Metallosupramolecular self-assembly has fast expanded as a field due to the possibility for relatively facile construction of large assemblies through reversible non-covalent interactions, compared to their more synthetically challenging covalent counterparts. Not least, it provides a fast and often quantitative route to the construction of three-dimensional structures with a cavity. These internal spaces have been shown to be effective for a variety of applications, including but not limited to catalysis, drug delivery, use as a noncovalent protecting group, a separations material etc. Thermodynamic processes, with the inherent advantages of atom efficient, high-yielding reactions, usually control these systems. However this can also be a double-edged sword, with these systems susceptible to changes to specific ambient conditions, and are thus often not kinetically stable. Herein, we report the expansion of a method utilising the one electron oxidation of high spin d7 cobalt(II) to low spin d6 cobalt(III) as a molecular locking mechanism as part of the assembly process. This allows for the formation of species under thermodynamic control in the CoII manifold, with the kinetic stability of these assemblies in the oxidised CoIII and has been used to synthesise a variety of tetrahedra and helicates with a series of bis-bidentate N,N’-chelate ligands, which have shown to be stable away from their thermodynamically preferred conditions for long periods of time. These containers can be made both water and organic soluble via counteranion exchange, and a series of guests have been shown to bind in the tetrahedral species. Alongside on going biological viability tests, these guests show promise for a variety of applications including fluorescent tagging and radio-diagnostic agents. Novel switching methods have also been demonstrated for transformations between these species going both energetically down and up hill.

This thesis introduces a new strategy to fabricate single molecular transistor by utilizing the covalent chemistry to reconnect the molecule with the electroburnt graphene nanogap. We studied the effect of coupling chemistry and molecular length on the efficiency of reconnection between the molecule and the graphene. With this technique, we are also able to observe the Coulomb Blockade phenomenon, which is a characteristics of single-electron transistors. The high yield and versatility of this approach augur well for creating a new generation of sensors, switches, and other functional devices using graphene contacts. This thesis also introduces a new type of organic single-crystal p-n heterojunction inspired from the ball-and-socket shape-complementarity between fullerene and contorted dibenzotetrathienocoronene (c-DBTTC). We studied the influence of temperature, pressure, and time on the self-assembly process of contorted dibenzotetrathienocoronene on the as-grown fullerene crystals. We also utilized fluorescence microscopy to investigate the charge transfer in this type of p-n heterojunction. Finally, this thesis introduces one-dimensional and two-dimensional programming in solid-state materials from superatom macrocycles. We find that the linkers that bridges the two superatoms determine the distance and electronic coupling between the two superatoms in the macrocycle, which in turn determines the way they self-assembled in the solid-state materials. The thesis is composed of four chapters. The first chapter introduces why we are in terested in molecular transistors and new functional materials, and what has been done so far. The second chapter described the approach we developed to assemble single molecule into circuits with graphene electrodes. The third chapter details the method to fabricate the organic single-crystal C60-DBTTC p-n heterojunction, which is of great importance to understand their charge transfer process. The last chapter introduced a new series of superatom macrocycles and their self-assembly into solid-state materials with electron acceptor tetracyanoethylene.

