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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
21

Aplicação de eletroforese capilar com detecção condutométrica sem contato à determinação de espécies neutras / Application of capillary electrophoresis with contactless conductivity detection to the determination of neural species

Carvalho, Alexandre Zatkovskis 20 August 2003 (has links)
Neste trabalho, foram desenvolvidos métodos para determinação de espécies neutras por eletroforese capilar (CE) com detecção condutométrica sem contato (CCD). Estratégias baseadas em eletroforese capilar em solução livre (FSCE) e cromatografia micelar eletrocinética (MEKC) foram utilizadas em três casos: misturas de álcoois alifáticos, misturas de açúcares e salbutamol. Estas substâncias foram escolhidas por apresentarem ampla distribuição de características químicas. Os n-álcoois possuem regiões polares e apoIares distintas ao longo da cadeia carbônica, sendo que em solução aquosa se apresentam invariavelmente como espécies neutras. Os açúcares, apesar das longas cadeias carbônicas, possuem grande número de hidroxilas uniformemente distribuídas e podem ser ionizados a valores elevados de pH. Já o salbutamol, pode ser encontrado como espécie catiônica, neutra ou aniônica, dependendo do pH do meio. A melhor aproximação para os álcoois foi MEKC, que permitiu a separação e detecção da ordem de 10-4 mol·L-1 para cinco isômeros de pentanol. A utilização de eletrólito de corrida com pH 12,1 permitiu a determinação de frutose, glicose, galactose e sacarose da ordem de 10-5 moI&middotL-1 por FSCE em capilares de 20 µm. Salbutamol pode ser detectado como cátion e ânion em FSCE em limites de detecção da ordem de dez vezes menores que aquele obtido para a espécie neutra por MEKC. Como o mecanismo pelo qual ocorre a detecção condutométrica em MEKC não era ainda bem conhecido, foram desenvolvidos experimentos que ajudassem a elucidá-Io. Medidas de condutividade, viscosidade e análise de impedância de soluções tampão com dodecilsulfato de sódio (SDS) com n-álcoois e experimentos com soluções similares em MEKC demonstraram que a resposta observada com CCD é bastante complexa, pois vários fenômenos contribuem para o comportamento da condutividade na região dos analitos. Os principais fenômenos, os quais não estavam sendo devidamente considerados em modelos anteriores, são a dissociação e a ionização provocadas pelos analitos sobre as micelas. Estes fenômenos seriam particularmente significativos para as mobilidades das espécies envolvidas nas micelas, provocando a propagação de vacâncias que seriam então detectadas. / In the present work, analytical methods for determination of neutral species based on capillary electrophoresis (CE) with contactless conductivity detection (CCD) were developed. Free solution capillary electrophoresis (FSCE) and micelar electrokinetic chromatography (MEKC) were applied to three cases: mixtures of aliphatic alcohols, mixtures of sugars, and salbutamol. These substances were selected due to their distinctiveness. The alcohols have well-defined polar and apoIar regions in their carbonic chain and are typical non-ionic species in aqueous medium. The sugars have a great number of hydroxyl groups along the carbonic chain, which give a polar nature and can be ionized at high pH values. The salbutamol is amphoteric. The best approach for the alcohols was MEKC that allowed separation of five pentanol isomers with limit of detection of 10-4 mol·L-1. A running electrolyte with pH 12.1 allowed determination of 10-5 mol·L-1 of fructose, glucose, galactose, and sucrose, using FSCE with 20-µm inner diameter capillary. The sensitivity for the cationic and anionic forms of albuterol in FSCE was about ten times greater than that one achieved by MEKC for the neutral species. Since the conductivity detection in MEKC was not clearly understood, some experiments were carried out in order to improve the knowledge about it. Conductivity and viscosity measurement as well as impedance analysis of buffered sodium dodecyl sulfate solution with n-alcohols and experiments using similar conditions in MEKC showed that CCD response is complex, because several phenomena contribute to the solution conductivity in the region of the analytes. The main phenomena, which are not properly considered in the previous models, are the effects of the analytes on the dissociation and ionization of the micelles. These phenomena would be responsible for the vacancies detected as negative peaks, which would be formed by the augment of the mobilities of the species involved in the micelle formation.
22

