Due to the high specific surface area and aspect ratio (length to diameter ratio, or L/D) of carbon nanotubes, they tend to bind strongly through the van der Waals interactions prevailing among tubes. Thus, they agglomerate and settle in water to form large conglomerates. The adsorption of natural organic matter (NOM) or surfactants onto raw multi-walled carbon nanotubes (MWCNTs) was shown to effectively enhance the dispersibility and stabilization of MWCNTs. The two kinds of dispersants used were humic acid and peptone. Also, two functionalized MWCNTs (-OH and -COOH functional groups) were also dispersed in humic acid (HA) to evaluate the effect of surface property on CNT biological interactions. Based on the dynamic light scattering (DLS) analyses, the use of surfactants increased the steric hindrance as well as the charge repulsion between adjacent CNT particles, thereby enhancing their suspension. HA and peptone sorption onto the surface of MWCNTs can cover their hydrophobic surfaces and help stabilize CNTs. Furthermore, hydroxyl modification of MWCNTs resulted in stable dispersions in water containing HA at 10 and 1000mg/L, while COOH-MWCNT suspensions displayed stable dispersion with lower negative surface charges solely at 100g/L. While, TEM images agreed with the DSL analysis that HA-stabilized MWCNTs were well-dispersed compared to pep-stabilized MWCNTs. Both f-MWCNT types showed a significant reduction in agglomerates as compared to the non-functionalized one. It was noted that the dispersion state as well as the surface properties of both MWCNTs and f-MWCNTs plays an effective role in the potential toxic effects of CNTs. Decreases in the growth rate, chlorophyll index, water uptake, dry weight, and root elongation rate along with a rise in mortality were detected as an indication of phyto-toxicity in both the pep-MWCNT suspensions at 1000mg/L and the peptone control seedlings in contrast to the seedlings treated with pep-MWCNTs at 10 and 100mg/L doses . This was an indicator for the presence of suspended MWCNTs as well as their unstable dispersion in the water column. However, the interaction between the HA-CNTs and the plants improved development in terms of water uptake, growth rate, chlorophyll index, dry weight and root elongation rate due to their well- dispersed stability in water. There were no differences among the f-MWCNT, MWCNT and HA plant groups in terms of their quantum yield and chlorophyll content. While the f-MWCNTs significantly enhanced the plants' growth, water transpiration, and dry root and shoot weight as compared to the non-functionalized MWCNTs. It appeared that exposure to OH-MWCNTs improved the development of tomatoes in terms of water uptake, root elongation rate, and growth rate as well as light- and dark-adaptation, whereas COOH-MWCNTs and non-functionalized MWCNTs were apparently toxic in terms of root leakage and dark-adaptation. Overall, our results suggest that the surface properties of CNTs associated with their dispersion stability specify their influence on the growth of tomato plants. Moreover, the nature of the dispersant agent itself plays an active role in the toxicity of MWCNTs on tomatoes. Our investigation indicated that there is a significant correlation between the toxicity of unfunctionalized MWCNTs and f-MWCNTs and the toxicity of the dispersant agent.

