Compounds with carboxylic and amidic functions belong to basic structural blocks, which are used for construction of functional molecules in organic, organometallic and also in carborane chemistry. However, considering cobalt bis(dicarbollide)(1-) ion, the synthetic ways to these derivatives have been virtually unknown. A published procedure on lithiation in THF and reaction with CO2 leading to mono- and dicarboxylic acids had failed in our hands. Nevertheless, a detailed revision of the experimental conditions provided finally good yields of mixture of both acids, which could be separated by chromatography and crystallization, and compound of general formulation [(1-HOOC-1,2-C2B9H10)(1',2'-C2B9H10)-3,3'-Co(III)]- and stereoisomeric mixture of [(HOOC)2-(1,2-C2B9H10)2-3,3'-Co(III)]- were characterized for the first time by combination of NMR, MS and HPLC. Also, the carboxylic acid derivatives with methylene and ethylene connectors of the general formula [(1-HOOC-(CH2)n-1,2- C2B9H10)(1',2'-C2B9H10)-3,3'-Co(III)]- were prepared by lithiation of Cs1 in DME at low temperatures followed by reaction with BrCH2COOEt and subsequent hydrolysis of the resulting ester or by oxidation of the respective propylhydroxy derivative. The acids were converted to reactive p-nitrophenyl esters...

The diploma thesis deals with a free play with building blocks during breaks. The aim of this work is to find out how the free play with building blocks is beneficial for pupils at primary school. The whole work is divided into 3 chapters and each of them is concerned with the importance of the play in one specific area. The first part deals with the benefits of the play for the development of pupils' mathematical skills, the second part deals with the benefits of the play for the development of social skills among pupils. The third part is then aimed at the value of observing pupils during the free play for teachers. The research was conducted using observation during which photographs and video records of pupils' play were made. The photographs and the video records were consequently analyzed from the perspective of all 3 categories mentioned earlier. Key words building blocks, math, geometry, social skills, communication, cooperation, school break

Contemporary approaches to cross-platform mobile application development, such as hybrid apps from PhoneGap and generated native apps from Xamarin, show promise in reducing development time towards Android, iOS and other platforms. At the same time, studies show that there are various problems associated with these approaches, including suffering user experiences and codebases that are difficult to maintain and test properly. In this thesis, a novel prototype framework called Building Blocks was developed with the purpose of investigating the feasibility of utilizing component-based software engineering in solving this problem. The prototype was developed towards Android along with a web interface that allowed users to assemble an Android app using software components. The report concludes that component-based software engineering can be – and already is – utilized successfully to improve cross-platform mobile app development with special regards to user experience. Qualitative data indicate that Building Blocks as a concept is flexible and shows promise for mobile app development in which functionality is often reused, such as enterprise apps. Rapid prototyping using the web-based visual editing tool was another promising area. However, future use of Building Blocks would require further work on the prototype to improve its ease of use.

Power electronics building blocks (PEBBs) are standardized building blocks used to integrate power electronics systems. The PEBB approach can achieve low cost, high redundancy, high reliability, high flexibility and easy maintenance for large-scale power electronics systems. This thesis presents the implementation of a 100kW PEBB-based soft-switched bus regulator for an 800V DC distributed power system. The zero current transition (ZCT) soft-switching technique is used to improve the performance of the bus regulator by minimizing switching loss and improving overall efficiency. PEBB modules and a digital control building block are the subsystems of the DC bus regulator. This thesis addresses the design issues at subsystem and system levels. These include: operational principles and design of ZCT PEBB modules; design and implementation of the digital control block, based on DSP and EPLD; and modeling and control design of the DC bus regulator. There are several considerations when using the ZCT soft-switching technique in three-phase applications: the timing of the auxiliary switch gate signals must be arranged differently; there are low-frequency harmonics caused by the pulse width limits; and there is high thermal stress on the resonant capacitors. These issues are resolved by utilizing the sensed phase current information and the design freedom in the PWM modulator. A PWM modulation technique is proposed that can considerably reduce the switching events and further remove the associated loss while keeping THD low. Reduced switching events alleviate the thermal issue of the resonant capacitors. The same modulation technique can avoid the low-frequency harmonics caused by the pulse width limits and double the sampling frequency. The phase current information is used to deal with the control timing issue of the auxiliary switches and to control the three-phase soft-switching operation in order to achieve better efficiency. Additionally, the phase current information is used to implement dead time compensation to reduce THD. The soft-switched DC bus regulator has been tested up to a 100kW power level with 20kHz switching frequency. Experimental results demonstrate that high performance of the DC bus regulator is accomplished in terms of wide control bandwidth, low THD, unity power factor, high efficiency and high power density. / Master of Science

