Thesis advisor: Chia-Kuang (Frank) Tsung / The core-shell hybrid structure is the simplest motif of two-component systems which consists of an inner core coated by an outer shell. Core-shell composite materials are attractive for their biomedical, electronic and catalytic applications in which interface between core and shell is critical for various functionalities. However, it is still challenging to study the exact role that interface plays during the formation of the core-shell structures and in the properties of the resulted materials. By studying the formation mechanism of a well interface controlled one-to-one metal nanoparticle (NP)@zeolite imidazolate framework-8 (ZIF-8) core-shell material, we found that the dissociation of capping agents on the NP surface results in direct contact between NP and ZIF-8, which is essential for the formation of core-shell structure. And the amount of capping agents on the NP surface has a significant effect to the crystallinity and stability of ZIF-8 coating shell. Guided by our understanding to the interface, one-to-one NP@UiO-66 core-shell structure has also been achieved for the first time. We believe that our research will help the development of rational design and synthesis of core-shell structures, particularly in those requiring good interface controls. / Thesis (MS) — Boston College, 2017. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Au cours de la dernière décennie, les progrès en Biologie Moléculaire ont accéléré le développement de techniques d'investigation à haut-débit. En particulier, l'étude du transcriptome a permis des avancées majeures dans la recherche médicale. Dans cette thèse, nous nous intéressons au développement de méthodes statistiques dédiées au traitement et à l'analyse de données transcriptomiques à grande échelle. Nous abordons le problème de sélection de signatures de gènes à partir de méthodes d'analyse de l'expression différentielle et proposons une étude de comparaison de différentes approches, basée sur plusieurs stratégies de simulations et sur des données réelles. Afin de pallier les limites de ces méthodes classiques qui s'avèrent peu reproductibles, nous présentons un nouvel outil, DiAMS (DIsease Associated Modules Selection), dédié à la sélection de modules de gènes significatifs. DiAMS repose sur une extension du score-local et permet l'intégration de données d'expressions et de données d'interactions protéiques. Par la suite, nous nous intéressons au problème d'inférence de réseaux de régulation de gènes. Nous proposons une méthode de reconstruction à partir de modèles graphiques Gaussiens, basée sur l'introduction d'a priori biologique sur la structure des réseaux. Cette approche nous permet d'étudier les interactions entre gènes et d'identifier des altérations dans les mécanismes de régulation, qui peuvent conduire à l'apparition ou à la progression d'une maladie. Enfin l'ensemble de ces développements méthodologiques sont intégrés dans un pipeline d'analyse que nous appliquons à l'étude de la rechute métastatique dans le cancer du sein. / Recent advances in Molecular Biology have led biologists toward high-throughput genomic studies. In particular, the investigation of the human transcriptome offers unprecedented opportunities for understanding cellular and disease mechanisms. In this PhD, we put our focus on providing robust statistical methods dedicated to the treatment and the analysis of high-throughput transcriptome data. We discuss the differential analysis approaches available in the literature for identifying genes associated with a phenotype of interest and propose a comparison study. We provide practical recommendations on the appropriate method to be used based on various simulation models and real datasets. With the eventual goal of overcoming the inherent instability of differential analysis strategies, we have developed an innovative approach called DiAMS, for DIsease Associated Modules Selection. This method was applied to select significant modules of genes rather than individual genes and involves the integration of both transcriptome and protein interactions data in a local-score strategy. We then focus on the development of a framework to infer gene regulatory networks by integration of a biological informative prior over network structures using Gaussian graphical models. This approach offers the possibility of exploring the molecular relationships between genes, leading to the identification of altered regulations potentially involved in disease processes. Finally, we apply our statistical developments to study the metastatic relapse of breast cancer.

