Raman spectroscopy, laser-induced fluorescence, and sum-frequency generation (SFG) spectroscopy are used to investigate the behavior of compressible mobile phases and stationary phases under a variety of chromatographic conditions. Efforts to understand and optimize separations employing compressible mobile phases have been limited by a lack of understanding of the mobile phase density gradient. Mobile phase compressibility leads to gradients in linear velocity and solute retention and affects separation speed and efficiency, especially in packed columns. This work describes on-column density measurement of CO2, a common carrier fluid for SFC and SGC, in packed capillary columns using Raman microspectroscopy. On-column detection by laser-induced fluorescence is used to observe the effect of the mobile phase density gradient on separation speed and efficiency, and experimental efficiency is compared to a theoretical model. Additionally, SFG spectroscopy allows for probing the structure of model monomeric and polymeric C18 stationary phases under pressure; this provides a basis for correlating selectivity with pressure-induced structural changes in stationary phase materials. Together, this work provides a more complete understanding of the role of column pressure and fluid compressibility on the speed, efficiency, and selectivity of chemical separations.

No description available.

O objetivo principal deste trabalho é o estudo da regularidade anallítica global de certos operadores diferenciais definidos no toro. Uma ferramenta fundamental utilizada neste estudo são as séries parciais de Fourier, que nos permitem caracterizar tanto as distribuições periódicas quanto as funções anallíticas reais periódicas através do comportamento assintótico de seus coeficientes parciais de Fourier. Neste sentido, apresentamos também um estudo detalhado das relações destes objetos com seus coeficientes parciais de Fourier / The main goal of this work is to study global analytic regularity properties of certain differential operators acting in the torus. A main tool that will be used to achieve our goals are the partial Fourier series, which allow us to characterize objects such as periodic distributions or periodic real analytic functions in terms of the growth of their partial Fourier coefficients

O objetivo principal deste trabalho é o estudo da regularidade anallítica global de certos operadores diferenciais definidos no toro. Uma ferramenta fundamental utilizada neste estudo são as séries parciais de Fourier, que nos permitem caracterizar tanto as distribuições periódicas quanto as funções anallíticas reais periódicas através do comportamento assintótico de seus coeficientes parciais de Fourier. Neste sentido, apresentamos também um estudo detalhado das relações destes objetos com seus coeficientes parciais de Fourier / The main goal of this work is to study global analytic regularity properties of certain differential operators acting in the torus. A main tool that will be used to achieve our goals are the partial Fourier series, which allow us to characterize objects such as periodic distributions or periodic real analytic functions in terms of the growth of their partial Fourier coefficients

Les travaux de cette thèse portent sur le développement de nouvelles méthodologies de purification des peptides pharmaceutiques par chromatographie de partage centrifuge (CPC) dans le but de l'introduction de cette technique comme outil de R&D mais surtout de production en milieu industriel. Le caractère original de ces travaux porte essentiellement sur l'introduction de nouveaux systèmes de solvants et la mise au point de nouveaux procédés de purification en mode CPC co-courant. Les différents aspects liés à l'industrialisation des différents procédés de purification ont également été étudiés.La première partie des travaux a consisté en l'étude de quelques nouveaux aspects de l'intérêt de l'application du mode co-courant en chromatographie de partage centrifuge. Une méthodologie originale de purification des peptides tensioactifs non ioniques en mode CPC co-courant a été mise au point. Cette méthodologie a permis de résoudre les problèmes de perturbations hydrodynamiques et de