Two designs of inorganic/organic hybrid micro-structures are discussed: (1) silver nanowire reinforced layer-by-layer (LbL) polyelectrolyte composite film and (2) bimetallic silver-gold core-shell nanoparticles. In this work, zero-dimensional spherical gold nanoparticles (AuNPs), one-dimensional silver nanowires (AgNWs), and two-dimensional silver nanoplates (AgNPls) represent the inorganic component. Three-arm star polymer and polyelectrolytes represent the organic component. In the first design, the one-dimensional AgNWs serves as a mechanical reinforcement for the fabrication of mechanically isotropic and anisotropic polyelectrolyte composite films. The composite film is mechanically isotropic when the AgNWs are randomly oriented, and it is anisotropic when the AgNWs are unidirectionally oriented within the LbL polyelectrolyte matrix. Furthermore, above the AgNWs percolation threshold, the AgNWs reinforced LbL composite film is electrically conductive. Therefore, it can find application in ultrathin LbL film-based sensor. In the second design, the zero-dmensional AuNPs were assembled onto one-dimensional AgNWs and two-dimensional AgNPls by means of star polymer linker, or alternatively using polyelectrolytes via electrostatics interaction. The unique feature of these bimetallic silver-gold core-shell nanoparticles is their ability to greatly enhance electric field, due to the silver-gold intra-particle interaction. This allows it to serve as a single-nanoparticle surface enhanced Raman scattering (SERS) substrate for chemical sensing.