xv, 116 p. : ill. A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / Aqueous solutes next to hydrophobic interfaces arc prevalent in a multitude of chemical and biological systems throughout the world. Their presence ranges from environmental processes such as soil and water remediation to biological processes such as ion transport, membrane formation, and enzyme activity. In these and other examples, the interface is an integral part of the system. Understanding these chemically complex systems requires that a molecular level picture be built as a starting basis. In this dissertation, vibrational sum-frequency spectroscopy (VSFS), a surface selective non-linear optical technique, is used to obtain a fundamental understanding of the interfacial properties of carboxylic acid based surfactants and polymers at the oil-water interface. Interfacial studies of the solvating environment around a carboxylate headgroup surfactant are presented first. By utilizing different VSFS polarization schemes, the carboxylate vibrational stretching region was used to monitor the headgroup environment. Results showed the oil-water interface provides a unique environment for adsorption and structuring, and distinct differences exist from the air-water and solid-water interface. With the information gained in the first study, the binding of metal ions to carboxylate headgroups is investigated using VSFS. Mg 2+ , Ca 2+ , Mn 2+ , Ni 2+ , Cu 2+ , and Zn 2+ were used to perturb the headgroup vibrations to further our understanding of the types of interactions and the binding strength between the ion and headgroup. The results show each ion to have a different interaction characteristics with the strongest being bi-dentate in nature and the weakest having ionic character. The final work presented involves moving VSFS studies towards macromolccular assemblies at the oil-water interface to model inherently complex biomolecular systems. These studies present adsorption structure and dynamics of poly(acrylic-acid) as a function of pH, molecular weight, concentration, and the presence of mono and divalent salts. Poly(acrylic-acid) was found to have ordered adsorption characteristics that were highly dependent on the pH and the presence of aqueous salts. This dissertation includes unpublished co-authored materials. / Committee in charge: Thomas Dyke, Chairperson, Chemistry; Geraldine Richmond, Advisor, Chemistry; John Hardwick, Member, Chemistry; Jeffrey Cina, Member, Chemistry; 1. Andrew Berglund, Member, Chemistry; John Conery, Outside Member, Computer & Information Science

OLIVEIRA, Ulisses Marcondes Freire de. Desenvolvimento de biocatalisadores utilizando lipases de Rhizomucor mihei (RML) imobilizada em suporte de quitosana e sua aplicação na síntese de ésteres butirato de metila e butirato de etila. 2012. 272 f. : Tese (doutorado) - Univerisdade Federal do Ceará, Doutorado em Biotecnologia da Rede Nordeste de Biotecnologia - RENORBIO, Fortaleza-CE, 2012. / Submitted by demia Maia (demiamlm@gmail.com) on 2016-05-30T14:39:42Z No. of bitstreams: 1 2012_tese_ umfoliveira.pdf: 5868740 bytes, checksum: fb87a06503cdae0af0e790f65341b983 (MD5) / Approved for entry into archive by demia Maia (demiamlm@gmail.com) on 2016-05-30T14:43:49Z (GMT) No. of bitstreams: 1 2012_tese_ umfoliveira.pdf: 5868740 bytes, checksum: fb87a06503cdae0af0e790f65341b983 (MD5) / Made available in DSpace on 2016-05-30T14:43:49Z (GMT). No. of bitstreams: 1 2012_tese_ umfoliveira.pdf: 5868740 bytes, checksum: fb87a06503cdae0af0e790f65341b983 (MD5) Previous issue date: 2012 / Lipases (glycerol ester hydrolases, EC3.1.1.3) are versatile catalysts with broad and diverse possibilities of industrial applications. Its main application is essentially catalyze the hydrolysis of triglycerides. However, in micro-aqueous environments these enzymes have the ability to catalyze the reverse reaction of esterification. These enzymes do not require cofactors, have relatively low cost, are regioespecific, enantioselectives and may act on a broad range of temperature and pH. This work aimed to develop alternative technologies using enzymatic routes mediated by lipase from Rhizomucor miehei (RmL) immobilized on chitosan support in the presence of some classes of surfactants for the production of methyl butyrate and ethyl butyrate, two esters widely used in cosmetic and food industries. In this study two immobilization strategies were evaluated. In the first, the enzymes were immobilized in the presence of selected surfactants on chitosan supports previously activated with glutaraldehyde. In the second immobilization strategy, chitosan was crosslinked with glutaraldehyde after prior adsorption of the enzymes in the presence of surfactants. Among the immobilization procedures studied, the best results were achived when the enzyme was immobilized onto chitosan support in the presence of the surfactant sodium dodecyl sulphate SDS (0.23% m v-1) for 1 h at 4 ° C and 220 rpm, followed by crosslinking with 0.6% glutaraldehyde (v v-1) for 1 h at 25 ° C. In esterification experiments conducted with the best derivative, a detailed study of the parameters