perte de phase stationnaire engendrés par le caractère tensioactif de ces molécules et a été appliquée avec succès à la purification d'une cyclosporine modifiée douée d'une activité anti-virale et faiblement soluble dans les solvants usuellement utilisés en CLHP. Une étude fondamentale de l'effet du peptide sur le comportement hydrodynamique des deux phases lors de la séparation et la visualisation des modèles d'écoulement au sein de la colonne CPC a permis la mise en évidence du role de la ciclosporine modifiée dans la perturbation de la composition des phases du système chromatographique. D'autres aspects de l'intérêt du mode co-courant en CPC ont été étudiés lors de cette étude, notamment l'amélioration de la robustesse et de la résolution de la séparation.La seconde partie des travaux a porté sur le développement de nouveaux systèmes biphasiques de solvants particulièrement adaptés à la purification des peptides hydrophobes non-ioniques, notamment les intermédiaires de synthèse protégés, qui sont très faiblement solubles dans la plupart des solvants communs utilisés en chromatographie. Deux gammes quaternaire et quinaire de systèmes biphasiques de solvants, ainsi qu'un système biphasique ternaire ont été introduits. L'originalité de ces systèmes porte sur l'usage de solvants verts à fort caractère solvatant tel que le Methyl-THF et le cyclopentyl methyl ether (CPME). Les systèmes développés ont été efficacement utilisés pour la purification en CPC d'une exénatide protégée de 39 acides aminés et d'un peptide protégé de 8 acides aminés intermédiaire de la synthèse de la bivalirudine. Ces systèmes devraient être utiles pour une utilisation générale en CPC pour la séparation des peptides synthétiques hydrophobes libres ou protégés. / The work presented in this thesis deals with the development of new methodologies for the purification of pharmaceutical peptides by centrifugal partition chromatography (CPC) in order to introduce this technique as a tool for R & D but also in industrial production. The original character of this work relies on the introduction of new solvent systems and the development of new purification processes based on the co-current CPC mode. The different aspects of the process intensification and industrialization have also been studied.In the first part of the work, a study of some new aspects of the interest of the application of the stationary phase co-current mode in CPC is described. An original method for the purification of non-ionic tensioactive peptides in the co-current CPC mode was developed. This method has been successfully applied to the purification of a modified cyclosporine showing a therapeutic interest. This particular elution mode, taking advantage of the liquid nature of the stationary phase, appears to be an efficient solution to get round some hydrodynamic instabilities that sometimes appears during a purification intensification by CPC. A fundamental study of the effect of the peptide on the hydrodynamic behavior of the two phases in the separation and visualization of flow patterns within the CPC column allowed highlighting the role of the peptide in the disruption of phases composition of the chromatographic system. Other aspects of the interest of the co-current mode in CPC were investigated in this study, including the improvement of the efficiency and the resolution of the separation.The second part of the work focused on the development of new biphasic solvent systems particularly suitable for the purification of hydrophobic non-ionic peptides, including protected intermediates, which are very poorly soluble in the most common solvents used in chromatography. Two new scales of biphasic solvent systems showing a wide range of polarity and a ternary biphasic system were introduced to overcome solubility problems often encountered with synthetic hydrophobic protected peptides. The originality of these systems relies on the use of green solvents with high solvating character such as Methyl-THF and cyclopentyl methyl ether (CPME). The developed systems have been effectively used for the purification in CPC of a 39mer protected exenatide and and a 8mer protected peptide intermediate of bivalirudin synthesis.