Submitted by Liliane Ferreira (ljuvencia30@gmail.com) on 2018-12-12T10:14:40Z No. of bitstreams: 2 Tese - Lauro Cássio Martins de Paula - 2018.pdf: 7484273 bytes, checksum: a3c47ef9c05d03a8dce4dce89a2df34b (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-12-12T10:36:08Z (GMT) No. of bitstreams: 2 Tese - Lauro Cássio Martins de Paula - 2018.pdf: 7484273 bytes, checksum: a3c47ef9c05d03a8dce4dce89a2df34b (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-12-12T10:36:08Z (GMT). No. of bitstreams: 2 Tese - Lauro Cássio Martins de Paula - 2018.pdf: 7484273 bytes, checksum: a3c47ef9c05d03a8dce4dce89a2df34b (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2018-12-06 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The procedure used to select a subset of suitable features in a given data set consists in variable selection, which is important when the dataset contains large number of variables and many of them are redundant. Multivariate calibration combines variable selection with statistical techniques to build mathematical models which relate the data to a given property of interest in order to predict this property by selecting informative variables. In this context, variable selection techniques have been widely applied to the solution of several optimization problems. For instance, Genetic Algorithms (GAs) are easy to implement and consist in a population-based model that uses selection and recombination operators to generate new solutions. However, usually in multivariate calibration the dataset present a considerable correlation degree among variables and this provides an evidence about the problem not being properly decomposed. Moreover, some studies in literature have claimed genetic operators used by GAs can cause the building blocks (BBs) disruption of viable solutions. Therefore, this work aims to claim that selecting variables in multivariate calibration is a non-completely decomposable problem (hypothesis 1) as well as that recombination operators affects the non-decomposability assumption (hypothesis 2). Additionally, we are proposing two heuristics, one local search-based operator and two versions of an Epistasis-based Feature Selection Algorithm (EbFSA) to improve model prediction performance and avoid BBs disruption. Based on the performed inquiry and experimental results, we are able to endorse the viability of our hypotheses and demonstrate EbFSA can overcome some traditional algorithms. / Seleção de variáveis é um procedimento para selecionar um subconjunto de características viáveis em um conjunto de dados, o qual se torna importante quando esse conjunto contém muitas variáveis redundantes. A calibração multivariada combina seleção de variáveis com técnicas estatísticas para construir modelos matemáticos com o intuito de predizer uma propriedade de interesse. Nesse contexto, técnicas de seleção têm sido aplicadas na solução de diversos problemas. Por exemplo, Algoritmos Genéticos (AGs) são fáceis de implementar e consistem em um modelo baseado em população, o qual utiliza operadores de seleção e recombinação para gerar novos indivíduos. No entanto, geralmente em calibração multivariada, o conjunto de dados apresenta um grau de correlação considerável entre as variáveis e isso nos fornece uma evidência de que tal problema não pode ser decomposto adequadamente. Além disso, alguns estudos da literatura têm afirmado que os operadores genéticos utilizados pelos AGs podem causar o rompimento dos Blocos Construtores (Building Blocks - BBs) das soluções viáveis. Portanto, este trabalho objetiva demonstrar que a seleção de variáveis em calibração multivariada é um problema não-completamente decomponível (hipótese 1), assim como que operadores de recombinação afetam a presunção de não-decomponibilidade (hipótese 2). Adicionalmente, este trabalho propõe duas heurísticas, um operador de busca local e duas versões de um Algoritmo para Seleção de Variáveis baseado em Epistasia (EbFSA) para aprimorar a capacidade de predição do modelo e evitar o rompimento de BBs. Baseando-se na pesquisa realizada e nos resultados obtidos, torna-se possível confirmar a viabilidade de nossas hipóteses e demonstrar que o EbFSA consegue superar alguns algoritmos tradicionais.

Les propriétés exceptionnelles des composés fluorés ont entrainées un développement considérable de la chimie du fluor depuis les années 1950. Aujourd'hui les substances fluorées se retrouvent dans la plupart des domaines tels que la chimie thérapeutique ou l'agrochimie. L'atome d'azote étant ubiquitaire en chimie médicinale, le développement de voies synthétiques permettant l'obtention de fluoroamines est donc essentiel.Au laboratoire, une étude a précédemment été menée sur la réaction de bromofluoration de composés azotés insaturés en milieu superacide de type HF/SbF5. Le NBS utilisé comme donneur d'ion broménium, après activation par polyprotonation, a permis d'accéder à des composés azotés bromofluorés difficiles à obtenir en milieux classiques. Cependant l'ion bromonium s'isomérise rapidement conduisant aux produits difluorés. Les ions chloroniums ayant une réactivité différente de celle des ions bromoniums, ce travail porte sur l'étude des ions chloroniums dans des systèmes dicationiques générés en milieu superacide.Dans un premier temps l'impact des paramètres expérimentaux a été étudié par analyse des produits de réaction et par des expériences de RMN in situ. L'étude a ensuite été étendue à un panel de substrats afin de mesurer l'impact de la structure du substrat sur la réaction de chlorofluoration. Enfin l'effet de substituants halogènes sur la double liaison carbone-carbone a été étudié. Ces travaux ont permis de mettre en lumière le mécanisme réactionnel impliqué dans cette réaction, puis d'appliquer la méthode pour la préparation de composés biologiquement actifs. / Exceptional properties of fluorinated compounds led to a considerable development of fluorine chemistry since the 1950's. Nowadays, fluorinated products have a key role in many domains going from medicinal chemistry to agricultural chemistry. As nitrogen atom is ubiquitous in pharmaceuticals, the development of new synthetic ways for the preparation of fluorinated nitrogen containing compound is of relevant interest.Previously, the superacid team developed a bromofluorination reaction of unsaturated nitrogen containing compounds in superacidic media HF/SbF5. The reaction was performed by using the NBS as halenium ion donor, activated through polyprotonation, permitting the access to bromofluorinated nitrogen containing compounds difficult to be obtained under classical organic conditions. Nevertheless the resulting bromonium ion isomerizes quickly to produce difluorinated products. Chloronium ions show different reactivities than the bromonium ones; so this study is focused on the reactivity of chloronium ion in dicationic systems generated by the use of superacidic media.The first step of the study was focused on the evaluation of the impact of experimental conditions by reaction products analysis and in situ NMR experiments. Then the influence of substrate structure on the reaction course was investigated. Finally the halosubstitution on the carbon-carbon double bound was studied. This work allowed us to highlight the chlorofluorination reaction mechanism and then to extend this method to bioactive compounds synthesis.