that affect the reaction rates were performed. The best yields were obtained when the reactions were conducted at 25 ° C, 6h and 150 rpm using n-heptane as a solvent. For methyl butyrate maximum esterification yield was 89% and for ethyl butyrate the maximum conversion observed was 92%. The results were comparable to yields observed when the esterification reactions were carried out with the commercial enzyme Lipozyme® and the soluble enzyme under the same reaction conditions. / Lipases (glicerol éster hidrolases, E.C.3.1.1.3) são catalisadores versáteis com amplas e diversificadas possibilidades de aplicação industrial. Sua principal aplicação é essencialmente catalisar a hidrólise de triglicerídeos. Entretanto, em ambientes micro-aquosos estas enzimas possuem a habilidade de catalisar a reação reversa de esterificação. Estas enzimas não requerem cofatores, possuem custo relativamente baixo, são regioespecíficas, enantiosseletivas, além de atuarem em uma larga faixa de temperatura e pH. Neste contexto, este trabalho teve por objetivo desenvolver tecnologias alternativas utilizando rotas enzimáticas mediadas por lipase de Rhizomucor miehei (RmL) imobilizada em suporte quitosana na presença de algumas classes de surfactantes para a produção de butirato de metila e butirato de etila, dois ésteres amplamente utilizados na indústria de cosméticos e de alimentos. Neste estudo, duas estratégias de imobilização foram avaliadas. Na primeira, a enzima foi imobilizada na presença dos surfactantes selecionados em suporte quitosana previamente reticulado com glutaraldeído. Na segunda estratégia de imobilização, o suporte utilizado foi reticulado com glutaraldeído após prévia adsorção da enzima na presença dos surfactantes. Dentre os procedimentos de imobilização estudados, os melhores resultados foram obtidos quando a enzima foi previamente adsorvida no suporte quitosana na presença do surfactante dodecil sulfato de sódio (0,23% m.v-1) por 1h a 4°C e 220 rpm, seguido de reticulação com glutaraldeído 0,6% (v.v-1) por 1h a 25°C. Nos ensaios de esterificação utilizando o melhor derivado obtido, foi efetuado um estudo detalhado dos parâmetros que afetam as taxas de conversão. Os melhores rendimentos foram obtidos quando as reações foram conduzidas a 25°C, 6h e 150 rpm utilizando n-heptano como solvente. Para o butirato de metila, o rendimento máximo de esterificação foi de 89% e para o butirato de etila a maior conversão observada foi de 92%. Os resultados obtidos foram comparáveis aos rendimentos de esterificação observados quando foi utilizada a enzima comercial Lipozyme® nas mesmas condições reacionais.

Dans les procédés liés aux émulsions, des écoulements turbulents et polyphasiques entrent en jeu. De tels procédés apparaissent dans des domaines variés. Dans l'industrie agro-alimentaire, la production de lait fait intervenir un homogénéisateur à haute pression, et certains produits tels que la mayonnaise sont des émulsions stables. On trouve aussi des émulsions dans le domaine de la santé : elles assurent le bon fonctionnement de nos poumons, tandis que d'autres peuvent être injectées par voie parentérale en tant que médicaments. On les retrouve aussi dans les procédés de séparation, par exemple eau-brut de pétrole dans l'industrie pétrochimique. Dans tous les cas, la fragmentation et la coalescence des bulles et gouttes doivent être maîtrisées, car elles influencent directement la distribution en taille de la phase dispersée. La fréquence d'apparition de ces phénomènes peut être prédite en utilisant des modèles adaptés. Cependant, la présence de molécules tensioactives modifie grandement cette fréquence et par conséquent la distribution en taille en sortie du procédé. Or, ce type de molécules est présent dans quasiment tous les procédés polyphasiques. L'étude des effets des tensioactifs dans ces procédés s'est alors imposée. Dans un des plus récents modèles, les bulles ou gouttes sont considérées comme des oscillateurs forcés par la turbulence de l'écoulement environnant. Il est alors nécessaire de connaître à la fois la turbulence dans le voisinage de la goutte et les propriétés dynamique de la goutte. La première peut être déterminée expérimentalement. La réponse de la goutte au forçage est alors décrite comme une somme d'harmoniques sphériques dont la dynamique est décrite pour chaque mode par une pulsation et un coefficient d'amortissement. Cette thèse aborde l’étude des effets des tensioactifs sur ces deux grandeurs. Elle s’est déroulée en collaboration entre l'IMFT et le LGC, ce qui a permis d'associer les compétences de chaque laboratoire dans les domaines de la physico-chimie, de l'hydrodynamique des phases dispersées et des écoulements turbulents diphasiques. Le projet lors de cette thèse est d'étudier numériquement les effets des tensioactifs sur les échelles temporelles caractéristiques des oscillations, dans le cas où la goutte est immobile ou bien en mouvement dans un fluide externe. Une équation de transport des tensioactifs ainsi que l'effet Marangoni à l'interface ont été modelisés dans le code DIVA, et validés à l'aide de cas tests. Ensuite, des simulations de