In this thesis, we aim to investigate the thermoresponsive behaviour, especially negative thermal expansion (NTE), in metal dicarboxylate metal organic frameworks (MOFs) using X-ray diffraction techniques. Four materials with the UiO-66 topology [Zr6O4(OH)4(bdc)12], [Zr6O6(bdc)12], [Zr6O6(bpdc)12] and [Zr6O6(2,6-ndc)12] (bdc = 1,4-benzenedicarboxylate, bpdc = 4,4’-biphenyldicarboxylate and 2,6-ndc = 2,6-napthalenedicarboxylate) were investigated, all of which contain a zero-dimensional inorganic cluster. All four members show NTE behaviour over the observed temperature ranges as a result of the twisting motion of the carboxylate groups of the organic linkers. This twisting motion introduces a concerted rocking motion within the inorganic cluster which causes an apparent decrease in the size of the cluster and hence overall volume contraction. Alteration of the structure of the organic linker has an effect on the magnitude of the expansivity coefficient which is believed to be related to the existence of specific vibrational modes of that particular organic linker. Four members of the MIL-53 family [Al(OH)(bdc)], [AlF(bdc)], [Cr(OH)(bdc)] and [VO(bdc)] were studied. All four materials show elements of NTE behaviour related to a “wine rack” thermo-mechanical mechanism which is determined by the connectivity of the framework. The thermoresponsive behaviour in these materials is dominated by the changes in the plane of the pore opening. These changes result from a combination of three distinct types of motion of the bdc linker including the rotation of the bdc linker about the chain of the inorganic octahedra, the “knee cap” bending mode of the carboxylate groups about the O-O vector and possibly the transverse vibrations within the bdc linker. The latter motion was not evident in this work due to the limitations of the structure refinements. The former two motions appear to be correlated and depend on the rigidity of the metal-centred octahedra which is determined by the constituent metal cation and anion types. The rigidity of the octahedra is also found to play an important role in determining whether the material undergoes a “breathing” phase transition at low temperature. [Sc2(bdc)3] shows NTE behaviour over the observed temperature range which is partially driven by a “wine rack” thermo-mechanical mechanism, but with an opposite framework compression direction when compared to the MIL-53 types MOFs. This is due to the presence of an additional bdc connecting linker in the plane of the pore opening. This extra connection inverses the compression direction and also impedes the structural changes in the plane of the pore opening. The contraction of the chain of inorganic octahedra is the main contributor to the overall unit cell contraction and is caused by the twisting motion of the carboxylate groups of the bdc linker while the magnitude of this contraction is determined by the flexibility of the chain of inorganic octahedra.

The aim of my thesis is to evaluate whether on the Slovak market there is opportunity for expansion of the Czech company Pelmi spol., s.r.o. Based on analysis of the target market, the SWOT analysis, competition, and economic characteristics of Slovak market I will suggest my own recommendation what kind of form entry is the most convenient for company.

The Master thesis "Expansion of Czech Companies to Brazil on the Example of mmcité a.s." describes positive and negative aspects of entering Brazilian market on an example of a concrete Czech company. The first chapter presents activities and products of mmcité a.s. Chapter 2 contains detailed PESTL analysis complemented by a part about business etiquette, Brazilian market with street furniture is described in the third chapter. On the basis of these three chapters, there follows a decision on an optimal form of mmcité's entry to the biggest Latin-American market and, in the fifth chapter, the author proposes an attitude to the single parts of its marketing mix. The sixth chapter is written as a guide for Czech companies which consider expansion to Brazil. Except from a system for deciding on the form of entry, it also presents an approximate figure of costs of each form. The author drew inspiration from professional books, guides for export to Brazil, Internet and, also, own experience gained during studies in Sao Paulo.

The thesis deals with possibilities of setting up an enterprise in Brazil. Specifically, it is focused on water management and wastewater treatment sector. Apart from political, economic, sociological and technological analysis, the thesis also contains the water management sector analysis, including current trends and opportunities. The main goal of the thesis is to create a suitable base for entrance of the Asio ltd. into brazilian wastewater market and propose an own solution regarding a possible expansion.

As organizations grow and expand past their operational headquarters, individual branches may reflect a different identity than that of the headquarters. The question then is, "Is senior management able to transcend geographical boundaries and communicate the identity that has shaped their strategy for the organization?" The purpose of this study is to examine the impact of geographical expansion on the reflected perceptions of internal stakeholders related to the organization's intended identity as defined by senior management. Through this study, four themes emerged from the data. The themes included a reliance on reputation, a sense of belonging, peer influence, and communication congruence. Based on this data, the study provides a marketing of identity process to assist organizations in communicating their identity throughout the organization and across geographic locations.

