Orientador: Isabel Cristina Sales Fontes Jardim / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-15T06:33:14Z (GMT). No. of bitstreams: 1 Maldaner_Liane_D.pdf: 4323260 bytes, checksum: 773bada382fd206c910361612918f566 (MD5) Previous issue date: 2010 / Resumo: Novas fases estacionárias (FE) fluoradas foram preparadas a partir da imobilização do poli(metil-3,3,3-trifluorpropilsiloxano) (PMTFS) em partículas de sílica Kromasil de 5 mm, por tratamento termico (TT) ou por radiação micro-ondas (RM). As condições de imobilização otimizadas através do emprego de planejamento de experimentos foram, 200 °C por 12 horas para o TT e 126 °C (760 W) por 50 minutos para a RM. A caracterização físico-quimica permitiu concluir que o polímero ficou fisicamente adsorvido e também quimicamente ligado a superfície do suporte cromatografico, em ambos os procedimentos de imobilização, resultando em porcentagens de carbono de 9 % e 10 % para as FE obtidas por TT e por RM, respectivamente. A caracterização cromatográfica mostrou que as FE desenvolvidas apresentaram eficiências > 70.000 N m, características hidrofóbicas, seletividade estérica e metilênica e uma pequena interação entre os compostos básicos e os grupos silanóis residuais. Esta redução das interações indesejáveis pode estar associada com a presença dos átomos de fluor que promovem diferentes interações com os compostos básicos e, dessa forma, reduzem estes efeitos. As FE fluoradas foram seletivas para a separação de isômeros de posição e de fármacos, sendo uma alternativa atrativa as FE tradicionais / Abstract: New fluorinated stationary phases (SP) were prepared through thermal or microwave immobilization of poly(methyl-3,3,3-trifluoropropylsiloxane) (PMTFS) onto 5 mm Kromasil silica particles. The immobilization conditions were optimized employing experimental design and resulted in 200 °C for 12 hours for thermal treatment and 126 °C (760 W) for 50 minutes for microwave irradiation. Physical-chemical characterization showed that the polymer was both physically adsorbed and chemically bonded to the chromatographic support, in both immobilization procedures, resulting in a percent carbon load of 9 % and 10 % for the SP immobilized by thermal treatment and by microwave irradiation, respectively. Chromatographic characterization showed that the SP developed presented efficiencies > 70 000 N m, hydrophobic characteristics, steric and methylene selectivity and small interactions between the basic compounds and the residual silanol groups. This reduction of the undesirable interactions can be associated to the presence of the fluorine atoms that promote different interactions with the basic compounds and thus reduce these effects. The fluorinated SP were selective for the separation of positional isomers and pharmaceuticals and are an attractive alternative to the classical reversed stationary phases / Doutorado / Quimica Analitica / Doutor em Ciências

Orientador: Carol Hollingworth Collins / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T03:41:41Z (GMT). No. of bitstreams: 1 SilvaJunior_EliasSeveroda_D.pdf: 2576422 bytes, checksum: 19c90c90e1e49e747a75a6260bb45eba (MD5) Previous issue date: 2014 / Resumo: Neste trabalho foram feitos estudos das condições de preparo de fases estacionárias para uso em Cromatografia Líquida de Alta Eficiência em Fase Reversa (CLAE-FR) da mistura de poli(metiloctadecilsiloxano) (PMODS) e poli(dimetilsiloxano) (PDMS), sorvidos e imobilizados por tratamento térmico (em atmosfera inerte) na superfície de sílica Kromasil (esférica, 5 µm) metalizada com titânia ou zircônia. As fases estacionárias foram avaliadas por testes químicos, físicos, cromatográficos e de estabilidade em fases móveis em condições agressivas. As melhores condições de preparo das fases estacionárias foram: sorção de 22 % de PMODS e 33 % de PDMS sobre sílica metalizada, mantendo períodos de 4 e 10 dias em repouso, respectivamente, após adição de cada polímero e depois imobilizados a 120 °C durante 16 horas. As fases estacionárias preparadas nas melhores condições apresentaram eficiências superiores a 45000 e 10000 pratos m-1, respectivamente, para os compostos naftaleno e N,N-dimetilanilina, além de picos