Com o aumento no uso de aglomerados e grades de computadores, cresce o interesse no estudo de comunicações entre processadores. Em um computador paralelo dedicado, ou em uma rede local homogênea, o tempo de comunicação é geralmente modelado de forma similar, independente de quais processadores estão se comunicando. Em uma rede onde os links entre os computadores são heterogêneos, computadores mais próximos tendem a apresentar menor latência e maior largura de banda do que computadores distantes. Além disso, a largura de banda agregada é diferente dependendo do número de conexões simultâneas existentes entre dois aglomerados distantes. Neste trabalho estudaremos a troca completa de mensagens de tamanhos diferentes entre aglomerados interligados por backbones. Proporemos um novo algoritmo de comunicação baseado em algoritmos conhecidos, apresentaremos simulações de escalonamentos dos algoritmos estudados para esta rede multi-aglomerado e analisaremos os resultados destas simulações. / The growth in popularity of clusters and computational grids caused an increase in the interest in studying interprocessors communications. The comunication time in a dedicated parallel computer or in a local homogeneous network is modeled in a similar way, regardless of which processors are communicating. In a network with heterogeneous links, closer computers generally have lower latency and larger bandwidth than wide area computers. Besides, the aggregated bandwidth depends on the number of simultaneous connections between two wide area clusters. In this work we study the complete exchange of messages of different sizes between interconnected clusters using a backbone. We propose a new comunication algorithm based on known algorithms, we present some scheduling simulations of the studied algorithms in this multi-cluster network and we present the results analysis of these simulations.

The Space Plug-and-Play Architecture (SPA) networking approach outlined in this dissertation is an improvement over the previous approach used by the Satellite Data Model(SDM). The first improvement is the introduction of a SPA network model based on the Open Systems Interconnection (OSI) model. Second, a new addressing and routing scheme is presented, which places the burden of routing on the network infrastructure instead of the network endpoints. These improvements have been implemented in a software infrastructure called the SPA Services Manager (SSM). The SSM was developed under an International Organization for Standardization (ISO) 9001 certified development process, the details of which are presented. A collection of network timing graphs that measure latency and jitter of the SPA network is contained in this dissertation, as well as a runtime memory footprint. The maturity of the development process and these initial performance measurements demonstrate that the SSM is qualified for spaceflight.