Invasive range expansion is correlated to life- history variation, boldness and dispersal behavior. The invasion of the African Jewelfish in Everglades National Park provides an opportunity to test life-history trait variation, boldness and dispersal behavior in the invasion success of this species. My study examined variation in somatic traits, boldness, and dispersal of jewelfish across their invaded range. Life histories were examined on wild individuals. Boldness and dispersal were tested in outdoor experimental tanks. Tested populations from the invasion front have higher somatic traits, but they were not bolder than longer established populations. Understanding the underlying mechanisms of invasions are key for the development of strategies looking to contain invaders and prevent their spread.

Les travaux exposés dans cette thèse sont consacrés à l’étude de méthodesprécises pour approcher des équations différentielles stochastiques ou deséquations aux dérivées partielles (EDP) déterministes. La première parties’inscrit dans le cadre du développement de méthodes visant à corriger le biaisdans les processus de diffusion paramétrique. Trois modèles sont étudiés enparticulier : Ornstein-Uhlenbeck, Auto-régressif et Moyenne mobile. A l’issuede ce travail, plusieurs approximations de biais ont été proposées suivant deuxapproches : la première consiste en un développement de Taylor del’estimateur obtenu alors que la seconde s'appuie sur une expansionstochastique de celui-ci.La deuxième partie de cette thèse porte sur l’approximation de l’équation de lachaleur obtenue après changement de variables à partir du modèle de Black etScholes. En général, on préfère utiliser des méthodes implicites pour résoudredes EDP paraboliques mais depuis quelques années, les méthodes dites deRunge-Kutta explicites stabilisées, sont de plus en plus utilisées. Nousmontrons que l’utilisation de ce type de méthodes explicites et notamment lesschémas ROCK donnent de très bons résultats même si les conditions initialessont peu régulières, ce qui est le cas dans les modèles financiers / The work presented in this thesis is devoted to the study of precise methods forapproximating stochastic differential equations (SDE) or deterministic partialdifferential equations (PDE). The first part is devoted to the development ofbias correction methods in parametric diffusion processes. Three models arestudied in particular : Ornstein-Uhlenbeck, auto-regressive and Movingaverage. At the end of this work, several approximations of bias have beenproposed following two approaches : the first consists in a Taylor developmentof the obtained estimator while the second one relies on a stochastic expansionof the latter.The second part of this thesis deals with the approximation of the heatequation obtained after changing variables from the Black-Scholes model. Likethe vast majority of PDE, this equation does not have an exact solution, sosolutions must be approached using explicit or implicit time schemes. Itis often customary to prefer the use of implicit methods to solve parabolic PDEsuch as the heat equation, but in the past few years, the stabilized explicitRunge-Kutta methods which have the largest possible domains of stabilityalong the negative real axis, are increasingly used. We show that the useof this type of explicit methods and in particular the ROCK (Runge-Orthogonal-Chebyshev-Kutta) schemes give very good results even if the initial conditionsare not very regular, which is the case in the financial models

abstract: Drainage flow of a viscous compressible gas from a semi-sealed narrow conduit is a pore-scale model for studying the fundamental flow physics of fluid recovery from a porous reservoir without using fluid injection. Thermal effect has been routinely neglected for these flows in the traditional petroleum engineering literature. Since the motion is entirely driven by volumetric expansion, temperature change always accompanies the density change. This thesis examines such thermal effects on the drainage flow. Thermal drainage flow is first studied by simultaneously solving the linearized continuity, momentum and energy equations for adiabatic walls. It is shown that even in the absence of an imposed temperature drop, gas expansion induces a transient temperature decrease inside the channel, which slows down the drainage process compared to the isothermal model and Lighthill’s model. For a given density drop, gas drains out faster as the initial-to-final temperature ratio increases; and the transient density can undershoot the final equilibrium value. A parametric study is then carried out to explore the influence of various thermal boundary conditions on drainage flow. It is found that as the wall transitions from adiabatic to isothermal condition, the excess density changes from a plane wave solution to a non-plane wave solution and the drainage rate increases. It is shown that when the exit is also cooled and the wall is non-adiabatic, the total recovered fluid mass exceeds the amount based on the isothermal theory which is determined by the initial and final density difference alone. Finally, a full numerical simulation is conducted to mimic the channel-reservoir system using the finite volume method. The Ghost-Cell Navier-Stokes Characteristic Boundary Condition technique is applied at the far end of the truncated reservoir, which is an open boundary. The results confirm the conclusions of the linear theory. / Dissertation/Thesis / Doctoral Dissertation Mechanical Engineering 2020