A series of boron-containing conjugated microporous polymers with hierarchical porous structures have been readily prepared via typical transition metal-catalyzed coupling reactions. The distribution of micro- and mesopores in the networks as well as the specific surface areas are tunable via tailoring the structures of the building blocks. The distinct capability of the resulting Lewis acid-based neutral porous polymers to selectively capture fluoride ions provides a high-efficiency conversion into stable anionic porous polymers. For the first time, fluoride anion binding to boron atoms in a solid sample was essentially characterized by solid-state 11B MAS NMR spectroscopy, clearly revealing such an efficient conversion from a neutral network to a negatively charged one only through Lewis acid–base adduct formation. Upon a simple ion-exchange process, various heavy metal cations were facile to be loaded into the networks of the anionic porous polymers. Furthermore, the cobalt(II)-loaded porous polymers were shown to promote the stoichiometric homocoupling reactions of the different aryl Grignard regents, and exert distinct size selectivities for the homocoupling products, highly dependent on their porous structures. Such a successful loading strategy might be used for design and synthesis of new types of zeolite-like porous polymers with desirable catalytic properties for a certain organic transformation, as well as other functional materials.

The exploitation of colloidal building blocks with morphological and functional anisotropy facilitates the generation of complex structures with unique properties, which are not exhibited by isotropic particle assemblies. Herein, we demonstrate an easy and scalable bottom-up approach for the programmed assembly of hairy oppositely charged homogeneously decorated and Janus particles based on electrostatic interactions mediated by polyelectrolytes grafted onto their surface. Two different assembly routes are proposed depending on the target structures: raspberry-like/half-raspberry-like or dumbbell-like micro-clusters. Ultimately, stable symmetric and asymmetric microstructures could be obtained in a well-controlled manner for the homogeneous–homogeneous and homogeneous–Janus particle assemblies, respectively. The spatially separated functionalities of the asymmetric Janus particle-based micro-clusters allow their further assembly into complex hierarchical constructs, which may potentially lead to the design of materials with tailored plasmonics and optical properties.

Companies cannot keep up with the change occurring in the ICT arena. As a result of companies being chased by an untamed animal namely IT evolution, they fear that they cannot run, as running feels like floating in air. This ICT evolution has become a fearful sight for Small Medium Enterprises (SMEs). This research project acknowledges this fear and provides a conceptual framework whereby SMEs can familiarise themselves when engaging in ICT investments from a South African point of view. The data collected in this qualitative study is based on ten different SMEs as well as one larger company, to try and obtain a benchmark which SMEs can strive towards. The outcome of this research project allows SMEs to be less fearful when deciding on ICT and seeing how ICT can benefit these organisations. Copyright / Dissertation (MCom)--University of Pretoria, 2010. / Informatics / unrestricted