O cloridrato de tramadol, analgésico sintético de ação central, possui dois centros quirais: o isômero cis é ativo e o isômero trans é uma impureza de processo. Ambos os enantiômeros do cloridrato de cis-tramadol contribuem para o efeito analgésico, mas através de mecanismos diferentes, complementares e interativos farmacologicamente. Os dois isômeros do cis-tramadol apresentam efeitos terapêuticos, e a presença de impurezas, incluindo os isômeros trans - decorrentes do processo de síntese ou devido à decomposição - podem comprometer a qualidade do produto comercializado. Assim, este trabalho teve como objetivo desenvolver e validar metodologia estereosseletiva para análise do cloridrato de cis-tramadol e das possíveis impurezas quirais ou não na matéria-prima e formulações farmacêuticas. Para a separação e quantificação dos enantiômeros do cloridrato de cis-tramadol e das impurezas trans-tramadol, 1,2-olefina e 1,6-olefina, foi utilizada a coluna Chiralcel® OD-H, fase móvel constituída por hexano (60% e 100% de n-hexano, 1:1, v/v):isopropanol:dietilamina:ácido trifluoracético (99,5:0,5:0,3:0,1, v/v/v/v), na vazão de 0,7 mL min-1 e detecção em 274 nm. A coluna Chiralpak® AD fase móvel constituída por hexano (60% de n-hexano):etanol absoluto:dietilamina (95:5:0,1, v/v/v), na vazão de 1,0 mL min-1 e o comprimento de onda para detecção dos compostos foi de 228 nm foi utilizada para a separação e quantificação das impurezas O-desmetiltramadol, N-desmetiltramadol e tramadol N-óxido. Os métodos desenvolvidos foram devidamente validados através dos parâmetros seletividade, linearidade, precisão, exatidão, intervalo, limite de detecção e limite de quantificação. Os resultados obtidos na validação mostraram que os métodos são adequados para a determinação do cis-tramadol e de suas impurezas na matéria prima e na formulação farmacêutica. / Tramadol hydrochloride is a centrally acting analgesic with two chiral centers; the cis isomer is the active drug and the trans isomer is a process impurity. Both enantiomers of cis-tramadol hydrochloride contribute to the analgesic effect through different, but complementary and interactive pharmacological mechanisms. Although both isomers of cis-tramadol hydrochloride show therapeutic effects, the presence of impurities, originated from the synthesis process or due to degradation, can compromise the quality of the marketed product. The aim of this present work was the development and validation of a stereosselective methodology for the analysis of the drug cis-tramadol hydrochloride and the possible chiral or non-chiral impurities in raw materials and pharmaceutical formulations. The separation and quantitation of cis-tramadol enantiomers and the impurities trans-tramadol, 1,2-olefin and 1,6-olefin were carried out using a Chiralcel® OD-H column, mobile phase of hexane (60% and 100% of n-hexane, 1:1, v/v):2-propanol:diethylamine:trifluoroacetic acid (99,5:0,5:0,3:0,1, v/v/v/v) at a flow rate of 0,7 mL min-1 and detection at 274 nm. For the separation and quantitation of the impurities O-desmethyltramadol, N-desmethyltramadol and tramadol N-oxide, a Chiralpak® AD column was used with a mobile phase of hexane (60% of n-hexane):ethanol absolute: diethylamine (95:5:0,1, v/v/v) at a flow rate of 1,0 mL min-1 and detection at 228 nm. The methods were validated using the parameters selectivity, linearity, precision, accuracy, range, detection limit and quantitation limit. The results obtained show that the methods are suitable for the analysis of cis-tramadol and its impurities in raw material and pharmaceutical formulation.

Three ionic liquids (ILs), trihexyltetradecylphosphonium tetrafluoroborate (TTPT), N-butyl-4-methylpyridinium tetrafluoroborate (BMPT), and 1-methyl-3- octylimidazolium tetrafluoroborate (MOIC), were utilized to prepare sol- gel sorbent coatings. Non-polar polydimethylsiloxane (PDMS) and polar poly(ethylene glycol) (PEG), poly(tetrahydrofuran) (PolyTHF) and bis[(3-methyldimethoxy-silyl)propyl] polypropylene oxide (BMPO) polymers were employed to develop novel ionic liquidmediated sol- gel hybrid organic- inorganic sorbents. The novel sorbents were first tested as coatings for capillary microextraction off-line hyphenated to gas chromatography. To gain an understanding of the role of the ionic liquids in the sol-gel process, the preconcentration abilities of these novel coatings were investigated for several classes of compounds utilizing CME-GC. This was accomplished by comparing GC peak areas of a series of analytes extracted on the ionic liquid mediated sol-gel CME coatings with that of analogous peak areas obtained on sol- gel coatings prepared without the ionic liquid. The morphology of these coatings was compared using scanning electron microscopy (SEM) imaging data. Overall, the ionic liquid-mediated sol- gel coatings had more porous morphologies than the sol-gel coatings prepared without ionic liquid. The PDMS andBMPO sol-gel coatings prepared with ionic liquid in the sol solution provided enhanced extraction sensitivity reflected in higher preconcentration effects and lower detection limits than the sol- gel coatings prepared without the ionic liquid. The polar IL-mediated BMPO sol- gel sorbent was further investigated by exploring the extraction profile and thermal stability of these coatings. A further application of ionic liquid-mediated sol-gel sorbents could be as stationary phases in a microchip-based separation system. Towards this goal, microfluidic channels were fabricated in glass substrates using microelectromechanical engineering. Spiral and serpentine channels were etched in Pyrex and fused silica wafers using wet and deep reactive ion etching (DRIE) techniques. Microfabrication protocols such as the use of hard mask and etching times were investigated for both techniques. DRIE produced microfluidic channels that had an etch quality that was superior to wet etched channels. Thus, the ultimate microchip-based separation system should by fabricated using DRIE.