Esta tese de doutorado aborda o desenvolvimento de sistemas microfluídicos eletroquímicos ultrassensíveis mediante a integração de eletrodos i) concêntricos e ii) nanoestruturados seletivos à detecção condutométrica sem contato acoplada capacitivamente (capacitively coupled contactless conductivity detection, C4D) e à amperometria, respectivamente. O uso dos eletrodos concêntricos, uma configuração inédita em microdispositivos na qual o filme fino metálico circunda todo o microcanal, se mostrou efetivo na melhora da detectabilidade da C4D para análises em fluxo de soluções padrão de LiClO4. O limite de detecção (LD) para esse sal foi igual a 343 pmol L-1, um valor aproximadamente quatro ordens de grandeza inferior àquele obtido com eletrodos planares. O microchip amperométrico nanoestruturado, por sua vez, consistiu de filmes de Au modificados com nanotubos de carbono de parede única (single-walled carbon nanotubes, SWCNTs) verticalmente alinhados e foi aplicado a padrões do neurotransmissor serotonina. A melhora na detectabilidade do método foi novamente apreciável; os valores de LD foram de 11,8 (Au liso) e 0,2 nmol L-1 (Au modificado com os SWCNTs verticalmente alinhados). Esse último é menor frente à grande maioria dos valores descritos na literatura, para os quais técnicas diversas foram empregadas, incluindo: i) potenciometria com eletrodos modificados (1,0 a 500 nmol L-1), ii) HPLC-MS (18,2 nmol L-1), iii) eletroforese capilar combinada com etapas de extração, empilhamento e préconcentração do analito (7,9 nmol L-1) e iv) sensor químico (200 nmol L-1). Finalmente, objetivando a fabricação de microchips de vidro, condutométricos e amperométricos, incorporando eletrodos concêntricos nanoestrurados, uma nova técnica de selagem foi desenvolvida. Essa técnica, designada como selagem adesiva de sacrifício, baseia-se no uso do resiste negativo SU-8 como camada intermediária de modo a permitir a vedação entre duas lâminas de vidro. Numa etapa posterior, a remoção seletiva do SU-8 sob o microcanal é realizada. Logo, canais microfluídicos com propriedades de superfície similares às do vidro foram obtidos. O protocolo experimental adotado é i) simples, ii) rápido, iii) não envolve níveis de pressão e temperatura elevados e iv) prescinde o uso de salas \"limpas\". Vedações com forças de adesão satisfatórias foram alcançadas, suportando pressões superiores a 4 MPa. / This PhD thesis reports the development of ultrasensitive electrochemical microfluidic systems by integrating concentric and nanostructured electrodes selective to capacitively coupled contactless conductivity detection (C4D) and amperometry, respectively. The use of the concentric electrodes, a new assembly in microdevices with thin films wrapping around the microchannel, showed to be effective towards improvement of the detectability in pressure-driven flow platforms incorporating C4D. The limit-of-detection (LOD) in flow analysis of LiClO4 solutions was 343 pmol L-1, ca. four orders of magnitude lower than to the levels obtained with planar electrodes alone. The nanostructured amperometric microchip, in turn, is related to integration of vertically aligned singlewalled carbon nanotubes (SWCNTs) over Au film. Such platform was applied to determination of serotonin standards. The nanomaterial influenced remarkably the sensitivity and detectability. Our system achieved a LOD of 0.2 nmol L-1, to the best of our knowledge one of the lowest values reported in the literature. Finally, in order to fabricate glass microdevices, conductometric and amperometric, with nanostructured concentric electrodes, we developed a new bonding method. This technique, called as sacrificial adhesive bonding, is based on SU-8 negative resist like intermediate layer so to allow the sealing between two glass slides. Next, the selective removal of the SU-8 under the microchannel is carried out. Thus, microfluidic channels presenting glass-like surface properties were achieved. The experimental protocol is simple and fast. In addition, neither high-pressure and elevated-temperature nor the use of \"clean\" rooms were not required. Bondings with satisfactory adhesion forces were obtained, supporting pressures above 4 MPa.

Magister Artium - MA / Collection development plays a significant role in the successful achievement of the library’s purpose. The reason for the existence of the library is to meet the information needs of the community it serves. To determine if the PIC is responsive to the information needs of parliamentary researchers, the study used a mixed method of data collection. A survey method in the form of a questionnaire was used to collect quantitative data from parliamentary researchers. Other researchers at Parliament, for example researchers employed by political parties are not part of this study. Qualitative data was collected through interviews with a selection of librarians involved in the PIC collection development process and an evaluation of the Collection Development Policy of the PIC. Four librarians from the PIC were interviewed, and the PIC Collection Development Policy was analysed to triangulate data collected from the questionnaire and interviews. The information needs of parliamentary researchers are triggered by the information needs of parliamentarians, and therefore it is significant that the PIC provide a collection that responds to the information needs of researchers so they can provide relevant information to parliamentarians. The findings indicate that the responsiveness of the library material varies according to the needs of the researchers. The PIC will benefit from a proactive involvement of parliamentary researchers in the collection development process. Customised orientation, proper needs analysis and collection evaluation will improve usage of the library resources and responsiveness of the library material to the clients.