Secure contactless mobile financial services with near field communication

Poroye, Adeola Oluwaseyi January 2011 (has links)
This thesis presents the results from work with three prototypes that use Near Field Communication technology to provide secure contactless mobile nancial services on mobile phones.
23

Side-Channel Monitoring of Contactless Java Cards

Berkes, Jem 21 January 2008 (has links)
Smart cards are small, portable, tamper-resistant computers used in security-sensitive applications ranging from identification and access control to payment systems. Side-channel attacks, which use clues from timing, power consumption, or even electromagnetic (EM) signals, can compromise the security of these devices and have been an active research area since 1996. Newer ``contactless'' cards communicate using radio frequency (RF), without physical contact. These contactless smart cards are sometimes grouped with radio frequency identification (RFID) devices in popular usage of the term. This thesis investigates devices that use the ISO 14443 (proximity card) protocol, a large class of contactless/RFID devices. Although contactless smart cards are increasingly common, very few reproducible practical attacks have been published. Presently, there are no known documented side-channel attacks against contactless Java Cards (open standard multi-application cards) using generic unmodified hardware. This thesis develops a research-friendly platform for investigating side-channel attacks on ISO 14443 contactless smart cards. New techniques for measurement and analysis, as well as the first fully documented EM side-channel monitoring procedure, are presented for a contactless Java Card. These techniques use unmodified, commercial off-the-shelf hardware and are both practical and broadly applicable to a wide range of ISO 14443 devices, including many payment cards and electronic passports.
24

Side-Channel Monitoring of Contactless Java Cards

Berkes, Jem 21 January 2008 (has links)
Smart cards are small, portable, tamper-resistant computers used in security-sensitive applications ranging from identification and access control to payment systems. Side-channel attacks, which use clues from timing, power consumption, or even electromagnetic (EM) signals, can compromise the security of these devices and have been an active research area since 1996. Newer ``contactless'' cards communicate using radio frequency (RF), without physical contact. These contactless smart cards are sometimes grouped with radio frequency identification (RFID) devices in popular usage of the term. This thesis investigates devices that use the ISO 14443 (proximity card) protocol, a large class of contactless/RFID devices. Although contactless smart cards are increasingly common, very few reproducible practical attacks have been published. Presently, there are no known documented side-channel attacks against contactless Java Cards (open standard multi-application cards) using generic unmodified hardware. This thesis develops a research-friendly platform for investigating side-channel attacks on ISO 14443 contactless smart cards. New techniques for measurement and analysis, as well as the first fully documented EM side-channel monitoring procedure, are presented for a contactless Java Card. These techniques use unmodified, commercial off-the-shelf hardware and are both practical and broadly applicable to a wide range of ISO 14443 devices, including many payment cards and electronic passports.
25

Secure contactless mobile financial services with near field communication

Poroye, Adeola Oluwaseyi January 2011 (has links)
This thesis presents the results from work with three prototypes that use Near Field Communication technology to provide secure contactless mobile nancial services on mobile phones.
26