Submitted by Geandra Rodrigues (geandrar@gmail.com) on 2018-01-09T14:43:53Z No. of bitstreams: 1 rafaelmarques.pdf: 2550703 bytes, checksum: 4694887625f47f1d8d4f3dbed5d78f1d (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2018-01-23T11:20:19Z (GMT) No. of bitstreams: 1 rafaelmarques.pdf: 2550703 bytes, checksum: 4694887625f47f1d8d4f3dbed5d78f1d (MD5) / Made available in DSpace on 2018-01-23T11:20:19Z (GMT). No. of bitstreams: 1 rafaelmarques.pdf: 2550703 bytes, checksum: 4694887625f47f1d8d4f3dbed5d78f1d (MD5) Previous issue date: 2017-09-29 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Esta tese de doutorado aborda o preparo, a caracterização e a utilização de fases estacionárias monolíticas para uso em colunas de separação cromatográfica em escala capilar. As fases estacionárias foram preparadas pela polimerização do monômero 3-(metacriloxipropil)-trimetoxisilano em duas etapas envolvendo primeiramente um processo sol-gel e depois um processo de adição radicalar fotoiniciado. A fotopolimerização foi feita in situ em capilares de sílica fundida transparentes à radiação UV com 100 μm de diâmetro interno. As colunas produzidas foram aplicadas qualitativamente com sucesso na separação de cinco hidrocarbonetos policíclicos aromáticos e três hormônios esteroides, tanto por cromatografia a líquido capilar quanto por eletrocromatografia capilar em um equipamento de eletroforese capilar. A eletrocromatografia foi usada para analisar quantitativamente uma amostra de emulsão transdérmica contendo estriol e 17-β-estradiol. Como tentativa de melhorar a separação entre alguns analitos, foi feita a modificação do polímero adicionando o monômero benzil metacrilato, porém sem sucesso. As colunas foram caracterizadas com relação à sua homogeneidade física usando um microscópio óptico e um detector condutométrico sem contato capacitivamente acoplado. O detector foi usado como um scanner não invasivo deslocando-se longitudinalmente ao longo da coluna externamente ao capilar. A caracterização química do polímero foi feita através da espectroscopia de ressonância magnética nuclear no estado sólido dos núcleos de 13C e de 29Si. Foi possível propor uma estrutura para o arranjo da cadeia carbônica e o grau de substituição do grupo silil indicando a reticulação das cadeias poliméricas através da formação de dímeros e trímeros condensação de grupos alcoxisilanos. / This doctoral thesis adresses the preparation, characterization and use of monolithic stationary phases for chromatographic separation columns in capillary scale. The stationary phases were prepared by polymerizing the 3- (methacryloxypropyl) trimethoxysilane monomer in two steps involving a sol-gel process followed by a photoinitiated radical addition. The photopolymerization was carried out in UV transparent coating fused silica capillaries with 100 μm of internal diameter. The columns were applied in the qualitative separation of five polycyclic aromatic hydrocarbons and three steroid hormones, both by capillary liquid chromatography and capillary electrochromatography in a capillary electrophoresis equipment. Electrochromatography was used to quantitative analyzis of a transdermal emulsion sample containing estriol and 17-β-estradiol. In an attempt to improve the separation between some analytes, the polymer was modified by adding the benzyl methacrylate monomer, but without success. The columns were characterized with respect to their physical homogeneity using an optical microscope and a capacitively coupled contactless conductivity detector. The detector was used as a non-invasive scanner moving longitudinally along the column externally to the capillary. The chemical characterization of the polymer was done by the solid state 13C and 29Si nuclear magnetic resonance spectroscopy. It was possible to propose a carbon chain strucuture and the substitution degree of the silyl group indicating the cross-linking of the polymer chains through the formation of dimers and trimers by condensation of the alkoxysilane groups.

