Knots are being discovered with increasing frequency in both biological and synthetic macromolecules and have been fundamental topological targets for chemical synthesis for the past two decades. However, only few synthetic molecular knots have been prepared to date and their properties remain largely unexplored. This thesis reports the synthesis of the most complex non-DNA molecular knot prepared to date: the self-assembly of five bis-aldehyde and five bis-amine building blocks around five metal cations and one chloride anion forms a 160-atom-loop molecular pentafoil knot (five crossing points). Chapter I aims to give the reader an overview of the current state of research in the field of template synthesis of molecular knots. Chapter II reports the synthesis and full characterisation of the most complex non-DNA molecular knot prepared to date, a pentafoil knot. Chapter III describes the synthesis of eleven pentameric cyclic double helicates derived from the scaffold of a pentafoil knot and presents an extensive study of the factors influencing the assembly process. Chapter IV reports the study of the self-sorting behaviour of a molecular Solomon link and a molecular pentafoil knot and their related non-interlocked systems. Chapter V the dynamic nature of pentameric circular helicates and a pentafoil knot is investigated, bringing insights on the subtle balance of thermodynamic and kinetic parametres involved in their self-assembly process. Chapter VI describes the halide binding properties of a synthetic molecular knot and doubly- and triply-entwined [2]catenanes based on circular Fe(II)-double-helicate scaffolds.

This thesis presents the synthesis and characterisation of a range of heterometallated porphyrin oligomers and other novel 3D π-conjugated porphyrin nanostructures. Subsequently, their physical organic properties were evaluated which revealed some fascinating electronic properties. Chapter 1 summarises some of the work done in the Anderson group on porphyrin nanostructures and reviews the literature regarding heterometallated porphyrin oligomers. In addition it introduces the main concepts and techniques used in the remainder of the thesis. In Chapter 2 the stabilities of a family of four linear porphyrin pentamer complexes are determined by UV-vis-NIR titrations and analysed using chemical double-mutant cycles which reveal that the binding energy of the copper centre to an axial pyridine ligand is -6.2 kJ mol^-1. Subsequently, the Zn-Zn-Cu-Zn-Zn pentamer is used in the synthesis of a heterometallated 10-porphyrin nanoring. Chapter 3 will describe the investigation of quantum interference phenomena in a bis-copper six-porphyrin nanoring by using EPR spectroscopy. We show that the exchange coupling between two spin centres is increased by a factor 4.5 in the ring structure with two parallel coupling pathways as compared to an otherwise identical system with just one coupling path. In Chapter 4 the syntheses of three isomers of the bis-copper 6-porphyrin nanoring are described. DFT calculations have indicated potential destructive interference phenomena in one of the isomers which would allow for the formation of a molecular system with behaviour resembling that of a hypothetical molecular interferometer. Chapter 5 reports on the template-directed synthesis of a π-conjugated 14-porphyrin nanoball. This bicyclic structure consists of two intersecting nanorings of 6 and 10 porphyrin units. Fluorescence up-conversion spectroscopy experiments demonstrate that electronic excitation delocalises over the whole 3D π-system within 0.3 ps if the nanoball is bound to its templates or within 5 ps if the nanoball is empty. In Chapter 6 the synthesis and characterisation of a D_4h symmetric analogue of the porphyrin nanoball is described. The structure consists of ten porphyrin units arranged as two perpendicular 6-porphyrin nanorings intersecting at two porphyrins. In the synthesis, a combination of magnesium and zinc porphyrins are used which allows for the introduction of a selective demetallation method crucial for accessing this novel structure.