simétricos para a maioria dos compostos. O estudo de caracterização através das misturas testes de Tanaka, Engelhardt, Neue e SRM 870 indicou a presença de silanóis residuais, mas os resultados dos parâmetros avaliados foram satisfatórias, principalmente comparados às fases PMODS e algumas comerciais. Quanto aos testes de estabilidade em meio básico as fases estacionárias mantiveram-se estáveis durante 550 e 800 volumes de coluna, respectivamente, SiTi(PMODS + PDMS) e SiZr(PMODS + PDMS), usando o acenafteno. Já no teste ácido as fases estacionárias mantiveram-se estáveis por 900 e 800 volumes de coluna, respectivamente, para SiTi(PMODS + PDMS), e SiZr(PMODS + PDMS). As fases estacionárias SiTi(PMODS + PDMS), e SiZr(PMODS + PDMS), sorvidas e imobilizadas por tratamento térmico, apresentam potencialidade na separação de diferentes classes de compostos, tais como, agrotóxicos e fármacos / Abstract: In this work the conditions for the preparation of stationary phases for use in reversed phase high performance liquid chromatography (RP-HPLC) with a mixture of poly(methyloctadecilsiloxane) (PMODS) and poly(dimethylsiloxane) (PDMS) sorbed and immobilized by thermal treatment (in an inert atmosphere) on metalized (titanium and zirconium) Kromasil silica (spherical, 5 µm) were studied. The stationary phases were evaluatied by chemical, physical and chromatographic tests and for stability in mobile phases having agressive conditions. The best conditions for preparation of the stationary phases were: sorption of 22 % PMODS and 33 % PDMS onto the metalized silica, storing for 14 days and then immobilizing at 120 °C for 16 hours. The stationary phases from these conditions showed higher efficiencies of 45000 and 10000 plates m-1 for naphthalene and N,N-dimethylaniline and symmetrical peaks for most compounds. Characterization studies using Tanaka¿s, Engelhardt¿s, Neue¿s and the SRM 870 test-mixtures indicated the presence of residual silanols, but evaluation parameters were still reasonable, compared to PMODS phases and to commercials phases. In the adverses stability tests the stationary phase was for stable 550 and 800 column volumes, respectively, for SiTi(PMODS + PDMS) and SiZr(PMODS + PDMS), in the basic test, showing a decrease of efficiency (60 %) for N,N-dimethylaniline. In the acid test the stationary phases maintained efficiency for 900 and 800 column volumes, respectively, for SiTi(PMODS + PDMS) and SiZr(PMODS + PDMS). The stationary phases SiTi(PMODS + PDMS) and SiZr(PMODS + PDMS) sorbed and immobilized by thermal treatment, showed potential for the separation of different compounds classes, such as, pesticides and pharmaceuticals / Doutorado / Quimica Analitica / Doutor em Ciências

Orientador: Carla Beatriz Grespan Bottoli / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-19T12:28:05Z (GMT). No. of bitstreams: 1 Aguiar_ValeskaSoares_M.pdf: 8050447 bytes, checksum: b6132fb136ec04b91b3bdb6e10fbeaf4 (MD5) Previous issue date: 2011 / Resumo: A Eletrocromatografia Capilar (CEC) é uma técnica de separação que combina a seletividade cromatográfica da Cromatografia Líquida de Alta Eficiência (HPLC) com a alta eficiência da Eletroforese Capilar (CE). A coluna capilar usada na separação é preenchida com uma fase estacionária, que pode ser do tipo particulada ou monolítica. Neste trabalho, monolitos poliméricos orgânicos foram preparados por polimerização in situ a partir dos monômeros octadecilmetacrilato (precursor e seletor hidrofóbico), etilenodimetacrilato (agente de entrecruzamento) e ácido 2-acriloilamido-2- metilpropanossulfóxido (monômero ionizável), além de diferentes tipos de solventes porogênicos, como álcool isoamílico, amílico, cicloexanol e 1,4- butanodiol, na presença e na ausência de água. Na primeira etapa do trabalho, variaram-se a natureza e a proporção entre os solventes porogênicos e, na segunda, o mesmo ocorreu com a proporção entre o conjunto de monômeros e de solventes porogênicos. As fases estacionárias foram caracterizadas por técnicas físicas como a microscopia eletrônica de varredura e a porosimetria; e as colunas moldadas com o material monolítico foram avaliadas pela técnica de CEC. As colunas apresentaram eficiência na faixa