O cloridrato de tramadol, analgésico sintético de ação central, possui dois centros quirais: o isômero cis é ativo e o isômero trans é uma impureza de processo. Ambos os enantiômeros do cloridrato de cis-tramadol contribuem para o efeito analgésico, mas através de mecanismos diferentes, complementares e interativos farmacologicamente. Os dois isômeros do cis-tramadol apresentam efeitos terapêuticos, e a presença de impurezas, incluindo os isômeros trans - decorrentes do processo de síntese ou devido à decomposição - podem comprometer a qualidade do produto comercializado. Assim, este trabalho teve como objetivo desenvolver e validar metodologia estereosseletiva para análise do cloridrato de cis-tramadol e das possíveis impurezas quirais ou não na matéria-prima e formulações farmacêuticas. Para a separação e quantificação dos enantiômeros do cloridrato de cis-tramadol e das impurezas trans-tramadol, 1,2-olefina e 1,6-olefina, foi utilizada a coluna Chiralcel® OD-H, fase móvel constituída por hexano (60% e 100% de n-hexano, 1:1, v/v):isopropanol:dietilamina:ácido trifluoracético (99,5:0,5:0,3:0,1, v/v/v/v), na vazão de 0,7 mL min-1 e detecção em 274 nm. A coluna Chiralpak® AD fase móvel constituída por hexano (60% de n-hexano):etanol absoluto:dietilamina (95:5:0,1, v/v/v), na vazão de 1,0 mL min-1 e o comprimento de onda para detecção dos compostos foi de 228 nm foi utilizada para a separação e quantificação das impurezas O-desmetiltramadol, N-desmetiltramadol e tramadol N-óxido. Os métodos desenvolvidos foram devidamente validados através dos parâmetros seletividade, linearidade, precisão, exatidão, intervalo, limite de detecção e limite de quantificação. Os resultados obtidos na validação mostraram que os métodos são adequados para a determinação do cis-tramadol e de suas impurezas na matéria prima e na formulação farmacêutica. / Tramadol hydrochloride is a centrally acting analgesic with two chiral centers; the cis isomer is the active drug and the trans isomer is a process impurity. Both enantiomers of cis-tramadol hydrochloride contribute to the analgesic effect through different, but complementary and interactive pharmacological mechanisms. Although both isomers of cis-tramadol hydrochloride show therapeutic effects, the presence of impurities, originated from the synthesis process or due to degradation, can compromise the quality of the marketed product. The aim of this present work was the development and validation of a stereosselective methodology for the analysis of the drug cis-tramadol hydrochloride and the possible chiral or non-chiral impurities in raw materials and pharmaceutical formulations. The separation and quantitation of cis-tramadol enantiomers and the impurities trans-tramadol, 1,2-olefin and 1,6-olefin were carried out using a Chiralcel® OD-H column, mobile phase of hexane (60% and 100% of n-hexane, 1:1, v/v):2-propanol:diethylamine:trifluoroacetic acid (99,5:0,5:0,3:0,1, v/v/v/v) at a flow rate of 0,7 mL min-1 and detection at 274 nm. For the separation and quantitation of the impurities O-desmethyltramadol, N-desmethyltramadol and tramadol N-oxide, a Chiralpak® AD column was used with a mobile phase of hexane (60% of n-hexane):ethanol absolute: diethylamine (95:5:0,1, v/v/v) at a flow rate of 1,0 mL min-1 and detection at 228 nm. The methods were validated using the parameters selectivity, linearity, precision, accuracy, range, detection limit and quantitation limit. The results obtained show that the methods are suitable for the analysis of cis-tramadol and its impurities in raw material and pharmaceutical formulation.