同質學習能力分組，並在社會技巧及英語學習上，顯著優於其他同學。 二. 低成就學生偏好異質學習能力分組，實施合作教學後，對於學習意願、上課態度上，有明顯進步。 三. 實施合作教學後，大部分學生在英語學習、學習興趣、態度、及社會技巧、人際關係上，皆有提升。 / The purpose of the study is to examine the effect of different groupings of Cooperative Learning on an English class of vocational high school students in Taiwan. Cooperative Learning is one of the teaching techniques applied in EFL classrooms, proved to be effective in promoting students’ academic achievement, affective domain as well as improving students’ interpersonal relationship. Although many EFL teachers in Taiwan have adopted cooperative learning to their teaching, not all of them paid attention to the grouping criteria. This study aims to investigate which ability grouping, heterogeneous or homogeneous, can bring most benefits to the students in their English learning and affective domain. In other words, this study tries to probe in the effectiveness of cooperative learning, by students’ perception, whether their learning attitude, achievement and social skills are enhanced through cooperative learning. And the relationship between different ability levels of the students and their preference for different groupings is also investigated. The grouping criteria, based on the participants’ academic achievement, divide the experiment into two stages—heterogeneous grouping and homogeneous grouping. Four cooperative learning methods are applied in the class—Students Team Achievement Division (STAD), Teams-Games-Tournaments (TGT), Learning Together (LT) and Jigsaw. Forty-two students, taught by the researcher, from the 2nd year class at a vocational high school in Taipei, have participated in this study. By conducting questionnaires after the two stages of different groupings and oral interviews at the end of the experiment, the researcher collected and analyzed the data. The findings of the study indicate that high-ability students prefer to work with the similar-ability peers, while low-ability ones prefer to work in heterogeneous groups. The participants are positive toward the effectiveness of cooperative learning in promoting their English learning, learning attitude and social skills. By running SPSS, the statistical results also show significant difference that high-achieving students are satisfied with the improvement of their social skills and English learning more than the students of other levels when they are placed in homogeneous groups. The study not only provides EFL teachers with an effective framework of applying cooperative learning in English class, but also offers teachers appropriate and useful suggestion in adopting different groupings. Based on the above results, some pedagogical implications for English teachers and suggestions for learning strategy instructions are provided at the end of the study.

Previous research has shown that the sample preparation method used to reconstitute specimens for granular materials can have a significant impact on its mechanistic behavior. As the Discrete Element Method becomes a more popular choice for modeling multiphysics problems involving granular materials, the sample heterogeneity should be correctly characterized in order to obtain accurate results. In order to capture the effect of sample preparation on the homogeneity of the sample, standard procedures were used to reconstitute samples composed of a homogeneous granular material. X-ray computed tomography and image analysis techniques were then used to characterize the spatial heterogeneity of a typical sample. The sample preparation method was modeled numerically using the Discrete Element program PFC3D. The resulting microstructure of the numerical sample was compared to the results of the image analysis to determine if the heterogeneity of the sample could be reproduced correctly for use in Discrete Element Modeling.

The synthesis and characterization of a series of chiral indium complexes bearing a tridentate NNO ligand are reported. The ligand 2-[[[(dimethylamino)cyclohexyl]amino]methyl]- 4,6-bis(tert-butyl) phenol (H₂NNO) was synthesized via a previously published procedure and bound to indium by both a protonolysis and salt metathesis route. A dimethylated indium complex (NNO)InMe₂ (1) was isolated by reaction of InMe₃ with H₂NNO. A one-pot saltmetathesis route was used to produce a unique mixed-bridge dinuclear indium complex [(NNO)InCl] ₂(μ-OEt)(μ-Cl) (3) from a mixture of indium trichloride, potassium ethoxide and the monopotassiated salt of the ligand, KH(NNO). Direct reaction of KH(NNO) and indium trichloride resulted in the formation of (NNO)InCl₂ (4) which was carried forward to 3 by reaction with sodium ethoxide. The complex 3 is active for the ROP of β-butyrolactone ε-caprolactone and lactide and is the first reported indium-based catalyst for lactide or β-butyrolactone ROP. Kinetic studies of 3 for ROP of LA revealed that catalyst was well-behaved, and that the rate was first order with regard to lactide and catalyst. The enthalpy and entropy of activation for the ROP were experimentally determined. Polymer produced by ROP by 3 has narrow molecular weight distribution and a good correlation is seen between the observed moleular weight and monomer loading. A mechanism was proposed for 3 acting as a catalyst for the ROP of lactide; however further experiments are required to confirm this mechanism. Polymer samples isolated from the ROP of rac-lactide by rac-3 show isotactic enrichment. It is postulated that the chiral catalyst 3 is exerting stereocontrol via an enantiomorphic site control mechanism.