Abstract Cobalt-based complexes are widely used in industry and organic synthesis as catalysts for the oxidation of hydrocarbons. The Co/Mn/Br (known as "CAB system") catalyst system is effective for the oxidation of toluene. The Co/Mn/Br/Zr catalyst system is powerful for the oxidation of p-xylene, but not for the oxidation of toluene. [Co3O(OAc)5(OH)(py)3][PF6] (Co 3+ trimer 5) is more effective than [Co3O(OAc)6(py)3][PF6] (Co 3+ trimer 6) as a catalyst in the CAB catalyst system. Higher temperatures favour the oxidation of toluene. Zr 4+ does not enhance the oxidation of toluene. Zr 4+ could inhibit the oxidation of toluene in the combination of Co/Br/Zr, Co/Mn/Zr or Co/Zr. NHPI enhances the formation of benzyl alcohol, but the formation of other by-products is a problem for industrial processes. Complex(es) between cobalt, manganese and zirconium might be formed during the catalytic reaction. However, attempts at the preparation of complexes consisting of Co/Zr or Mn/Zr or Co3ZrP or Co8Zr4 clusters failed. The oxidation of cyclohexane to cyclohexanone and cyclohexanol is of great industrial significance. For the homogeneous catalysis at 50 o C and 3 bar N2 pressure, the activity order is: Mn(OAc)3 �2H2O > Mn12O12 cluster > Co 3+ trimer 6 > [Co3O(OAc)3(OH)2(py)5][PF6]2 (Co 3+ trimer 3) > Co 3+ trimer 5 > Co(OAc)2 �4H2O > [Co2(OAc)3(OH)2(py)4][PF6]-asym (Co dimerasym) > [Co2(OAc)3(OH)2(py)4][PF6]-sym (Co dimersym); whereas [Mn2CoO(OAc)6(py)3]�HOAc (Mn2Co complex) and zirconium(IV) acetate hydroxide showed almost no activity under these conditions. But at 120 o C and 3 bar N2 pressure, the activity order is changed to: Co dimerasym > Co(OAc)2 �4H2O > Co trimer 3 and Mn(OAc)3 �2H2O > Co 3+ trimer 6 > Mn2Co complex > Co 3+ trimer 5 > Co dimersym > Mn12O12 cluster. The molar ratio of the products was close to cyclohexanol/cyclohexanone=2/1. Mn(II) acetate and zirconium(IV) acetate hydroxide showed almost no activity under these conditions. Among those cobalt dimers and trimers, only the cobalt dimerasym survived after the stability tests, this means that [Co2(OAc)3(OH)2(py)4][PF6]-asym might be the active form for cobalt(II) acetate in the CAB system. Metal-substituted (silico)aluminophosphate-5 molecular sieves (MeAPO-5 and MeSAPO-5) are important heterogeneous catalysts for the oxidation of cyclohexane. The preparation of MeAPO-5 and MeSAPO-5 and their catalytic activities were studied. Pure MeAPO-5 and MeSAPO-5 are obtained and characterised. Four new pairs of bimetal-substituted MeAPO-5 and MeSAPO-5(CoZr, MnZr, CrZr and MnCo) were prepared successfully. Two novel trimetal-subtituted MeAPO-5 and MeSAPO-5 (MnCoZr) are reported here. Improved methods for the preparation of four monometal-substituted MeAPO-5 (Cr, Co, Mn and Zr) and for CoCe(S)APO-5 and CrCe(S)APO-5 are reported. Novel combinational mixing conditions for the formation of gel mixtures for Me(S)APO-5 syntheses have been developed. For the oxidation of cyclohexane by TBHP catalysed by MeAPO-5 and MeSAPO-5 materials, CrZrSAPO-5 is the only active MeSAPO-5 catalyst among those materials tested under conditions of refluxing in cyclohexane. Of the MeAPO-5 materials tested, whereas CrCeSAPO-5 has very little activity, CrZrAPO-5 and CrCeAPO-5 are very active catalysts under conditions of refluxing in cyclohexane. MnCoAPO-5, MnZrAPO-5 and CrAPO-5 are also active. When Cr is in the catalyst system, the product distribution is always cyclohexanone/cyclohexanol equals 2-3)/1, compared with 1/2 for other catalysts. For MeAPO-5, the activity at 150 o C and 10 bar N2 pressure is: CrZrAPO-5 > CrCeAPO-5 > CoZrAPO-5. For MeAPO-5 and MeSAPO-5, at 150 o C and 13 bar N2 pressure, the selectivity towards cyclohexanone is: CrZrAPO-5 > CrZrSAPO-5 > CrCeAPO-5 > CrAPO-5 > MnCoAPO-5 > MnZrAPO-5; and the selectivity towards cyclohexanol is: MnZrAPO-5 > CrZrAPO-5 > MnCoAPO-5 > CrZrSAPO-5 > CrCeAPO-5 > CrAPO-5. Overall the selectivity towards the oxidation of cyclohexane is: CrZrAPO-5 > CrZrSAPO-5 > CrCeAPO-5 > CrAPO-5 > MnCoAPO-5 > MnZrAPO-5. The amount of water in the system can affect the performance of CrCeAPO-5, but has almost no effect on CrZrAPO-5. Metal leaching is another concern in potential industrial applications of MeAPO-5 and MeSAPO-5 catalysts. The heterogeneous catalysts prepared in the present work showed very little metal leaching. This feature, coupled with the good selectivities and effectivities, makes them potentially very useful.

In this thesis, we propose some innovative developments for the implementation of mean-field homogenization schemes adapted to the prediction of the behavior of elasto-plastic and elasto-viscoplastic composites. For elasto-plastic materials, the local constitutive laws written in a rate form are linearized incrementally over several time-steps so that homogenization schemes developed in the context of linear elasticity can apply over each time interval. Since the original implementation gave too stiff predictions, we propose different stiffness reductions for the matrix tangent operator and study theoretically and numerically the influence on the final macroscopic prediction. Definition of the per phase reference state in also studied and linked to the fields heterogeneity effect. Predictions thus obtained are confronted with those of a secant (or total) formulation of the constitutive laws. For elasto-viscoplastic composites, we use the affine formulation which reduces the constitutive laws to fictitious linear thermo-elastic relations in the Laplace domain where the homogenization can apply. Our main contribution is a full treatment of internal variables in the linearization procedure. This enables to deal with realistic constitutive behaviors and general loading histories. We illustrate the influence of viscous effects under various loading conditions and study the accuracy of the method with respect to the loading rate. For both classes of composites, numerous predictions obtained by mean-field homogenization schemes are confronted against those of three-dimensional finite element simulations and experimental results. For a wide range of materials and loading conditions, a good agreement at the macroscopic level between our predictions and the reference results is observed.