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-04-27T12:33:46Z No. of bitstreams: 1 fernandoantoniosimasvaz.pdf: 40063052 bytes, checksum: f272ddc4d930b7d243c50223436e02b2 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-05-13T13:00:49Z (GMT) No. of bitstreams: 1 fernandoantoniosimasvaz.pdf: 40063052 bytes, checksum: f272ddc4d930b7d243c50223436e02b2 (MD5) / Made available in DSpace on 2017-05-13T13:00:49Z (GMT). No. of bitstreams: 1 fernandoantoniosimasvaz.pdf: 40063052 bytes, checksum: f272ddc4d930b7d243c50223436e02b2 (MD5) Previous issue date: 2011-07-22 / FAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais / Nesta tese é descrita a preparação de novas fases estacionárias monolíticas (FEM) polimerizadas por fotoiniciação, através do método sol-gel, em capilares de sílica fundida revestidos com poliacrilato, para aplicação em eletrocromatografia capilar (ECC). Dentre as principais técnicas de separação em Química Analítica, a ECC tem despertado grande interesse no meio acadêmico, pelo fato desta combinar as vantagens tanto da cromatografia a líquido de alta eficiência quanto da eletroforese capilar. Grande parte do desenvolvimento da ECC se deve ao uso das FEM, as quais são semelhantemente aplicadas em outras técnicas cromatográficas. Ao contrário do revestimento de poliimida, amplamente empregado, o revestimento de poliacrilato, transparente acima de 370 nm e à luz visível, facilita a visualização da solução de sol no interior do capilar, o que permite controlar a injeção desta e de outras soluções, bem como observar a formação in situ da FEM. Além disso, é possível que seja feita a polimerização fotoiniciada sem a necessidade de remoção do revestimento polimérico que protege a coluna. O objetivo central deste trabalho foi entender e aprimorar o processo de fabricação das FEM para aplicações em ECC. Para isso, foram feitas modificações da câmara fotorreatora homemade utilizada para a polimerização das FEM, como uma correção na faixa espectral de trabalho de 350 a 700 nm para 350 a 400 nm; e instalação de dispositivos de segurança tanto para o operador quanto para o sistema elétrico. Para que fosse alcançado um melhor controle de injeção de fases líquidas no interior de tubos com dimensões capilares, a construção de um dispositivo de alta pressurização (DAP) que forneceu, além da pressão, grande precisão foi indispensável. O DAP, além de simples, teve ótima relação custo-benefício, comparado a modelos comerciais. O preparo das FEM foi otimizado mediante auxílio de planejamento fatorial fracionário 24-1, onde se buscou analisar propriedades eletrocromatográficas frente diferentes proporções dos reagentes empregados e tempo de incidência de luz ultravioleta (UV). Este último fator não apresentou significância e foi desconsiderado, de forma que o planejamento fosse devidamente reduzido para um planejamento fatorial completo 23, o que possibilitou uma análise mais apurada dos efeitos significativos. O fator mais influente foi a proporção de porogênio (tolueno), sendo que a melhor condição obtida foi utilizando 80,0 % (v/v) de solução porogênica; 3,5 % (m/m) de fotoiniciador óxido de bis(2,4,6-trimetilbenzoil)-fenilfosfino (Irgacure 819); razão molar água/ metacriloxipropiltrimetoxisilano (MPTMS) igual a 4 e tempo de incidência de luz UV de 10 minutos. As características morfológicas, espectroscópicas e porosidade foram avaliadas através de microscopia eletrônica de varredura, infravermelho e porosimetria por adsorção de nitrogênio, respectivamente. As FEM foram testadas em ECC pela separação de hidrocarbonetos policíclicos aromáticos (naftaleno, acenafteno, fluoreno, fenantreno e antraceno) e alquilbenzenos (etilbenzeno, propilbenzeno, butilbenzeno e hexilbenzeno), todos compostos eletricamente neutros, diluídos em metanol (1 mmol L-1 cada), utilizando tiouréia como marcador de fluxo. Como fase móvel foi utilizada a mistura de acetato de amônio 16,7 mmol L-1 pH 7,0 (60 %) e acetonitrila (40 %). A voltagem aplicada foi -20 kV; a temperatura de análise foi 20 ºC; a injeção dos analitos foi -25 mbar por 5 s; e a detecção no UV foram nos comprimentos de onda de 220 nm e 250 nm. Foi utilizado o modo ECC-rápida, que consiste na inversão do sentido de análise e injeção de padrões pela extremidade curta do capilar. Este modo se mostrou muito mais rápido, repetitivo e eficiente do que o modo normal, fornecendo em pouco mais de 12 minutos de análise, mais de 51400 pratos/m de coluna e desvios