Thesis (Ph. D.)--Miami University, Dept. of Educational Leadership, 2006. / Title from second page of PDF document. Includes bibliographical references (p. 94-98).

Στην παρούσα εργασία θα μελετήσουμε κάποιες συνθήκες υπό τις οποίες συγκεκριμένες κλάσεις πολλαπλοτήτων σημαιών (flag manifolds) δέχονται ομογενείς ισογεωδαισιακές καμπύλες. Μια λεία πολλαπλότητα M διάστασης n είναι ένας Hausdorff και 2ος αριθμήσιμος τοπολογικός χώρος, τοπικά ομοιομορφικός με έναν Ευκλείδειο χώρο διάστασης n, εφοδιασμένος με μια διαφορική δομή. Ένα παράδειγμα πολλαπλότητας διάστασης 2 είναι μια επιφάνεια του χώρου. Ο εφοδιασμός μιας λείας πολλαπλότητας M με μια μετρική g στον εφαπτόμενο χώρο κάθε σημείου της επιτρέπει την εισαγωγή γεωμετρικών ιδιοτήτων στην M (μήκη καμπυλών, καμπυλότητα κλπ.). Μια σημαντική κλάση καμπυλών σε μια πολλαπλότητα M είναι οι γεωδαισιακές καμπύλες που έχουν την ιδιότητα να ελαχιστοποιούν την απόσταση μεταξύ δύο αρκετά κοντινών σημείων της M. Επιπλέον, δεδομένου ενός σημείου p μιας πολλαπλότητας M και εφαπτόμενου διανύσματος v στο p, υπάρχει μοναδική γεωδαισιακή καμπύλη διερχόμενη από το p με κατεύθυνση το v. Μια ομάδα Lie G είναι μια λεία πολλαπλότητα με δομή ομάδας τέτοια ώστε οι πράξεις του πολλαπλασιασμού και αντιστροφής να είναι διαφορίσιμες. Μια τέτοια ομάδα είναι και η μοναδιαία σφαίρα. Βασικό χαρακτηριστικό των ομάδων Lie είναι ότι η γεωμετρία τους παραμένει αναλλοίωτη σε όλα τα σημεία τους. Συνεπώς, η μελέτη της γεωμετρίας μιας ομάδας Lie G ανάγεται στη μελέτη της γεωμετρίας σε μια περιοχή του ουδετέρου στοιχείου της e και συγκεκριμένα, στη μελέτη της άλγεβρας Lie της G, δηλαδή τον εφαπτόμενο διανυσματικό χώρο της G στο e. Οι πολλαπλότητες που γενικεύουν αυτή την ιδιότητα ονομάζονται ομογενείς χώροι. Ένας ομογενής χώρος είναι μια λεία πολλαπλότητα M στην οποία δρα με συγκεκριμένο τρόπο μια ομάδα Lie G. Η G ορίζει μια γεωμετρία στην M που είναι αναλλοίωτη σε κάθε σημείο της M. Αυτό επιτυγχάνεται με τον ορισμό των G-αναλλοίωτων μετρικών στον ομογενή χώρο M. Στην περίπτωση που η G είναι συμπαγής και ημιαπλή ο ομογενής χώρος ονομάζεται πολλαπλότητα σημαιών. Αποδεικνύεται ότι κάθε ομογενής χώρος M δέχεται ομογενείς γεωδαισιακές καμπύλες, δηλαδή γεωδαισιακές που αποτελούν τροχιές, μέσω της δράσης της G στη M, μιας κατηγορίας υποομάδων της G που ονομάζονται μονοπαραμετρικές υποομάδες. Στην παρούσα εργασία θα μελετήσουμε την ύπαρξη ισογεωδαισιακών καμπυλών σε πολλαπλότητες σημαιών, δηλαδή καμπυλών που είναι ομογενείς γεωδαισιακές ανεξάρτητα της G-αναλλοίωτης μετρικής που θα ορίσουμε στην πολλαπλότητα. / In this thesis we study homogeneous geodesics on certain classes of flag manifolds.