Many online services access a large number of autonomous data sources and at the same time need to meet different user requirements. It is essential for these services to achieve semantic interoperability among these information exchange entities. In the presence of an increasing number of proprietary business processes, heterogeneous data standards, and diverse user requirements, it is critical that the services are implemented using adaptable, extensible, and scalable technology. The COntext INterchange (COIN) approach, inspired by similar goals of the Semantic Web, provides a robust solution. In this paper, we describe how COIN can be used to implement dynamic online services where semantic differences are reconciled on the fly. We show that COIN is flexible and scalable by comparing it with several conventional approaches. With a given ontology, the number of conversions in COIN is quadratic to the semantic aspect that has the largest number of distinctions. These semantic aspects are modeled as modifiers in a conceptual ontology; in most cases the number of conversions is linear with the number of modifiers, which is significantly smaller than traditional hard-wiring middleware approach where the number of conversion programs is quadratic to the number of sources and data receivers. In the example scenario in the paper, the COIN approach needs only 5 conversions to be defined while traditional approaches require 20,000 to 100 million. COIN achieves this scalability by automatically composing all the comprehensive conversions from a small number of declaratively defined sub-conversions. / Singapore-MIT Alliance (SMA)

Thesis (Ph.D.)--University of Delaware, 2006. / Principal faculty advisor: Jochen Lauterbach, Dept. of Chemical Engineering. Includes bibliographical references.

In this thesis, the development and use of a transient heterogeneous 2D model for monolithic catalytic converter is presented. Study on the cold flow hydrodynamics, temperature effect and CO conversion and light off behaviour of different models is developed. Different models are studied based on different parameters such as monolith brick CPSI configuration, size of the converter, inlet cone sizing and inlet velocity of the converter. The results for both steady state and transient modes are presented in detail. It is shown that monolith brick CPSI has a significant effect on pressure drop and light-off behaviour of the converter. Also, converter size has a major effect on the performance of a converter. Inlet cone sizing showed to have a significant effect on the hydrodynamics of the converter but it did not have a major effect on light-off behaviour of the converter. / Chemical Engineering

This thesis has two parts, each with a different subject. Part 1 studies the macroeconomic implications of alternative health care reforms. Part 2 studies the computation and simulation of dynamic competitive equilibria in models with heterogeneous agents and market frictions. In 2007, 44.5 million non-elderly in the U.S did not have health insurance coverage. Empirical studies suggest that there are serious negative consequences associated with uninsurance. Consequently, there is wide agreement that reforming the current health care system is desirable and several proposals have been discussed among economists and in the political arena. However, little attention has been paid to quantify the macroeconomic consequences of reforming the health insurance system in the U.S. The objective of this section is to develop a theoretical framework to evaluate a broad set of health care reform plans. I build a model that is capable of reproducing a set of key facts of health expenditure and insurance demand patterns, as well as key macroeconomic conditions of the U.S. during the last decade. Then, I use this model to derive the macroeconomic implications of alternative reforms and alternative ways of funding these reforms. The second part of this thesis studies the computation and simulation of dynamic competitive equilibria in models with heterogeneous agents and market frictions. This type of models have been of considerable interest in macroeconomics and finance to analyze the effects of various macroeconomic policies, the evolution of wealth and income distribution, and the variability of asset prices. However, there is no reliable algorithm available to compute their equilibria. We develop a theoretical framework for the computation and simulation of dynamic competitive markets economies with heterogeneous agents and market frictions. We apply these methods to some macroeconomic models and find important improvements over traditional methods.