Materiais naturais nanoestruturados, tipo smectita, têm sido amplamente usados em nanocompósitos poliméricos, com ganhos expressivos em muitas propriedades. Porém, devido a sua natureza polar, seu uso em nanocompósitos de poliolefinas apresenta uma série de problemas. Entre esses problemas está a dificuldade de esfoliação na matriz, o que geralmente resulta um sistema não nano-estruturado e, por conseqüência, com pouco ou nenhum ganho em propriedades. Para tentar resolver esse problema, materiais tipo esmectita têm sido modificados com sais de amônio quartenário. Esses, por sua vez, possuem características tóxicas, impedindo seu uso em embalagens de alimentos. Com o objetivo de estudar uma nova alternativa que contorne esses problemas, dois materiais lamelares nano-estruturados, tipo esmectita, contendo grupos alquila ligados por ligação sigma com a rede inorgânica, foram sintetizados. Ambos apresentaram excelente ordem mesoestrutural. Um dos materiais sintetizados, formado por um Alsilsesquioxano lamelar, contendo alto teor de cadeia alquila entre as lamelas inorgânicas, foi usado na formação de compósito de polietileno. Comparativamente, uma argila natural, modificada com sais de amônio quaternário (Cloisite 15A), foi usada para fins comparativos. Os compósitos, então obtidos, foram caracterizados para avaliar diferenças microestruturais, morfológicas e mudanças em suas propriedades mecânicas e reológicas. Comparativamente à argila comercial Cloisite 15A, os compósitos contendo os materiais sintéticos apresentaram reologia diferenciada, melhor resistência ao impacto e ao Tensofissuramento Acelerado pelo Ambiente (ESCR). / Nanostructured natural materials, as smectites, have been widely used in polymeric nanocomposites, with significant gains in many properties. However, due to its polar nature, the use in nanocomposites of polyolefins presents a series of drawbacks. Among these problems, its difficulty exfoliation in the matrix, which generally results in a system not nanostructured and, consequently, with little or no gain on properties. To try to resolve this problem, materials type smectite have been modified with quaternary ammonium salts. These salts, in turn, have toxic characteristics, preventing its use in food packaging. In order to study a new alternative that bypasses these problems, two lamellar nanostructured materials, like smectite, with alkyl groups containing sigma links connected to lamellar inorganic network, were synthesized. Both materials had excellent mesostructural order. One of the synthesized materials, formed by a lamellar Al-silsesquioxane, containing high levels of alkyl chain between the inorganic lamella, was used in the formation of a polyethylene composite. Commercial natural clay, modified with quaternary ammonium salts (Cloisite 15A), was used for comparative purposes. The composites then obtained, were characterized to assess microstructural differences, morphological change, and its mechanical and rheological properties. Comparatively to commercial clay (Cloisite 15A), the composites containing synthetic materials, showed differented rheologics properties, better impact resistance and better Environmental Stress Cracking Resistance (ESCR).

With the progress achieved to this date in mobile computing technologies, mobile devices are increasingly being used to store sensitive data and perform security-critical transactions and services. However, the protection available on these devices is still lagging behind. The primary and often only protection mechanism in these devices is authentication using a password or a PIN. Passwords are notoriously known to be a weak authentication mechanism, no matter how complex the underlying format is. Mobile authentication can be strengthened by extracting and analyzing keystroke dynamic biometric from supplied passwords. In this thesis, I identified gaps in the literature, and investigated new models and mechanisms to improve accuracy, usability and resilience against statistical forgeries for mobile keystroke dynamic biometric authentication. Accuracy is investigated through cost sensitive learning and sampling, and by comparing the strength of different classifiers. Usability is improved by introducing a new approach for typo handling in the authentication model. Resilience against statistical attacks is achieved by introducing a new multimodal approach combining fixed and variable keystroke dynamic biometric passwords, in which two different fusion models are studied. Experimental evaluation using several datasets, some publicly available and others collected locally, yielded encouraging performance results in terms of accuracy, usability, and resistance against statistical attacks. / Graduate / 2019-09-25

We present a novel method for building 3D models from a user sketch. Given a 2D sketch as input, the approach aligns and deforms a chosen 3D template model to match the sketch. This is guided by a set of user-specified correspondences and an algorithm that deforms the 3D model to match the sketched profile. Our primary contribution is related to fitting the 3D deformable geometry to the 2D user sketch. We demonstrate our technique on several examples. / Science, Faculty of / Computer Science, Department of / Graduate