Multi-frequency Electrical Conductivity Imaging Via Contactless Measurements

Ozkan, Koray Ozdal 01 February 2006 (has links) (PDF)
A multi-frequency data acquisition system is realized for subsurface conductivity imaging of biological tissues. The measurement procedures of the system at different frequencies are same. The only difference between the single frequency experiments and the multi-frequency experiments is the hardware, i.e. the sensor and the power amplifier used in the single frequency experiments was different than that were used in the multi-frequency experiments. To avoid confusion the measurement system with which the single frequency experiments were performed is named as prototype system and the measurement system with which the multi-frequency experiments were performed is named as multi-frequency system. This system uses magnetic excitation (primary field) to induce eddy currents inside the conductive object and measures the resulting magnetic field due to eddy currents (secondary field). For this purpose, two differential-coil sensors are constructed / one is for the single frequency measurements and the other is for the multi-frequency measurements. Geometrically the coils are same, the only difference between them is the radius of the wires wound on them. The sensor consists of two differentially connected identical receiver coils employed to measure secondary field and in between the receiver coils is placed a transmitter coil, which creates the primary field. The coils are coaxial. In the prototype system the transmitter coil is driven by a sinusoidal current of 300 mA (peak) at 50 kHz. In the multi-frequency system the transmitter coil is driven by a sinusoidal current of 217 mA (peak), 318 mA (peak), 219 mA (peak) and 211 mA (peak) at 30 kHz, 50 kHz, 60 kHz and 90 kHz, respectively. A data acquisition card (DAcC) is designed and constructed on a printed circuit board (PCB) for phase sensitive detection (PSD). The equivalent input noise voltage of the card was found as $146.80 hspace{0.1 cm}nV$. User interface programs (UIP) are prepared to control the scanning experiments via PC (HP VEE based UIP, LabVIEW based UIP) and to analyze the acquired data (MATLAB based UIP). A novel sensitivity test method employing resistive ring phantoms is developed. A relation between the classical saline solution filled vessel (45mm radius, 10 mm depth) phantoms and the resistive ring phantoms is established. The sensitivity of the prototype system to saline solutions filled vessels is 13.2 $mV/(S/m)$ and to resistive rings is 155.02 mV/Mho while the linearity is 3.96$%$ of the full scale for the saline solution filled vessels and 0.12$%$ of the full scale for the resistive rings. Also the sensitivity of the multi-frequency system is determined at each operation frequency by using resistive ring phantoms. The results are in consistence with the theory stating that the measured signals are linearly proportional with the square of the frequency. The signal to noise ration (SNR) of the prototype system is calculated as 35.44 dB. Also the SNR of the multi-frequency system is calculated at each operation frequency. As expected, the SNR of the system increases as the frequency increases. The system performance is also tested with agar phantoms. Spatial resolution of the prototype system is found 9.36 mm in the point spread function (PSF) sense and 14.4 mm in the line spread function (LSF) sense. Spatial resolution of the multi-frequency system is also found at each operation frequency. The results show that the resolving power of the system to distinguish image details increases as the frequency increases, as expected. Conductivity distributions of the objects are reconstructed using Steepest-Descent algorithm. The geometries and the locations of the reconstructed images match with those of the real images. The image of a living tissue, a leech, is acquired for the first time in the literature. Magnetic conductivity spectroscopy of a biological tissue is shown for the first time in electrical conductivity imaging via contactless measurements. The results show the potential of the methodology for clinical applications.
27

Modélisation et commande des systèmes de manipulation sans contact. : Vers l'amélioration du diagnostic en endoscopie digestive. / Modeling and contrôl of contractless magnetic manipulation systems : Towards improving diagnosis in digestive endoscopy