de 3000 a 50000 pratos m. A análise das isotermas de adsorção e dessorção de nitrogênio e das curvas de distribuição de poros permitiu afirmar que o material monolítico sintetizado é essencialmente micro e mesoporoso. Os macroporos para fluxo de fase móvel foram nitidamente observados em imagens de microscopia eletrônica de varredura. Assim, as fases monolíticas apresentaram três tipos de poros: micro, meso e macroporos. Na segunda parte do trabalho, avaliou-se a repetibilidade de preparo das fases monolíticas e notou-se grande falta de repetibilidade em termos de eficiência de separação. As fases monolíticas apresentaram alto caráter apolar e seletividade metilênica adequada para separação de analitos apolares e aromáticos, como alquilbenzenos, alquilparabenos e hidrocarbonetos policíclicos aromáticos / Abstract: Capillary Electrochromatography (CEC) is a separation technique that matches the chromatographic selectivity of High Performance Liquid Chromatography (HPLC) with the high efficiency of Capillary Electrophoresis (CE). The capillary column used in the separation is filled with a stationary phase, which can be particulate or monolithic. In this work, organic polymeric monoliths were prepared through in situ polymerization from the monomers octadecyl methacrylate (precursor and hydrophobic selector), ethylene dimethacrylate (cross-linking agent) and 2-acryloylamido-2-methylpropanesulfonic acid (ionizable component), using different types of porogenic solvents, such as isoamyl alcohol, amyl alcohol, cyclohexanol and 1,4-butanediol, in the presence or absence of water. In the first step, the nature and proportion between the porogenic solvents were varied and, in the second, the same occurred with the proportion between the set of monomers and porogenic solvents. The stationary phases were characterized by physical techniques such as scanning electron microscopy and porosimetry; and the columns prepared with the monolithic material were evaluated through the CEC technique. The columns presented efficiencies in the range of 3000 to 50000 plates m. Analysis of the nitrogen adsorption and desorption isotherms and the pore distribution curves enable affirming that the synthesized monolithic material is essentially micro- and mesoporous. The macropores for the flow of the mobile phase were clearly observed in images of scanning electron microscopy. So, the monolithic phases have three types of pores: micro-, meso- and macropores. In the second part of this work, the repeatability of synthesis of the monolithic phases was evaluated and a lack of repeatability related to separation efficiency was noted. The monolithic phases had high apolar character and adequate methylenic selectivity for separation of apolar and aromatic analytes, such as alkylbenzenes, alkylparabens and polycyclic aromatic hydrocarbons / Mestrado / Quimica Analitica / Mestre em Química

The aim of this work was finding suitable conditions for separation of enantiomers of citalopram and citadiol, optimization of chromatographic system and validation of the analytical method for determination of selected enantiomers in drugs. Drugs are often chiral compounds. In many cases, only enantiomer has required pharmacological effects. Advanced chemical technologies associated with the synthesis, separation and analysis of the individual enantiomers caused an increase of the number of new chiral drugs in the form of single pure enantiomers, the chiral switch. Citalopram is one of the widely used antidepressants of selective serotonin reuptake inhibitors (SSRI). Citalopram is used for treatment of depression, panic anxienty or obsessive compulsive disorder of pathological laughing and crying. The pharmacological activity is associated with the S-citalopram, while R-enantiomer is essentially inactive and even counteracts the activity of escitalopram. Citadiol is a chiral syntetic precursor of citalopram. This thesis was focused on monitoring enantioseparation "behaviour" of selected enantiomers. HPLC method with chiral stationary phases based on macrocyclic antibiotics, cyclofructans and cellulose was applied for enantioseparation of the above-mentioned compounds. The optimized chromatographic...