padrão relativos em tempo de migração/retenção entre 0,09 e 3,3 % e em área de pico relativa entre 0,14 e 1,6 %. Os perfis de separação em ECC corroboraram com os resultados de porosidade e morfologia obtidos. / This thesis describes the preparation of new monolithic stationary phases (MSP) polymerized by photoinitiation through sol-gel approach in polyacrylate-coated fused silica capillary, for application in capillary electrochromatography (CEC). CEC has been concentrated much attention among the major separation techniques in analytical chemistry because it combines the advantages of both high performance liquid chromatography and capillary electrophoresis. Much of the CEC development is due to the use of MSP, which are similarly applied to other chromatographic techniques. Unlike polyimide-coating, widely used, the polyacrylate-coating, which is transparent above 370 nm and visible, enables the visualization of the sol solution within the capillary, allowing one to control the injection of sol and other solutions, in addition to observe the in situ formation of the MSP. Furthermore, it is possible to perform the photoinitiated polymerization without removing this polymeric coating that protects the capillary. The main purpose of this work was to comprehend and improve the fabrication process of MSP, for CEC applications. For this, some changes were set in the homemade photo reactor chamber, used for the MSP polymerization, like correction in the work range from 350 – 700 nm to 350 – 400 nm; and installation of security devices for both operator and electric system safeties. For better control of liquid phases injection within tubes with capillary dimensions, the build of a high-pressure device (HPD) that provides a great precision, in addition to the high-pressure, was essential. HPD is simpler and relatively cheaper when compared to commercial models. The preparation of the MSP has been optimized through assistance of a 24-1 fractional factorial design, with the intention to investigate electrochromatographic properties with different amounts of employed reagents and ultraviolet (UV) light incidence time. The later factor did not show significance and was unconsidered, making the design possible to be reduced to a 23 complete factorial design, which allowed analyzing the significant effects accurately. The most influent factor was the porogen (toluene) proportion, and the best condition was obtained using 80.0 % (v/v) of porogenic solution; 3.5 % of photoinitiator bis(2,4,6 trimetylbenzoyl)-phenylphosphine oxide (Irgacure 819); water to metacryloxypropyltrimethoxysilane (MPTMS) molar ratio equal to 4 and 10 minutes of UV light incidence time. The MSP morphological, spectroscopic characteristics and porosity were evaluated through scanning electron microscopy, infrared spectroscopy and nitrogen adsorption porosimetry, respectively. The MSP has been tested in CEC through the separation of polycyclic aromatic hydrocarbons (naphthalene, acenaphthene, fluorene, phenanthrene and anthracene) and alkylbenzenes (ethylbenzene, propylbenzene, butylbenzene and hexylbenzene), which are electrically neutral compounds, after dilution in methanol (1 mmol L-1 each), using thiourea as the flow marker. As mobile phase a mixture of ammonium acetate 16.7 mmol L-1 at pH 7.0 (60.0 %) and acetonitrile (40.0 %) was used. The applied voltage was -20 kV, the temperature of analysis was 20 °C, the analyte injection was -25 mbar for 5 s, and UV detection was done at 220 and 250 nm. A fast-CEC mode, which consists to reverse the analysis direction and to introduce the analyte by capillary short-end injection, was performed. This mode was much more fast, repetitive and efficient than the normal one, providing in a little more than 12 minutes over than 51400 plates per meter of column and relative standard deviations ranging from 0.09 to 3.3 % for migration/retention time and from 0.14 to 1.6 % for relative peak area. The separation profiles in CEC corroborate with the porosity and morphology results.