Veron, Baptiste 28 November 2014 (has links)
Les techniques de diagnostic actuellement utilisées en endoscopie digestive ne permettentpas une observation complète et précise de l’intestin grêle. Les capsules endoscopiquestentent de répondre à cette problématique, mais le médecin n’a aucune maîtrise de leurdéplacement une fois qu’elles sont avalées par les patients. Dans ce contexte, les travauxdéveloppés dans cette thèse portent sur l’utilisation des champs magnétiques afin demanipuler un objet (comme une capsule) sans contact sur un large espace de travail. Pourcela, nous étudions les systèmes de manipulation magnétique à électroaimants mobiles.Nous étudions dans un premier temps la manière de modéliser le champ magnétiquecréé par un électroaimant. Nous développons un modèle hybride (analytique recalé surdes mesures) prenant en compte le noyau ferromagnétique des électroaimants. Dans unsecond temps, nous nous intéressons à un système générique de manipulation magnétique,composé de n électroaimants pouvant se déplacer dans tout l’espace. Nous développons unmodèle de ce système, en intégrant les mobilités de chacun des électroaimants. Ce modèleest ensuite linéarisé, ce qui nous permet d’introduire une commande linéarisante. Cettecommande permet une gestion indépendante du déplacement de chacun des électroaimants,ainsi que du courant qui les traverse. Enfin, les développement théoriques sont testés ensimulation et sur un dispositif expérimental. / Diagnostic techniques currently used in gastrointestinal endoscopy do not allow a completeand accurate observation of the small bowel. Endoscopic capsules were designed to solvethis problem, but the doctor cannot control their movement once they are swallowed bypatients. In that context, the work developed in this thesis focuses on the use of magneticfields to manipulate an object (such as a capsule) without contact, on a large workspace.For this, we study magnetic systems with mobile electromagnets. We study first how tomodel the magnetic field created by an electromagnet. We develop an analytical modeltaking into account the ferromagnetic core of electromagnets. Then, we study a genericsystem composed of n electromagnets which can move throughout space. We develop amodel of the system, integrating the mobility of each of the electromagnets. This modelis then linearized, allowing us to introduce a linearizing control. This command allowsindependent management of the movement of each of the electromagnets, and the currentflowing in it. Finally, the model and the command are tested in simulation and on anexperimental device.Keywords: Magnetism,
28

Biossensor condutométrico sem contato em microchip contendo ácido fólico como biorreceptor / Contactless conductometric biosensor in microchip containing folic acid as bioreceptor