The aim of this work was to develop and to optimize HPLC method for enantioseparation of newly synthesized derivatives of amino acids. The set of these analytes contained four N- blocked derivatives of D,L-Phenylalanine, three N-unblocked derivatives of D,L- Phenylalanine, , one methylated derivative of D,L-Tyrosine and D,L-Tyrosine. Two separation modes i.e. reversed phase and polar-organic modes and two columns i.e. Chirobiotic® T and Chirobiotic® T2 were used. Chiral stationary phases of these columns were composed of macrocyclic antibiotic teicoplanin coated on silica gel support. As mobile phases in revesed phase mode, methanol and acetate buffer were used with Chirobiotic® T column. The most suitable concentration were 20 mM and the most suitable pH value were 4.00. Under the above mentioned conditions eight analytes of ten were separated and the optimal conditions were found. Polar-organic mode and Chirobiotic® T column were suitable only for enantioseparation of three N-blocked derivatives of D,L- Phenylalanine. Mobile phases were composed of methanol with small additions of triethylamine and acetic acid. Chirobiotic® T2 column in reversed phase mode was not suitable for tested set of analytes. Only partial separation of D,L-Tyrosine derivative and one N-unblocked D,L-Phenylalanine...

This diploma thesis is focused on the comparison of enantioselective potential of chiral stationary phases based on derivatized cellulose by high performance liquid chromatography (HPLC). Polysaccharide - based chiral stationary phases are suitable choice for enantioseparation of various chiral compounds. In this work Chiralpak IB column containing cellulose tris(3,5-dimethylphenylcarbamate) selector immobilized onto silica gel and Chiralpak IC column containing cellulose tris(3,5- dichlorophenylcarbamate) selector immobilized onto silica gel were used. Their ability of enantioseparation was tested on 28 structurally different chiral analytes. Reversed- phase separation mode was used for enantioseparation. Mobile phases were composed of organic modifiers acetonitrile or methanol and the aqueous part was selected according to the nature of analytes. Acidic analytes were separated in mobile phases containing aqueous solution of formic acid (pH 2.1). Analytes of bifunctional nature were separated in the presence of aqueous solution of formic acid (pH 2.1), 10 mM ammonium acetate buffer (pH 8.8) or 100 mM solution of KPF6. Mobile phases containing 10 mM ammonium acetate buffer (pH 8.8) or 100 mM solution of KPF6 were used for enantioseparation of alkaline chiral analytes. Twelve chiral analytes were...

Capillary electrochromatography (CEC) is a major capillary electrophoresis (CE) mode that have been interfaced to mass spectrometry (MS) for sensitive and selective analysis of chiral compounds. This research expands CEC applications in cancer biomarker and chiral CE analysis. Chapter 1 is a review of liquid chromatography-mass spectrometry (LC/MS), gas chromatography-mass spectrometry (GC/MS), and capillary electrophoresis mass spectrometry (CE/MS) for analysis of metabolites in prostate cancer diagnostics and therapies. In this chapter, a literature survey was performed within the databases PubMed, 4 Caplus/Webline and Web of Sciences. A total 17 studies reporting on various analytical platforms for metabolite identification in prostate cancer research, which often include case-control comparison were identified and reviewed. Chapter 2 described the analysis of metabolite biomarkers in prostate cancer tissues by capillary electrochromatography mass spectrometry. In this chapter, a capillary CEC–MS/MS method was developed for the simultaneous determination and separation of eight proofs of concept (POC) metabolites (betaine, malate, proline, N-acetyl aspartate, N-acetylglucosamine, uracil, xanthine, and alanine) as potential prostate cancer diagnostic markers. A polymeric monolith column with a hydrophilic crosslinker and strong anion-exchange mixed-mode has been fabricated by an in situ copolymerization of vinyl benzyl trimethylammonium chloride, and bisphenol A glycerolate dimethacrylate (BisGMA) in the presence of methanol and dodecyl alcohol as porogens and AIBN as initiator. After CEC separation, samples were analyzed by a triple–quadrupole mass spectrometer operated in positive ion mode. After optimization, the data showed that the