Delays on electrical engineering projects are a phenomenon at Eskom distribution due to a wide range of causes. These project delays result in Eskom to contravene with Electricity Regulation Act 4 of 2006 in terms of providing efficient, effective and sustainable operation of electricity supply infrastructure, promoting the use of renewable energy sources and energy efficiency as well as to facilitate universal access to electricity for South African consumers (Gazette, 2006). Eskom strives to comply with the Electricity Regulation Act by initiating and implementing strengthening projects, refurbishment (reliability) projects, direct customer projects, infills projects and electrification projects (Eskom, 2014).The severe delays experienced in the delivery of electrical distribution projects have a negative impact on South African economic growth and population. This research study adopted interactive management methodology for the identification of project delay factors in Eskom distribution projects through the use of the idea writing technique, nominal group technique, and interpretive structural modelling technique. The interactive management methodology allows a group of people collaboratively to develop a structure that defines the relationship among the system elements. Using interactive management approach, a total of one hundred and twelve project delay factors were reduced to twenty six significant project delays which formed part of interpretive structural modelling. This research study revealed the hierarchical model illustrating interrelationships between the twenty six identified project delay factors. The research study identified three root causes of delays in electrical distribution projects at Eskom Northern Cape Operating Unit, namely "poor communication", "poor planning", and "project scheduling not properly done". The three identified root causes can be used as critical points for eradicating delays in electrical distribution projects at Eskom Northern Cape Operating Unit. The research study found that a total of ten out of twenty six project delay factors were unique to electrical distribution projects at Eskom Northern Cape Operating Unit.

Thesis advisor: Abhishek Chatterjee / In the last two decades, unnatural amino acid (UAA) mutagenesis has emerged as a powerful new method to probe and engineer protein structure and function. This technology enables precise incorporation of a rapidly expanding repertoire of UAAs into predefined sites of a target protein expressed in living cells. Owing to the small footprint of these genetically encoded UAAs and the large variety of enabling functionalities they offer, this technology has tremendous potential for deciphering the delicate and complex biology of the mammalian cells. We describe the application of this technology to the modification of adeno-associated virus (AAV) for the first time, enabling the generation of vectors with precisely re-engineered cell-targeting for gene therapy. Our UAA-AAV production platform enables the incorporation of UAAs bearing bio-orthogonal reactive handles into multiple specific sites on the virus capsid and their subsequent functionalization with various labeling molecules. Incorporation of an azido-UAA enabled site-specific attachment of a cyclic-RGD peptide onto the capsid, retargeting the virus to the αv β3 integrin receptors, which are overexpressed in tumor vasculature. This work provides a general chemical approach to introduce various receptor binding agents onto the AAV capsid with site selectivity to generate optimized vectors with engineered infectivity. Next, we used our unique UAA-AAV vector as a tool for the directed evolution of more active UAA incorporation machinery in mammalian cells. It is well known that the efficiency of unnatural amino acid mutagenesis in mammalian cells is limited by the suboptimal activity of the suppressor tRNAs currently in use. The ability to improve their performance through directed evolution can address this limitation, but no suitable selection system was previously available to achieve this. We have developed a novel platform for virus-assisted directed evolution of enhanced suppressor tRNAs (VADER) in live mammalian cells. Our system applies selective pressure for tRNA activity via the nonsense suppression-dependent production of UAA-AAV, and selectivity for the specific incorporation of interest comes from a novel virus purification strategy based on the unique chemistry of the UAA. We demonstrated > 10,000-fold selectivity for active tRNAs out of mock libraries and used this system to evolve libraries generated from the commonly used archaeal pyrrolysyl suppressor tRNA, ultimately identifying a variant which is three times as active as the original tRNA. Finally, we used next-generation sequencing to analyze the fate of every library member over the course of the selection and found that our VADER selection scheme is indeed selective for the enrichment of more active tRNA variants. This work provides a general blueprint for the evolution of better orthogonal suppressor tRNAs in mammalian cells. / Thesis (PhD) — Boston College, 2019. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.