Renato Sousa Lima 29 July 2010 (has links)
Este trabalho descreve o desenvolvimento de um biossensor contendo transdução condutométrica sem contato (C4D, capacitively coupled contactless conductivity detection) e ácido fólico (FA) como biorreceptor em microchip, uma nova alternativa que poderá ser utilizada na determinação do biomarcador tumoral FR-α. Essa espécie exibe interações com FA altamente específicas, com constantes de formação da ordem de 109-1010. Os dispositivos microfluídicos, os quais consistiram de uma lâmina de vidro (integrando os eletrodos), dielétrico (contendo a fase biossensora) e substrato de poli(dimetilsiloxano) (PDMS, incorporando os microcanais), foram fabricados utilizando-se processos de fotolitografia e deposição de filmes finos em fase vapor. Objetivando melhorias nos níveis de detecção da C4D, estudos de sensibilidade com base em parâmetros da curva analítica foram conduzidos alterando-se a natureza do dielétrico e a configuração dos eletrodos. Posteriormente, estudos de caracterização foram realizados para as superfícies modificadas com os intermediários de imobilização; condições reacionais distintas (reagente, concentração, solvente e tempo) foram consideradas. As técnicas de microscopia eletrônica de varredura e espectroscopia de fotoelétrons excitados por raios-X foram usadas, respectivamente, a fim de se verificar a possível formação de aglomerados e permitir determinações qualitativas e quantitativas sobre as composições químicas das superfícies. Como resultado dos experimentos de sensibilidade e caracterização de superfície, adotamos os parâmetros seguintes para os ensaios de interações biomoleculares posteriores: filme de SiO2 como dielétrico, eletrodos seletivos à C4D com formato retangular e orientação antiparalela e monocamadas automontadas do reagente 3-aminopropil(trietoxisilano) como intermediário de imobilização de FA. As duas etapas finais do trabalho foram: otimização do tempo de funcionalização com FA (3, 5 e 7 h) e caracterização da fase biossensora, realizada a partir de medidas de C4D e microscopia de força atômica (AFM). Para o primeiro caso, os microchips foram aplicados a um padrão de anticorpo monoclonal específico a FA (α-FA). Os ensaios biomoleculares indicaram uma adsorção efetiva de FA junto à superfície de SiO2 silanizada, sem a ocorrência (ao menos em níveis significativos) de impedimentos estéricos de sua espécie bioativa. Dentre os tempos de funcionalização investigados, 3 h foi aquele que resultou em uma maior sensibilidade do método. Em termos da etapa de caracterização eletroquímica da fase biossensora, seus resultados mostraram haver correlação entre a resposta analítica e as interações FA/α-FA. Em adição, conforme indicaram as medidas de AFM, não houve alterações drásticas na morfologia do substrato (SiO2) em função dos processos de modificação química de superfície. Por fim, o uso da C4D como uma técnica de transdução em biossensores mostrou-se uma alternativa promissora para a análise do biomarcador tumoral FR-α. Dentre outros aspectos, essa plataforma analítica requer uma instrumentação simples, barata e portátil, não apresenta inconvenientes relacionados ao contato eletrodo/solução, dispensa o uso de mediadores redox e permite a determinação simultânea de multianalitos. Neste ínterim, alterações no transdutor devem ser implementadas visando um aumento na sensibilidade do método, o qual representa seu fator limitante principal. / This work describes the development of a biosensor containing capacitively coupled contactless conductivity transduction (C4D) and folic acid (FA) as bioreceptor in microchip, a new alternative that can be used in FR-α tumor biomarker analysis. FR-α exhibits highly specific interactions with FA, showing formation constants of the order of 109-1010. The microfluidic devices consisted of a glass layer (integrating the electrodes), dielectric (containing the biosensor phase), and poly(dimetilsiloxane) substrate (PDMS, incorporating microchannel). The microfabrication stage evolved photolithography processes, metal adsorption via sputtering, and plasma-enhanced vapor film deposition. In order to improve detection levels of C4D, sensitivity studies were conducted by changing the dielectric nature and electrode configuration. Through flow analysis with given electrolyte standards, the limits of detection and quantification were calculated based on analytical curve parameters. Subsequently, researches were performed to characterize the modified surfaces with immobilization intermediate considering reaction conditions distinct (reagent, concentration, solvent, and time). The techniques of scanning electron microscopy and X-ray photoelectron spectroscopy were employed, respectively, aiming to verify the clusters formation and allow qualitative and quantitative determinations about the surfaces chemical composition. From the results of sensitivity experiments and surface characterization, we adopt the following parameters for the biomolecular interactions assays: SiO2 film as dielectric, C4D selective electrodes with rectangular shape and antiparallel orientation, and self-assembled monolayers of 3-aminopropyl(triethoxysilane) as intermediary for immobilization of FA. The two final steps of the work were: optimizing the FA functionalization time (3, 5, and 7 h) and phase biosensor characterization, made from measures of C4D and atomic force microscopy (AFM). For the first case, due to the absence of FR-α standard for purchase, the microchips were applied to FA specific monoclonal antibody (α-FA). The biomolecular assay indicated effective adsorption of FA, without occurrence (at least in significant levels) of steric hindrance of its bioactive specie. Among the investigated times of functionalization, 3 h resulted in a higher sensitivity of the method. In terms of biosensor phase electrochemical characterization stage, their results evidenced correlation between analytical response and FA/α-FA interactions. Additionally, as the AFM measurements showed, drastic changes in the morphology of the substrate (SiO2) with the surface modification processes did not occur. Finally, the use of the C4D as transduction technical in biosensors proved to be a promissory alternative for FR-α tumor biomarker analysis. Among other features, this platform has not drawbacks related to the electrode/solution contact, dispenses the use of redox mediators, allows the simultaneous determination of multianalytes, and employs an instrumentation that is simple, cheap, and portable. Nevertheless, changes in the transducer should be implemented to increase the method sensitivity, which represents its main limiting factor.
29

Desenvolvimento de metodologia de baixo custo para determinação de glifosato usando microdispositivos eletroforéticos fabricados em poliéster-toner / Development of low cost methodology for determination of glyphosate using electrophoretic microdevices fabricated in polyester-toner

Eduardo Rodrigues da Silva 15 April 2011 (has links)
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.
30

Aplicação de eletroforese capilar com detecção condutométrica sem contato à determinação de espécies neutras / Application of capillary electrophoresis with contactless conductivity detection to the determination of neural species