CEC-MS/MS method using monolithic column achieved a much better chromatographic selectivity compared to coated columns and increased sensitivity than bare fused silica column The effect of mobile phase pH, ACN percentage and additive were studies. Under the optimum mobile phase conditions, this method was carried out to separate and detect eight metabolites in the biopsy sample. The LOD for the metabolites is between 50nM-100nM. This method has successfully used to examine patients’ prostate cancer with an accuracy of 95%. Chapter 3 demonstrates Insights into Chiral Recognition Mechanisms in CEC using linear salvation energy relationship. By varying the linker (amide and carbamate), head group (alanine, leucine, and valine) and chain length (C8, C10 and C12) of the amino acid bound surfactants; monolithic column was made to ultimately understand the factors governing chiral stationary solid phase. Through the comparison of system parameters, we can see that surfactant head group, linker and chain length affect the separation of achiral and chiral compounds. Also, with the same type surfactant, data was presented to show how the trend of LSER parameters and how it affects separation between in CEC. This study showed the predictive capability of LSER to understand the aforementioned intermolecular processes controlling retention and by doing so, be able to quantitatively predict the experimental conditions to achieve an acceptable chiral separation.

Orientador: Isabel Cristina Sales Fontes Jardim / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-10T09:05:57Z (GMT). No. of bitstreams: 1 Fioravanti_LiviaMariaAndrekowisk_M.pdf: 984234 bytes, checksum: 0c41c940c79a927bb0f835b15b3739d0 (MD5) Previous issue date: 2007 / Resumo: Em cromatografia líquida de alta eficiência (CLAE), a coluna é um dos principais componentes do sistema cromatográfico, pois é nela que ocorre a separação. Dessa forma, a busca por fases estacionárias (FE) capazes de realizar separações com alta eficiência e bom desempenho tem sido uma constante em muitos laboratórios de pesquisa. Polissiloxanos substituídos com grupos fenil têm sido intensamente utilizados em cromatografia gasosa, mas a sua aplicação em CLAE tem despertado pouca atenção. Este trabalho apresenta a preparação de FE para CLAE a partir da imobilização de poli(metilfenilsiloxano), por radiação microonda, sobre suporte de sílica. As FE foram caracterizadas por testes físico-químicos e cromatográficos. Escolheu-se a radiação microonda por se mostrar promissora e pouco estudada para imobilização de FE. Para a escolha das melhores condições de radiação foi aplicado um planejamento fatorial, sendo que a potência e o tempo de radiação que resultaram em fases com melhor desempenho cromatográfico foram de 720 W por 70 minutos. Nestas condições, as FE apresentaram alta eficiência (78.000 pratos m), picos simétricos (com fator de assimetria entre 0,9 e 1,2) para compostos apolares e básicos e boa resolução entre os compostos analisados. Os parâmetros cromatográficos indicaram que a radiação microonda melhorou o desempenho das FE, proporcionou um aumento da sua estabilidade frente à fase móvel alcalina e forneceu um bom recobrimento da superfície da sílica pelo polímero. A FE preparada mostrou-se promissora na separação de compostos aromáticos neutros e básicos, como fármacos contendo grupos nitrogenados e agrotóxicos / Abstract: In high performance liquid chromatography (HPLC), the column is one of the most important components of the chromatographic system, because it is in the column that the separation occurs. In this way, the search for stationary phases (SP) able to achieve separations with high efficiency has been a constant in many research laboratories. Phenyl substituted polysiloxanes have been used extensively in gas chromatography, but their application in HPLC has received little attention. This work presents the development of stationary phases for use in HPLC by immobilization of poly(methylphenylsiloxane) by microwave radiation on a silica support. The SP were characterized by physiochemical and chromatographic tests. Microwave radiation was chosen because it appears to be promising and has been little studied for SP immobilization. The best conditions of radiation were chosen using an experimental design, with the microwave power and the radiation time that provided phases with the best