This thesis is concerned with the formulation of a suitable notion of monotonicity of discrete and continuous-time dynamical systems on Lie groups and homogeneous spaces. In a linear space, monotonicity refers to the property of a system that preserves an ordering of the elements of the space. Monotone systems have been studied in detail and are of great interest for their numerous applications, as well as their close connections to many physical and biological systems. In a linear space, a powerful local characterisation of monotonicity is provided by differential positivity with respect to a constant cone field, which combines positivity theory with a local analysis of nonlinear systems. Since many dynamical systems are naturally defined on nonlinear spaces, it is important to seek a suitable adaptation of monotonicity on such spaces. However, the question of how one can develop a suitable notion of monotonicity on a nonlinear manifold is complicated by the general absence of a clear and well-defined notion of order on such a space. Fortunately, for Lie groups and important examples of homogeneous spaces that are ubiquitous in many problems of engineering and applied mathematics, symmetry provides a way forward. Specifically, the existence of a notion of geometric invariance on such spaces allows for the generation of invariant cone fields, which in turn induce notions of conal orders. We propose differential positivity with respect to invariant cone fields as a natural and powerful generalisation of monotonicity to nonlinear spaces and develop the theory in this thesis. We illustrate the ideas with numerous examples and apply the theory to a number of areas, including the theory of consensus on Lie groups and order theory on the set of positive definite matrices.

Actuellement, les principaux thèmes pour le secteur de transport sont le réchauffement global et la crise énergétique, ce qui encourage les chercheurs à développer des technologies alternatives et efficaces. Le concept ‘HCCI’ (combustion d’une charge homogène, allumée par compression) est l’une des solutions pour le moteur de véhicules. Ce mode de combustion, indépendant d’une notion de propagation de flamme, permet de réduire fortement les émissions critiques de NOX et de suies dans les gaz d'échappement. Cette combustion de type HCCI du carburant diesel se caractérise par une combustion à deux étapes. Parallèlement, l’apparition de nouveaux carburants, comme le bio-alcool, est une autre voie de recherche. Les bio-alcools ont un nombre d’indice d'octane élevé qui peut se mélanger avec du carburant diesel pour optimiser la combustion de HCCI des carburants diesel. L’objectif de cette thèse est donc de caractériser les deux étapes de la combustion HCCI en étudiant l’influence de l’impact de l’ajout d’une fraction d’alcools dans diesel. La comparaison avec un mélange d’iso-octane, hydrocarbure à indice d'octane élevé de paraffine et des mélanges dilués via les gaz d’échappement est aussi analysée en tant que verrous potentiels pour améliorer la combustion de type HCCI. Dans cette thèse, le n-heptane est choisi comme composé principal représentatif du diesel, l'éthanol et 1-butanol sont choisis comme bio-alcools. L’analyse présentée ici se repose sur trois approches différentes : l’analyse expérimentale de la pression cylindre, l'analyse d'images de chimiluminescence spontanée de certaines espèces et les résultats issus de la modélisation cinétique de la combustion. / Currently, the major issues for the transportation sector are the global warming and energy crisis which encourage researchers to develop an alternative green efficient technology. The homogeneous charge compression ignition (HCCI) can be one of solutions for the automotive engine. This combustion concept is independent on the high temperature flame propagation which releases lowest critical emissions (NOX and PM) in the exhaust gas. HCCI combustion of diesel fuel presents specific characteristic of two-stage ignition that over-advances the main heat release. As the importance of bio-alcohol fuels increases, it is interesting to evaluate the potential of the fuels, to optimize the HCCI combustion of diesel fuels. This is the objective of this phD thesis. The two-stage ignition characteristic of the diesel hydrocarbon is described and the influence of alcohol fuel fraction in diesel blends is investigated in comparison with high octane paraffin hydrocarbon diesel blends and EGR addition. All potentials are concluded to the potential for HCCI combustion improvement. In this thesis, n-heptane was selected as the major diesel representative component and ethanol and 1-butanol as the considered alcohol fuels. Three approaches were used based on experimental cylinder pressure analysis, the chemiluminescence emissions image analysis and the chemical kinetic analysis results from the engine modeling. A detailed chemical kinetic scheme was specifically developed from sub-scheme of all considered fuel.