gouttes subissant des oscillations de forme suivant le mode 2 des harmoniques sphériques ont permis de décrire les effets des tensioactifs sur la dynamique des interfaces. Ils ont été validés par la théorie pour des oscillations linéaires. Le couplage entre le mouvement d'ascension et les oscillations de formes a aussi été étudié, afin de comprendre l'effet d'un fort effet Marangoni, généré par l'ascension de la goutte, sur les oscillations. Les viscosités de surface peuvent aussi influencer radicalement la dynamique interfaciale. Lors de cette thèse, une méthode a été développée et validée pour permettre à l'outil de simulation de prendre en compte des viscosités de surface en se basant sur le modèle de Boussinesq-Scriven. Leur effet sur la dynamique des oscillations de forme a été étudié. / In many industrial processes, such as high-pressure homogenisation or water-oil separation, turbulent and multiphase flows are involved. To optimize those processes, coalescence and fragmentation need to be controlled since they impact directly the size distribution of drops and bubbles. The occurrence of those phenomena can be predicted using adapted models. However, the presence of surfactant molecules at the interface between two fluid phases can change radically the phenomenology of drops break up and coalescence, and their effect has not been properly included in existing models yet. In one of the latest models, drops are considered as forced oscillators driven by the local turbulence of a flow. It is therefore required to know the local turbulence of the flow and the dynamic properties of the drop. It is possible to measure experimentally the local velocities in a flow to determine the local average turbulent Weber number, which represents the forcing term of the oscillator. The dynamic response of the drop is described as a series of oscillators, the principal mode of which is characterized by two time scales, the pulsation and damping coefficient. The goal of this PhD is to study numerically the impact of surfactants on the two time scales mentioned above, whether the drop is still or in motion in the surrounding fluid. An equation of transport of surfactants and the Marangoni effect at the interface have been implemented in the code, and validated. Simulations of a drop undergoing shape oscillations along its eigenmode n = 2 have allowed to study the effects of surfactants on the time scales of oscillations, which were validated with theoretical predictions for linear oscillations. Surface viscosities can also influence the time scales of oscillations. Therefore, a numerical method has been developped and validated to take surface viscosities into account. The stress jump is based on the expression of the Boussinesq-Scriven model. Their effect is studied on the dynamic of oscillations.

Os líquidos iônicos, por geralmente apresentar, em sua estrutura, uma cadeia alquílica apolar e uma parte polar, como o cátion imidazólio, podem ser considerados estruturas anfifílicas, e apresentam semelhanças com os tensoativos. Tais estruturas, devido a este caráter anfifílico, podem interagir com estruturas do tipo Lipossomas ou até mesmo com biomoléculas, como a BSA. Neste trabalho, foram sintetizados três líquidos iônicos inéditos, com rendimentos de 52 a 66%, acoplados a sistemas quirais derivados de aminoácidos naturais e de fácil obtenção, como a L-Cisteína, a L-Serina e a L-Treonina. Estes foram caracterizados tanto do ponto de vista estrutural, quanto por suas propriedades fotofísicas. Como procedimento metodológico utilizou-se de ciclocondensação de aminoácidos, esterificação de Steglich e alquilação para inserção de cadeia carbônica ao anel metil-imidazol. Para investigação e confirmação dessas estruturas utilizou-se de estudos de Ressonância Magnética de 1H e de 13C, Infravermelho, além das espectroscopias de absorção na região do UV-Vis e de emissão de fluorescência. Por fim, estes novos líquidos iônicos foram testados com lipossomas e BSA, cujos resultados mostraram boa interação com essas biomoléculas. / Ionic liquids can be considered as amphiphilic structures and have similarities with the surfactants, once they generally have an apolar alkyl chain and a polar moiety, such as the imidazolium cation. Such structures, due to this amphiphilic character, may interact with liposome structures or even with biomolecules, such as BSA. In this work, three new ionic liquids containing chiral systems derived from naturally occurring amino acids, such as L-Cysteine, L-Serine and L-Threonine were synthesized, with yields ranging from 52 to 66%. They were fully characterized both from the structural point of view, and by its photophysical properties. As methodological procedures, amino acid cyclocondensation, Steglich esterification and alkylation were used. In order to investigate and confirm these structures, magnetic resonance studies of 1H and 13C, infrared, as well as absorption spectroscopies in the UV-Vis region and fluorescence emission were used. At last, these new ionic liquids were tested with liposomes and BSA, and the results showed good interaction with these biomolecules.