chromatographic performance, these being 720 W and 70 minutes. In these conditions, the SP showed high efficiency (78000 plates m), symmetrical peaks (asymmetry factor between 0.9 and 1.2) for nonpolar and basic compounds and good separation for the compounds analyzed. The chromatographic parameters show that microwave radiation improved the performance of the SP and provided an increase in stability in alkaline mobile phases. Besides, it provided a good polymer cover on silica surface, being a promising SP for the separation of neutral and basic aromatic compounds, such as pharmaceuticals with nitrogen groups and agrochemicals / Mestrado / Quimica Analitica / Mestre em Química

Orientador: Carol Hollingworth Collins / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-18T09:08:43Z (GMT). No. of bitstreams: 1 Souza_EndlerMarcelBorgesde_D.pdf: 24501631 bytes, checksum: 4fd1866c1e1f40857962b738d98e6eb5 (MD5) Previous issue date: 2011 / Resumo: As propriedades cromatográficas e a estabilidade de fases estacionárias preparadas pela imobilização térmica do poli(metiloctilsiloxano) ou do poli(metiltetradecilsiloxano) sobre a sílica foram avaliadas. Para isso, fora empregados os testes de Engelhardt, Tanaka e SRM 870. O estudo dos mecanismos envolvidos na retenção de solutos básicos nestas fases estacionárias foi feita com um teste desenvolvido em nosso laboratório, que consiste em avaliar os fatores de retenção e a assimetria de solutos hidrofóbicas e hidrofílicas em fases móveis com diferentes valores de pH, preparadas com diferentes tipos e concentrações de tampão. A avaliação das fases estacionárias com os testes SRM 870 e de Tanaka mostram uma alta contribuição dos fenômenos de troca iônica para retenção dos solutos básicos e a comparação dos valores obtidos com o teste de Tanaka, segundo o modelo de Euerby, mostrou que estas fases estacionárias apresentam propriedades cromatográficas distintas da maioria das fases comerciais, embora alguma similaridade tenha sido observada com as fases estacionárias que também apresentam altas contribuições de fenômenos de troca iônica na retenção de solutos básicos. O novo teste desenvolvido mostrou que a retenção de solutos básicos acontece devido a interações sinérgicas dos silanóis residuais com os polisiloxanos imobilizados na forma de gotas sobre a sílica. Devido a estas interações, o pH da fase móvel, o tipo e a concentração de tampão afetam intensamente os fatores de retenção e a assimetria de solutos básicos. Algumas das fases estacionárias apresentaram boa seletividade e picos simétricos para solutos básicos em fases móveis neutras, onde os solutos estam protonados e os silanóis residuais estão desprotonados. Os testes de estabilidade demonstraram que algumas das fases estacionárias são altamente estáveis em fases móveis neutras em temperatura ambiente e em fases móveis ácidas, mesmo a altas temperaturas. No entanto, estas se mostraram instáveis em fases móveis alcalinas mesmo em temperatura ambiente, conforme esperado para fases estacionárias preparadas pela imobilização de polissiloxanos sobre a sílica / Abstract: This work has evaluated the chromatographic properties and the stability of stationary phases prepared by with poly(methyloctylsiloxane) or poly(methyltetradecylsiloxane) thermally immobilized onto a silica surface. The stationary phases were chromatographically evaluated using the Engelhardt, SRM 870 and Tanaka tests. The retention mechanisms involved during the separation of basic solutes with these stationary phases were evaluated using a test developed in our laboratory that evaluates the effect of the mobile phases with different pH, and type and concentration of buffer on the retention factors and asymmetry of several basic solutes (with hydrophobic or hydrophilic characteristics). Evaluations with the SRM 870 and Tanaka tests showed that there is a high contribution of ionexchange interactions at neutral pH. Classifications using the Euerby¿s procedure indicate that the stationary phases developed in this work are different from most commercial ones, although some similarity was found with the phases that have high ion-exchange interactions. Also, the retention of basic solutes occurs due to synergetic interactions between the free silanols with the immobilized polysiloxanes, which are in the form of plugs on the silica surface. Due to these interactions the pH of the mobile