Digitized by Kansas Correctional Industries

Os objetivos desta pesquisa foram levantar os benefícios auferidos pela aplicação de melhorias na ergonomia dos postos de trabalho e no abastecimento planejado de peças em uma linha de montagem automotiva, bem como identificar e verificar até que ponto pode-se gerar vantagens competitivas na redução do tempo de montagem do veículo, com a aplicação de investimentos tecnológicos em ergonomia na área de manufatura. A metodologia Methods Time Measurement (MTM), foi escolhida para mensurar as diferenças de tempos de processo, e para coleta e identificação de dados. Foram observadas duas linhas de montagem: a primeira denominada de inovadora, construída há três anos com investimentos em soluções ergonômicas, tanto no abastecimento quanto no processo, e outra, tradicional, construída há 20 anos, com poucos investimentos na área. De posse dos dados necessários dos sistemas estudados e com o uso da tecnologia MTM, a pesquisa avalia e propõe meios de mensurar os ganhos com a redução de atividades que não agregam valor ao produto, com o intuito de viabilizar investimentos em ergonomia em postos de trabalho padronizados, manipuladores, instalações mais modernas e até possuir um time de planejamento de processos de produção mais robusto. Neste trabalho, analisa-se também a influência da ergonomia no custo do produto final, qualidade, retrabalhos, afastamentos médicos e absenteísmo entre outros. / The objectives of this research were raise the benefits gained for the application of improvements in the ergonomics of the workstation in the planned supplying of parts in the automotive assembly line. As well as identifying and verifying until the point that can generate competitive advantages in the assembly time reduction of the vehicle, with the application of technological investments in ergonomics in the area of manufacture. The methodology Methods Time Measurement (MTM) was chosen to measure the differences of times of process, and for collection and identification of data. Two assembly lines were observed, the first called innovator, built three years ago with investments in ergonomic solutions, as much in the supplying as in the process, and another traditional one built 20 years ago, with few investments in the area. Using all necessary data of the studied systems and with the use of MTM technology, the research evaluates and recommends ways to measure the profits with the reduction of activities that not add value to the product. With the intention to make possible investments in ergonomics standardized workstation, manipulators, more modern installations and until have a planning process production team more robust. This work, also analyze the medical influence of the ergonomics in the cost of the final product, quality, rework, medical dismissal and absenteeism among others.

An important goal of nanoscience is the self-assembly of nanoscale building blocks into complex nanostructures. DNA is an important and versatile building block for nanostructures because of its small size, predictable base pairing, and numerous sequence possibilities. I use DNA origami to design and fold DNA into predesigned shapes, to assemble thin, branched DNA nanostructures as templates for nanoscale metal features. Using a PCR-based scaffold strand generation procedure, several wire-like nanostructures with varying scaffold lengths were assembled. In addition, more complex prototype circuit element structures were designed and assembled, demonstrating the utility of this technique in creating complex templates. My fabrication method for DNA-templated nanodevices involves a combination of techniques, including: solution assembly of the DNA templates, surface orientation and placement, and selective nanoparticle attachment to form nanowires with designed gaps for the integration of semiconducting elements to incorporate transistor functionality. To demonstrate selective surface placement of DNA templates, DNA origami structures have been attached between gold nanospheres assembled into surface arrays. The DNA structures attached with high selectivity and density on the surfaces. In a similar base-pairing technique, 5 nm gold nanoparticles were aligned and attached to specific locations along DNA templates and then plated to form continuous metallic wires. The nanoparticles packed closely, through the use of a high density of short nucleotide attachment sequences (8 nucleotides), enabling a median gap size of 4.1 nm between neighboring nanoparticles. Several conditions, including hybridization time, magnesium ion concentration, ratio of nanoparticles to DNA origami, and age of the nanoparticle solution were explored to optimize the nanoparticle attachment process to enable thinner wires. These small, branched nanowires, along with the future addition of semiconducting elements, such as carbon nanotubes, could enable the formation of high-density self-assembled nanoscale electronic circuits.

Dynamic Kinetic Selection (DKS) suggests that kinetic, rather than thermodynamic, stability will dictate the composition of a replicating population of biomolecules. Here, the results obtained from a series of five related reactions involving gradually increasing percentages of randomly-mutated substrate fragments to generate variants of full-length Azoarcus group I intron through an autocatalytic self-assembly reaction involving a series of recombination events, showed DKS as a driving factor in dictating the population composition of full-length product assembled from substrates that had fewer positions available to randomization. In trying to elucidate a plausible scheme for the origins of complex biomolecules on the prebiotic Earth, the suggestion that networks comprised of interacting molecules were more likely to evolve into biomolecules capable of obtaining and sustaining characteristics attributed to living molecules has gained traction within the past few years. Of specific interest is the catalytic efficacy of ribozymes whose genotypes require that they interact with molecules of the same genotype (selfish systems) to be effective catalysts versus those that are more effective when accomplishing catalysis by cooperating with ribozymes of a different genotype (cooperative systems). Here, the Azoarcus I ribozyme was used to compare these two types of system. Both systems were shown to robustly produce full-length product. Two different methods of introducing random mutations into substrate fragments for the reactions described in this thesis were employed. The differences in the preparation methods for the substrates was not expected to have an impact on the nature of the full-length product. However, there was no correlation between the positions that tended to be more tolerant of accepting random mutations between the products arising from the two preparation methods. One preparation method yielded full-length ribozymes more consistent with the secondary structure of the wild-type ribozyme and followed substitution patterns found in in vivo nucleic acid substitutions, whereas the other method provided full-length ribozymes that tolerated mutations that would be expected to greatly affect the secondary structure of the ribozyme and those positions tended to mutate evenly to any of the three possible alternative nucleobases. Point mutations introduced into ribozyme substrate fragments may have a deleterious, neutral, or beneficial effect, depending on their impact on the catalytic capability of the molecule vis-á-vis the effect, if any, the change has to the secondary and tertiary structure of the ribozyme. In this dissertation, the results of two series of point mutation reactions are addressed. The first set showed a point mutation to have a deleterious effect, whereas concerted mutations did not significantly affect activity of the ribozyme. The second series of reactions involved point mutations at a position that had previously been determined to be highly tolerant of random mutations. Results suggested that substitutions at this position had a minimal impact on ribozyme activity.