Os estudos que envolveram os três capítulos da minha tese englobam padrões de distribuição dos insetos aquáticos, agregando informações sobre características funcionais dessas comunidades. No primeiro capítulo avaliei a influência da heterogeneidade do substrato sobre as características funcionais dos insetos bentônicos. Concluí que em ambientes naturais o substrato heterogêneo apresentou combinações específicas de atributos, associados principalmente ao tamanho do corpo e hábitos alimentares. Esses atributos exercem forte influência sobre o funcionamento do ecossistema dos riachos. No segundo capítulo verifiquei a variação temporal dos atributos funcionais dos insetos aquáticos, com enfoque para organismos especialistas e generalistas. Nos primeiros estágios da colonização organismos coexistem independente dos atributos, isso porque a comunidade mostrou atributos similares. Nos estágios mais avançados de colonização os organismos generalistas resistiram a fatores bióticos e abióticos, mostrando uma variedade de atributos superior à que foi encontrada no início da colonização. Conclui que a ausência ou diminuição de organismos especialistas pode ser um indicador de degradação ambiental. No terceiro capítulo avaliei se existe efeito da presença/ausência de cobertura vegetal considerando a distância entre os riachos sobre as comunidades de insetos. Concluí que a cobertura vegetal no entorno dos riachos é um fator determinante para a distribuição espacial dos insetos aquáticos. Em locais com cobertura vegetal, insetos aquáticos com maior habilidade de dispersão apresentaram decaimento da similaridade com a distância, contrário do que foi verificado para locais sem vegetação. Já para dispersores menos hábeis, riachos mais distantes apresentaram comunidades menos similares para locais come sem cobertura vegetal. Com isso, conclui que a presença de vegetação no entorno dos riachos pode ser uma barreira física que limita a dispersão dos insetos com maior capacidade de voo. Finalizando, este trabalho ressalta a influência de fatores locais (substrato) e regionais (vegetação/limitação de dispersão) sobre as características funcionais da fauna aquática. Além disso, a manutenção da heterogeneidade do substrato e da vegetação ripária, contribuiu para a manutenção da diversidade funcional das comunidades de insetos aquáticos. / Studies of my thesis include aspects of distribution patterns of aquatic insects and aggregate information on functional characteristics. In the first chapter, I evaluated the influence of substrate heterogeneity on the functional characteristics of benthic insects. I concluded that in natural environments, heterogeneous substrate select specific traits combinations associated mainly to body size and feeding habits, attributes that exert a strong influence on the functioning of ecosystems. In the second chapter, I verified the temporal variation of the functional attributes of aquatic insects, focusing on specialist and generalist taxa. In early stages of colonization, organisms coexist independent of the attributes, because the community showed similar attributes. In the last stages, specialists were able to resist to biotic and abiotic factors showing a variety of attributes that was not founded at the beginning of colonization. In conclusion, the absence or decrease of specialists can be an indicator of environmental degradation. In the third chapter, I used a functional approach with emphasis on attributes related to dispersion. We conclude that the canopy cover of streams is a determining factor for the distribution of aquatic insects. Aquatic insects with greater ability to disperse showed a weak pattern of distance decay of similarity, only in streams with grassland. For weak dispersers patterns of was similar for the two streams (open and forest riparian vegetation). Thus, we conclude that the presence of vegetation streams can be a physical barrier that limits the insect dispersal, especially taxa with greater abilities to disperse. Finally, this study highlights the influence of local (substrate) and regional (limiting dispersion) factors on the functional characteristics of the aquatic fauna. In addition, maintaining the diversity of substrate and riparian vegetation, contributes to the functional and taxonomic diversity of aquatic insect communities.