phase, and the type and concentration of buffer have a strong effect on the retention factors and asymmetry factors of basic solutes. The stationary phases present good selectivity at near neutral pH, where both the basic solutes and free silanols are protonated, suggesting the use of intermediate pH for basic solute analyses. Stability tests show that the stationary phases have high stability in neutral mobile phases at room temperature and also in acidic mobile phases, even at high temperatures. However, these phases have low stability in alkaline mobile phases, even at room temperature, which was expected for polysiloxanes immobilized onto silica / Doutorado / Quimica Analitica / Doutor em Ciências

Orientador: Carla Beatriz Grespan Bottoli / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T03:14:53Z (GMT). No. of bitstreams: 1 Sato_MarianaRobertoGama_D.pdf: 4595333 bytes, checksum: 8882cf8d1d6576b19fd550c9d1d84f8b (MD5) Previous issue date: 2014 / Resumo: O desenvolvimento da cromatografia líquida capilar (CLC), como uma alternativa à cromatografia líquida de alta eficiência, tem se destacado no âmbito da miniaturização, uma tendência geral em instrumentação analítica para separações cromatográficas. O objetivo deste trabalho foi desenvolver e caracterizar fases estacionárias monolíticas para uso em CLC, empregando monolitos poliméricos orgânicos baseados em metacrilatos hidrofóbicos e hidrofílicos. O preparo das fases estacionárias monolíticas foi realizado in situ, ou seja, o recheio foi moldado no interior das colunas capilares de 150 µm de diâmetro interno. Foram empregados os monômeros butil metacrilato, lauril metacrilato e trimetilolpropano trimetacrilato no preparo de fases estacionárias monolíticas para separações no modo fase reversa; o polietileno glicol dimetacrilato foi empregado no preparo de fases estacionárias para separações no modo HILIC. As condições de preparo das fases estacionárias monolíticas foram comparadas e envolveram a aplicação de diferentes métodos de iniciação da reação de polimerização, como iniciação por radiação UV e iniciação térmica. O simples entrecruzamento de um monômero multifuncional e a polimerização controlada via radical livre também foram aplicados como métodos de preparo dos materiais monolíticos. As fases estacionárias monolíticas foram caracterizadas por técnicas físicas, como microscopia eletrônica de varredura e porosimetria por sorção de nitrogênio; as colunas preparadas foram avaliadas cromatograficamente pela técnica de CLC. As fases estacionárias monolíticas mostraram eficiência cromatográfica de até 47000 pratos m-1 para a separação de alquilbenzenos no modo fase reversa e de até 45000 pratos m-1 para a separação de acrilamidas no modo HILIC / Abstract: The development of capillary liquid chromatography (CLC), as alternative to high performance liquid chromatography, has emerged in miniaturization studies, a common trend in analytical instrumentation for chromatographic separations. The goal of this work was to develop and characterize monolithic stationary phases for use in CLC, using organic polymer monoliths based on hydrophobic and hydrophilic methacrylates. Stationary phases were prepared in situ by molding of the material inside the capillary columns of 150 µm of internal diameter. The monomers butyl methacrylate, lauryl methacrylate and trimethylolpropane trimethacrylate was employed to prepare monolithic stationary phases for separations by reversed phase; polyethylene glycol was used to prepare monolithic stationary phases for separations by HILIC mode. The preparation conditions were compared and involved the application of different initiation methods for polymerization reactions, such as initiation by UV radiation and initiation by heating. The single crosslinking of multifunctional monomer and controlled free-radical polymerization were also applied as preparation methods of monolithic materials. The monolithic stationary phases were characterized by physical techniques as scanning electronic microscopy and nitrogen sorption porometry; the columns prepared were chromatographic evaluated by CLC. Stationary phases showed chromatographic efficiency up to 47000 plates m-1 for the separation of alkylbenzenes in reversed phase mode and up to 45000 plates m-1 for the separation of acrylamides by HILIC mode / Doutorado / Quimica Analitica / Doutora em Ciências