Alexandre Zatkovskis Carvalho 20 August 2003 (has links)
Neste trabalho, foram desenvolvidos métodos para determinação de espécies neutras por eletroforese capilar (CE) com detecção condutométrica sem contato (CCD). Estratégias baseadas em eletroforese capilar em solução livre (FSCE) e cromatografia micelar eletrocinética (MEKC) foram utilizadas em três casos: misturas de álcoois alifáticos, misturas de açúcares e salbutamol. Estas substâncias foram escolhidas por apresentarem ampla distribuição de características químicas. Os n-álcoois possuem regiões polares e apoIares distintas ao longo da cadeia carbônica, sendo que em solução aquosa se apresentam invariavelmente como espécies neutras. Os açúcares, apesar das longas cadeias carbônicas, possuem grande número de hidroxilas uniformemente distribuídas e podem ser ionizados a valores elevados de pH. Já o salbutamol, pode ser encontrado como espécie catiônica, neutra ou aniônica, dependendo do pH do meio. A melhor aproximação para os álcoois foi MEKC, que permitiu a separação e detecção da ordem de 10-4 mol&middot;L-1 para cinco isômeros de pentanol. A utilização de eletrólito de corrida com pH 12,1 permitiu a determinação de frutose, glicose, galactose e sacarose da ordem de 10-5 moI&middotL-1 por FSCE em capilares de 20 &#181;m. Salbutamol pode ser detectado como cátion e ânion em FSCE em limites de detecção da ordem de dez vezes menores que aquele obtido para a espécie neutra por MEKC. Como o mecanismo pelo qual ocorre a detecção condutométrica em MEKC não era ainda bem conhecido, foram desenvolvidos experimentos que ajudassem a elucidá-Io. Medidas de condutividade, viscosidade e análise de impedância de soluções tampão com dodecilsulfato de sódio (SDS) com n-álcoois e experimentos com soluções similares em MEKC demonstraram que a resposta observada com CCD é bastante complexa, pois vários fenômenos contribuem para o comportamento da condutividade na região dos analitos. Os principais fenômenos, os quais não estavam sendo devidamente considerados em modelos anteriores, são a dissociação e a ionização provocadas pelos analitos sobre as micelas. Estes fenômenos seriam particularmente significativos para as mobilidades das espécies envolvidas nas micelas, provocando a propagação de vacâncias que seriam então detectadas. / In the present work, analytical methods for determination of neutral species based on capillary electrophoresis (CE) with contactless conductivity detection (CCD) were developed. Free solution capillary electrophoresis (FSCE) and micelar electrokinetic chromatography (MEKC) were applied to three cases: mixtures of aliphatic alcohols, mixtures of sugars, and salbutamol. These substances were selected due to their distinctiveness. The alcohols have well-defined polar and apoIar regions in their carbonic chain and are typical non-ionic species in aqueous medium. The sugars have a great number of hydroxyl groups along the carbonic chain, which give a polar nature and can be ionized at high pH values. The salbutamol is amphoteric. The best approach for the alcohols was MEKC that allowed separation of five pentanol isomers with limit of detection of 10-4 mol&middot;L-1. A running electrolyte with pH 12.1 allowed determination of 10-5 mol&middot;L-1 of fructose, glucose, galactose, and sucrose, using FSCE with 20-&#181;m inner diameter capillary. The sensitivity for the cationic and anionic forms of albuterol in FSCE was about ten times greater than that one achieved by MEKC for the neutral species. Since the conductivity detection in MEKC was not clearly understood, some experiments were carried out in order to improve the knowledge about it. Conductivity and viscosity measurement as well as impedance analysis of buffered sodium dodecyl sulfate solution with n-alcohols and experiments using similar conditions in MEKC showed that CCD response is complex, because several phenomena contribute to the solution conductivity in the region of the analytes. The main phenomena, which are not properly considered in the previous models, are the effects of the analytes on the dissociation and ionization of the micelles. These phenomena would be responsible for the vacancies detected as negative peaks, which would be formed by the augment of the mobilities of the species involved in the micelle formation.

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