La chimie du solide des composes hybrides organiques inorganiques contenant l’uranium a été récemment enrichie par une multiplication de publications concernant des matériaux bi ou tri dimensionnels. Ce travail porte sur la synthèse hydrothermale de composés des systèmes uranyle-vanadate-amines et uranyle-phosphate-amines. La résolution des structures de ces composés s’est faite par diffraction des rayons X sur monocristal. Leur stabilité thermique a aussi été étudiée. Suivant le pH de la solution, et l’amine utilisée, différentes familles de composés apparaissent. A pH basique, les composés obtenus sont bidimensionnels avec des couches correspondant à celles des phases naturelles, à savoir couches de type carnotite pour les uranyle-vanadates ou de type autunite pour les uranyle-phosphates. A pH acide, des composés à charpente tridimensionnelle sont stabilisés par la présence des amines. Les arrangements résultent de couches uranyle-vanadate ou uranyle-phosphate de type uranophane reliées par des piliers uranyle. Ces arrangements présentent différents rapports U/V ou U/P selon l’isomérie géométrique de la couche uranophane. L’identification de nouveaux isomères géométriques a généré une classification de ces isomères qui permet une comparaison simple et la compréhension de leur formation. Enfin, l’utilisation de l’éthylène diamine dans le système uranyle-phosphate permet la réduction in situ de l’uranium (VI) en uranium (IV) et la formation d’un phosphate d’uranium (IV) où les couches uranium-phosphate alternent avec des couches d’éthylène diamine diprotonnée / Solid state chemistry of hybrid organic-inorganic compounds containing uranium has been enriched recently by a multiplication of papers dealing with two and three dimensional inorganic materials. This work deals with hydrothermal synthesis of compounds in the uranyl-phosphate-amine and uranyl-vanadate-amine systems. Determination of their structure was done by X-ray diffraction on single crystals. Their thermal stability was also studied. According to the pH of the initial solutions, and nature of the amine used, different families of compounds appear. With a basic pH, the obtained compounds are two dimensional with the layers corresponding to those found in naturally occurring phases, such as carnotite type layer for the uranyl-vanadate system and autunite for the uranyl-phosphate system. With an acidic pH, compounds with three dimensional frameworks are stabilized by the presence of the amines. The frameworks result from uranophane type uranyl-vanadate or uranyl-phosphate layers connected by uranyl pillars. They display different U/V or U/P ratios depending on the geometric isomer of the uranophane layer. Identification of new geometric isomers has led to a simple classification of the isomers which helps to their comparison and to the understanding of their formation. Finally, using ethylene diamine in the uranyl-phosphate system reduces in situ uranium (VI) into uranium (IV) and forms a uranium (IV) phosphate in which the uranium-phosphate layers alternate with diprotonated ethylene diamine layers.

E-government, in both developed and developing countries, has become the focus of governments' agenda because it offers enormous opportunities to reform the public sector and improve its performance. However, the evolution of e-government initiatives in developing countries is not at a satisfactory level which indicates that there are still enormous barriers and concerns that need to be addressed and solved.The major aim of this research is to investigate the supply-side stakeholders' perspectives of drivers and barriers forces that stimulate or impede the development of e-government initiative in Jordan and recommend strategies to e-government leaders on how to overcome and manage the encountered forces.This is a case study based qualitative research that employs semi-structured interviews as the primary source for data collection. In addition, template analysis approach and NVivo qualitative software have been used to analyze the gathered data. Moreover, a novel conceptual framework was initially developed by the researcher in order to be used as a helpful guide in the process of data collection and analysis. The framework was then applied to the research context to establish an overall view of the key drivers and barriers that influence the implementation of e-government at national level in Jordan.Research findings indicate that there are various drivers and barriers that affect the development of e-government initiative in Jordan. Most of the research findings confirmed what was already revealed by previous studies. However, this study added new and unique findings that were not discovered before including; The Holy Month of Ramadan, Ministers Reshuffling, Religious Beliefs, Preach Without Practicing, Wasta, and Improper Use of Technology. These new findings emerged distinctively from the Jordanian, Arabic and Islamic contexts. Finally, various recommendations have been proposed to demonstrate how challenges could be handled in practice. The value of this study is threefold. First, it contributes as new reference in e-government literature with respect to drivers and barriers to e-government in developing countries in general and in Arab nations in particular. Second, it proposes a conceptual framework that could be used as a tool to understand drivers and barriers that affect the development of e-government and their correlation to e-government initiatives success or failure. Third, it motivates changes in practice as it provides practical recommendations and guidance for practitioners and leaders of e-government in Jordan on how they should take actions to overcome and manage the encountered forces in order to reduce the possibility of the initiative failure and enhance the chance of its success.

This Masters thesis deals with the design of implementation of the extension of given framework for making web applications in PHP language by a definition of website templates in XML with the possibility of implementing own additional tags in PHP. Frameworks are tools used for simple creation of web applications, and this thesis also describes systems of definitions and the utilization of templates in existing frameworks. The part of the design is also a possibility of definition of relation between state of the element of user interface and web application data. Further, the creation of sample libraries of components demonstrating functionality of the solution is described. In the conclusion, the thesis summarizes achieved results and deals with possibilities of further development.

The purpose of this thesis is to develop a guideline template that should supportthe industrial partner when designing lifting equipment. A newly updated standardwith focus on fatigue was the base of the project. The standard divides load cyclesinto over and under 16 000 cycles and they have different requirements. Thisproject explains how to reach these requirements. By interpretation of neededvariables/calculation and how to solve these calculations. A workflow for Finiteelement analysis is presented and analysis is done on lifting equipment. The resulta guideline template with focus on fatigue which indicates which requirementsneeds which solution.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18296号 / 工博第3888号 / 新制||工||1596(附属図書館) / 31154 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 澤本 光男, 教授 中條 善樹, 教授 赤木 和夫 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM