The origin of fluorous interaction was explored and experimentally examined based on both HPLC and CEC data in this project. It was found that the selective fluorous interaction is a kind of reduced instantaneous or induced dipole interaction compared to the hydrophobic interaction. A series of FPPM preparation parameters were optimized. The optimized FPPM column can resolve the components in a manner that was otherwise not possible with its non-fluorous (hydrocarbon) counterpart. Following, the CEC separation of fluorous analytes on FPPM stationary phase based upon fluorous-fluorous interaction was realized for the first time. It was also found that, quantitatively, hydrophobic stationary phases have better methylene selectivity (〖 α〗_(-CH_2-)), while fluorous stationary phases have better perfluoromethylene selectivity (〖 α〗_(-CF_2-)). Thermodynamically, ∆G_(-CF_2- → -CF_2-)^° : ∆G_(-CH_2- → -CH_2-)^° (Gibbs free energy change of transferring a –CF2– unit to pure fluorous stationary phase versus Gibbs free energy change of transferring a –CH2– unit to pure hydrophobic stationary phase) is approximately equal to 8:1. A new concept, hypothetical water percentage (HWP) based on the comparison of 〖 α〗_(-CH_2-) and〖 α〗_(-CF_2-) was proposed for the first time to quantitatively evaluate the hydrophobicity/fluorophilicity of a stationary phase. A stationary phase can be classified as fluorous stationary phase when the HWP is less than 0 (more negative indicates more fluorous), or as a hydrophobic stationary phase when the HWP is larger than 100. For the range between 0 and 100, the stationary phase can be treated as either fluorous or hydrophobic due to the similar values of〖 α〗_(-CH_2-) and〖 α〗_(-CF_2-). Fluorous tagged peptides and proteins (up to 5800 Da) were effectively separated from their non-fluorous counterparts on the FPPM stationary phase in capillary-based columns and detected both on-line with ESI-MS and off-line with MALDI-MS. Finally, the FPPM solid-phase extraction (SPE) stationary phase was transplanted from the capillary to a microchip format. This microchip exhibits the merits of both selective fluorous interaction and micro total analysis system (µTAS). / Thesis (Ph.D, Chemistry) -- Queen's University, 2013-11-19 23:11:16.636

Um grande crescimento no interesse por microdispositivos eletroforéticos tem sido observado nos últimos anos. Vantagens atrativas como baixo consumo de reagentes e diminutos tempos de analise são verificados. Microdispositivos fabricados usando toner de impressora e folhas de transparência (poliéster) vem a somar valores como baixo custo e simplicidade de confecção à técnica de micro-separação eletroforética. Entretanto, a aplicação analítica utilizando esse tipo de microdispositivo tem sido pouco explorada. <br />Neste trabalho o uso de microchips eletroforéticos fabricados em poliéster-toner (PT) é utilizado para a determinação simultânea do herbicida glifosato e seu maior metabólito, AMPA (ácido aminometilfosfônico). Em um primeiro momento, o trabalho apresenta o desenvolvimento de uma metodologia no qual utiliza condutometria sem contato (C4D) como sistema de detecção, aliada à separação eletroforética em microchips de PT. Vários parâmetros que regem uma boa confiabilidade analítica, tanto quanto otimizam a sensibilidade do sistema foram avaliados. <br />Em um segundo momento, ainda aliada à microchips de PT, a técnica de cronoamperometria foi utilizada como sistema de detecção. Nessa etapa do projeto estudos eletroquímicos foram inicialmente realizados em eletrodos convencionais de ouro e cobre, buscando averiguar qual metal apresenta maior sensibilidade para o herbicida glifosato. Tendo o metal cobre como melhor escolha, eletrodos planares foram construídos a partir da combinação das tecnologias da produção de máscaras de toner, e placas de circuito impresso como fonte de cobre. <br />Em ambas as metodologias desenvolvidas, picos bem resolvidos foram encontrados para os analitos em estudo. Tempos menores que 80 s foram gastos entre o processo de separação e detecção; uma boa repetibilidade também foi encontrada. Os valores de limite de detecção (LD) utilizando C4D foram 60,8 e 74,8 &micro;mol L-1 para glifosato e AMPA respectivamente. Como esperado, menores valores de LD foram obtidos na detecção amperométrica, com 1,88 &micro;mol L-1 para glifosato e 16,45 &micro;mol L-1 para AMPA. A aplicabilidade dos métodos foi verificada através da analise do herbicida e seu metabólito em amostras de água. Etapas de derivatização e pré-concentração off-line não foram usadas nesse trabalho, dessa forma os dois métodos desenvolvidos apresentaram como principais vantagens o extremo baixo custo, e a simplicidade de uso. / A large increase in interest in electrophoretic microdevices has been observed in recent years. Advantages attractive as low reagent consumption and low analytical time are checked. Microdevices fabricated using printer toner and polyester transparency sheets are the sum values as low cost and simplicity of the technique of making micro-electrophoretic separation. However, the analytical application using this type of microdevice has been little explored. <br />In this work the use of microchip electrophoresis fabricated on polyester-toner (PT) is used for the simultaneous determination of the herbicide glyphosate and its major metabolite, AMPA (aminomethylphosphonic acid). In a first moment, the work presents the development of a methodology in which the use capacitively coupled contactless conductivity detection (C4D) for determination of analytes is employed, coupled with electrophoretic separation in PT microchips. Several parameters that govern a good analytical reliability and with the intuit of optimizing the sensitivity of the system were evaluated. <br />In a second time and still allied to the PT microchips, the technique of chronoamperometry was used for detection. Electrochemical studies were initially conducted in conventional electrodes of gold and copper, looking for determine which metal is more sensitive to detect the herbicide glyphosate. Having the best choice planar copper electrodes were constructed from a combination of technologies for the production of toner masks, and printed circuit boards. <br />In both, C4D and chronoamperometric detection methodologies, well-resolved peaks were found for the glyphosate and AMPA. Time analysis of less than 80s were found including the separation and detection processes, and a good analytical repeatability was also found. The limits of detection (LOD) using C4D were 60,8 and 74,8 &micro;mol L-1 respectively for glyphosate and AMPA. As expected, lower LOD were obtained in the amperometric detection methodology, 1.9 &micro;mol L-1 for glyphosate, and 16.5 &micro;mol L-1 for AMPA. The applicability of the methods was tested by analyzing the herbicide and its metabolite in fortified water samples. Steps of derivatization and preconcentration off-line were not applied in this work, so the two methods showed as main advantages very low cost and time analysis, and simplicity of application.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-06-20T14:21:30Z No. of bitstreams: 1 vaneidamariameurer.pdf: 2513462 bytes, checksum: e60f0acb50beb60e528dbf29fee51cad (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-07-13T15:24:14Z (GMT) No. of bitstreams: 1 vaneidamariameurer.pdf: 2513462 bytes, checksum: e60f0acb50beb60e528dbf29fee51cad (MD5) / Made available in DSpace on 2016-07-13T15:24:14Z (GMT). No. of bitstreams: 1 vaneidamariameurer.pdf: 2513462 bytes, checksum: e60f0acb50beb60e528dbf29fee51cad (MD5) Previous issue date: 2014-01-31 / O leite é um alimento de grande relevância na alimentação humana. Não obstante, dos diferentes setores da indústria alimentícia, o setor de laticínios destaca-se por estar entre os mais expressivos economicamente no Brasil. O leite de vaca, o mais consumido, pode ser substituído pelo leite de cabra principalmente porque este apresenta maior digestibilidade e baixo potencial alergênico. No entanto, uma prática fraudulenta consiste na adulteração do leite caprino com leite bovino. Dentre alguns fatores que contribuem para tal, estão o menor rendimento na produção de leite de cabra, em conjunto com o preço mais baixo do leite de vaca. O presente estudo objetivou avaliar as técnicas de eletroforese em gel de poliacrilamida na presença de ureia (UREIA-PAGE) e eletroforese microfluídica lab-on-a-chip, a fim de caracterizar o perfil proteico do leite de cabra e vaca e estabelecer técnicas rápidas e eficientes para detecção de fraude no leite de cabra. A detecção da fraude no leite de cabra por adição do leite de vaca foi testada pelo perfil eletroforético das proteínas usando os dois métodos citados acima. Os dois métodos avaliados mostraram que a fração αS1 - caseína bovina pode ser utilizada como um marcador para detecção desta fraude. Com a técnica de UREIA-PAGE foi possível detectar a presença da αS1-caseína do leite bovino a partir de 2% de leite bovino adicionado ao leite caprino. Entretanto com a técnica lab-on-a-chip só foi possível detectar a partir de 20% de adição. Pelo método de eletroforese microfluídica foi possível visualizar o perfil proteico do leite das diferentes espécies (bovino e caprino) traçando seus respectivos perfis eletroforético, com disponibilização rápida dos resultados. O que permite uma investigação de fraude de leite para laboratórios de rotina por meio de um método rápido, já que todo o procedimento dura cerca de 4 horas e permite um grau de automação maior. Devido à necessidade de técnicas eficientes, rápidas, automatizadas para atender a demanda da indústria de laticínios e dos órgãos de fiscalização, faz-se necessário o aperfeiçoamento da técnica lab-on-a-chip com o intuito de melhorar seu desempenho e aplicabilidade, possibilitando a detecção de níveis mais baixos de fraude. / Milk is a food of great relevance in human nutrition. In addition, among the different food industries in Brazil, the dairy industry is one of the economically expressive. Cow's milk was be substituted for goat‟s milk in any situation. The goat‟s milk presents better digestibility and low allergenic potential. However, it is common adulteration of goat milk with cow‟s milk. Some factors like low income of goat milk and the lower price of cow‟s milk contribute for this kind of fraud. The present study aimed to evaluate polyacrylamide gel electrophoresis techniques in presence of urea (UREA-PAGE) and microfluidic lab–on–a–chip, in order to characterize the protein profile of milk in the different species goat and cow. In addition, establish faster and efficient techniques for fraud detection in goat‟s milk. The fraud detection in goat‟s milk by the addition of cow milk was analyzed using the electrophoretic profiles of the proteins by the polyacrylamide gel electrophoresis methods UREA–PAGE and microfluidic lab-on-a-chip electrophoresis. Both studded methods showed the αs1 – casein bovine as a marked for this fraud detection. The UREA–PAGE techniques detected the bovine‟s milk αs1- casein from 2% of cow milk added to caprine milk. However lab-on–a-chip technique detected bovine‟s milk αs1- casein from 20% of addition. The microfluidic electrophoresis in microchip allowed the separation of the milk‟s proteins from the both species tracing their respective electrophoretic profiles with fast results availability; this method has great relevance in milk‟s fraud investigations in routine labs. The use of lab-on-a-chip has resulted in the rapid procedures as the run time is about four hours. Due to the need for automated, fast and efficient techniques to attend the dairy industry and the regulatory agencies request, it‟s necessary the development of the lab-on-a–chip technique in order to improve their performance and applicability.

No description available.

This thesis aims to explain the evolution and transformation of the microchip industry. It focuses on the changes and prediction of the future state including its causes and consequences. The analysis starts on the general description of the market and continues through its subjects ending on relationships between them. This serves as a source of information to the prediction in the final part of the thesis. In the beginning the products, which are taken into consideration in this work (namely CPUs, GPUs and APUs), are described. Following this, there is an analysis of the competition environment that defines a structure of the market upon which further work is based. (Three levels; the manufacturer of photolithographic machines, makers of the chips and their designers and OEM and aftermarket subjects.) The penultimate part defines the barriers to entry to this market and three categories are drawn up: economic, technical and geoeconomic, which are applied to every level of the market. Thus all prerequisites to a successful prediction are satisfied. In the last part of the thesis the prognosis is made and defined, along with its assumptions and limitations. In the concluding part of this work the consequences and results are summarized.

The past few years have seen a rapid expansion in interest in the characterization of the entire complement of proteins, or proteome. Micro total analysis systems (μTAS) are an emerging promising method, offering rapid, sensitive and low sample consumption separations. I have demonstrated microchip capillary electrophoresis (CE) devices made of CaF2. New methods have been developed for micromachining enclosed capillaries in CaF2. CE analysis of fluorescently labeled amino acids was used to illustrate bioanalytical applications of these microdevices. Initial on-chip infrared spectroscopy results for qualitative analyte identification were achieved in microfluidic CaF2 channels. I have also shown the evaluation of poly(methylmethacrylate) (PMMA) and thermoset polyester (TPE) microchips for use in protein profiling. To improve separation efficiency and reduce protein adsorption, dynamic coating and poly(ethylene glycol) (PEG) grafting using atom transfer radical polymerization (ATRP) have been used in PMMA microdevices. Proteins, peptides and protein digests have been separated electrophoretically in these PMMA microchips. My results demonstrate that PMMA microdevices should be well suited as microfluidic systems for high performance separations of complex biological mixtures. In-channel ATRP has been developed for the surface modification of TPE microdevices. Characterization indicates that PEG-modified microchannels have much lower and more pH-stable electroosmotic flow, more hydrophilic surfaces and reduced nonspecific protein adsorption. CE of amino acid and peptide mixtures in these PEG-modified TPE microchips had good reproducibility. Phosducin-like protein and phosphorylated phosducin-like protein were also separated to measure the phosphorylation efficiency. My results show that PEG-grafted TPE microchips have broad potential application in biomolecular analysis. Cancer marker analysis is important for medical research and applications. I report a method that can covalently attach appropriately oriented antibodies of interest on monolith surfaces. To reduce nonspecific adsorption, protein solutions were used to effectively block the monolith surface. Selective preconcentration and elution of human chorionic gonadotropin have been performed in my affinity columns, demonstrating that this type of system should have promising applications in cancer marker detection.