Designing self-assembling DNA nanostructures often requires the identification of a route for a scaffolding strand of DNA through the target structure. When the target structure is modeled as a graph, these scaffolding routes correspond to Eulerian circuits subject to turning restrictions imposed by physical constraints on the strands of DNA. Existence of such Eulerian circuits is an NP-hard problem, which can be approached by adapting solutions to a version of the Traveling Salesperson Problem. However, the author and collaborators have demonstrated that even Eulerian circuits obeying these turning restrictions are not necessarily feasible as scaffolding routes by giving examples of nontrivially knotted circuits which cannot be traced by the unknotted scaffolding strand. Often, targets of DNA nanostructure self-assembly are modeled as graphs embedded on surfaces in space. In this case, Eulerian circuits obeying the turning restrictions correspond to A-trails, circuits which turn immediately left or right at each vertex. In any graph embedded on the sphere, all A-trails are unknotted regardless of the embedding of the sphere in space. We show that this does not hold in general for graphs on the torus. However, we show this property does hold for checkerboard-colorable graphs on the torus, that is, those graphs whose faces can be properly 2-colored, and provide a partial converse to this result. As a consequence, we characterize (with one exceptional family) regular triangulations of the torus containing unknotted A-trails. By developing a theory of sums of A-trails, we lift constructions from the torus to arbitrary n-tori, and by generalizing our work on A-trails to smooth circuit decompositions, we construct all torus links and certain sums of torus links from circuit decompositions of rectangular torus grids. Graphs embedded on surfaces are equivalent to ribbon graphs, which are particularly well-suited to modeling DNA nanostructures, as their boundary components correspond to strands of DNA and their twisted ribbons correspond to double-helices. Every ribbon graph has a corresponding delta-matroid, a combinatorial object encoding the structure of the ribbon-graph's spanning quasi-trees (substructures having exactly one boundary component). We show that interlacement with respect to quasi-trees can be generalized to delta-matroids, and use the resulting structure on delta-matroids to provide feasible-set expansions for a family of delta-matroid polynomials, both recovering well-known expansions of this type (such as the spanning-tree expansion of the Tutte polynnomial) as well as providing several previously unknown expansions. Among these are expansions for the transition polynomial, a version of which has been used to study DNA nanostructure self-assembly, and the interlace polynomial, which solves a problem in DNA recombination.

Salvia hispanica L. (commonly known as chia) is gaining popularity worldwide and specially in US as a healthy oil and food supplement for human and animal consumption due to its favorable oil composition, and high protein, fiber, and antioxidant contents. Despite these benefits and its growing public demand, very limited gene sequence information is currently available in public databases. In this project, we generated 90 million high quality 150 bp paired-end sequences from the chia leaf and root tissues. The sequences were de novo assembled into 103,367 contigs with average length of 1,445 bp. The resulted assembly represented 92.2% transcriptome completeness. Around 69% of the assembled contigs were annotated against the uniprot database and represented a diverse array of functional and biological categories. A total of 14,267 contigs showed significant expression difference between the leaf and root tissues, with 6,151 and 8,116 contigs upregulated in the leaf and root, respectively. The sequence data generated in this project will provide valuable resources for future functional genomic research in chia. With the availability of transcriptome sequences, it would be possible to identify genes involved in the important metabolic pathways that give chia its unique nutritional and medicinal properties. Finally, the generated data will contribute to the genetic improvement efforts of chia to better serve the public demand.