The aim of this study was to evaluate temperature data collected from Thoroughbred foals between birth and shortly after weaning. It provides a valuable survey with epidemiological conclusions providing insight into the temperature trends and pyretic occurrences of Thoroughbred foals during this age period. Temperature data were collected using telemetry from temperature sensitive microchips implanted into newborn foals. The system of inputting and storing temperature data was completely electronic and this study evaluated this system. It was found that this system was stable and allowed the evaluation of large amounts of frequently acquired data with little human intervention. The data obtained resulted in the valuable evaluation of age associated body temperature trends within the foals as well as providing an indication of the extent and epidemiology of pyrexia within the study cohort. The system of evaluating temperatures based both on the individual day value as well as on each individual foals prior series of temperatures shows that the use of these two criteria can be utilised simultaneously. The study provides basic information which future researchers using similar systems can use to objectively set criteria for pyrexia. An outbreak of equine encephalosis also occurred during the study period and this provided much needed prospective epidemiological information for such an outbreak, something which has not previously been documented. Copyright / Dissertation (MSc (Veterinary Science))--University of Pretoria, 2009. / Production Animal Studies / unrestricted

No description available.

This thesis details the design, fabrication, and testing of two optofluidic platforms, a square fused silica capillary and a MgF2-PDMS microfluidic chip to detect radiation-induced biochemical changes in cells during radiation treatment (radiotherapy). The platforms integrate a near-infrared Raman system of 785 nm excitation and a fiber-based optical trap at 1064 nm in a dual-beam configuration for the manipulation and subsequent examination of single polystyrene beads (5µm) and two breast carcinoma cell lines, MCF-7, and MDA-MB-23 (20-30 µm). Particular attention was paid to the role of MgF2 as a novel substrate for microfluidic fabrication and the device background contributions that could hinder spectral contributions from the samples. Successful optical trapping within the platforms was performed, which allowed the sample immobilization for the entire Raman acquisition time (10-30 s) via an orthogonally positioned objective for the excitation and collection of Raman signal. Data collected in the MgF2-PDMS microchip yielded high-quality spectra with no presence of PDMS characteristic Raman peaks in the spectral region of 450-1800 cm-1. / Graduate / 2023-04-08

Over the past 15 years, research in the field of microfluidics has rapidly gained popularity. By seeking to miniaturize and automate separation-based analysis, microfluidic research seeks to improve current methods through decreased cost, analysis time, and sources of contamination. My work has focused on developing a novel fabrication method, based on standard microfabrication techniques, to create thin-film microfluidic devices. This microfabrication format makes it possible to generate devices that provide high efficiencies, enable mass fabrication, and provide a platform capable of integrating the microfluidic and electronic components necessary for a micro-total analysis system (μ-TAS). Device fabrication combines the processes of photolithography, thermal evaporation, plasma enhanced chemical vapor deposition (PECVD), and wet chemical etching to ultimately provide hollow-core channels. When these microcapillaries are filled with buffer and potentials are applied across them, control of the flow in the channels can be established. By designing intersecting microchannels having an offset “T†geometry, I have been able to inject and electrophoretically separate three fluorescently labeled amino acids and obtain efficiencies of over 2500 theoretical plates. Through the addition of commercially available electroosmotic flow reducing coatings, I have been able to improve the separation of these amino acids, decreasing the run time by approximately 6 fold and increasing the efficiency by as much as 10 fold. Through the use of these coatings I have also been able to carry out electrophoretic separations of three peptides. My most recent work has focused on the polymerization of acrylamide gels in these channels. A method for the selective placement of a gel has been developed using a prepolymer solution with a light-sensitive initiator. Further work to adjust the polymer pore size and interface with ampholyte-containing gels should allow methods such as capillary gel electrophoresis (CGE), preconcentration, and two dimensional (isolectric focusing and CGE) separations to be performed. The development of gel-based analysis methods, along with other fluidic and electrical capacities, should move thin-film microdevices toward the realization of the lab-on-a-chip concept.