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Os líquidos iônicos, por geralmente apresentar, em sua estrutura, uma cadeia alquílica apolar e uma parte polar, como o cátion imidazólio, podem ser considerados estruturas anfifílicas, e apresentam semelhanças com os tensoativos. Tais estruturas, devido a este caráter anfifílico, podem interagir com estruturas do tipo Lipossomas ou até mesmo com biomoléculas, como a BSA. Neste trabalho, foram sintetizados três líquidos iônicos inéditos, com rendimentos de 52 a 66%, acoplados a sistemas quirais derivados de aminoácidos naturais e de fácil obtenção, como a L-Cisteína, a L-Serina e a L-Treonina. Estes foram caracterizados tanto do ponto de vista estrutural, quanto por suas propriedades fotofísicas. Como procedimento metodológico utilizou-se de ciclocondensação de aminoácidos, esterificação de Steglich e alquilação para inserção de cadeia carbônica ao anel metil-imidazol. Para investigação e confirmação dessas estruturas utilizou-se de estudos de Ressonância Magnética de 1H e de 13C, Infravermelho, além das espectroscopias de absorção na região do UV-Vis e de emissão de fluorescência. Por fim, estes novos líquidos iônicos foram testados com lipossomas e BSA, cujos resultados mostraram boa interação com essas biomoléculas. / Ionic liquids can be considered as amphiphilic structures and have similarities with the surfactants, once they generally have an apolar alkyl chain and a polar moiety, such as the imidazolium cation. Such structures, due to this amphiphilic character, may interact with liposome structures or even with biomolecules, such as BSA. In this work, three new ionic liquids containing chiral systems derived from naturally occurring amino acids, such as L-Cysteine, L-Serine and L-Threonine were synthesized, with yields ranging from 52 to 66%. They were fully characterized both from the structural point of view, and by its photophysical properties. As methodological procedures, amino acid cyclocondensation, Steglich esterification and alkylation were used. In order to investigate and confirm these structures, magnetic resonance studies of 1H and 13C, infrared, as well as absorption spectroscopies in the UV-Vis region and fluorescence emission were used. At last, these new ionic liquids were tested with liposomes and BSA, and the results showed good interaction with these biomolecules.

Neste trabalho de tese aplicamos a espectroscopia de Ressonância Paramagnética Eletrônica (RPE) junto com a chamada técnica do grupo repórter, aliada a simulação espectral por meio do programa NLSL, para investigar a interação da nicotina dependente com membranas. Também empregamos Ressonância Ferromangnética (RFM), que é uma técnica similar em muitos aspectos ao RPE, para investigamos células-tronco marcadas com nanopartículas superparamagnéticas de óxido de ferro (NSOF), previamente preparada no laboratório de nanotecnologia do Instituto Israelita de Ensino e Pesquisa Albert Einstein (IIEPAE). Os resultados relativos à primeira parte da tese, mostraram que a nicotina quando em meio ácido interage com a região da cabeça polar dos fosfolipídios estudados e tem ação penetrante em meio básico. A interação da nicotina com o DPPC resulta em uma desestabilização da fase gel do fosfolipídio. Este fato pode estar relacionado com a ocorrência de doenças respiratórias em tabagistas devido ao fato de que o DPPC é o maior constituinte do complexo surfatante pulmonar. Na segunda parte, fomos capazes de marcar células-tronco com nanopartículas superparmangéticas e também quantificá-las pelo cálculo da área, dupla integral do espectro de RFM das NOSF. Finalmente, fizemos uma caracterização das nanopartículas por meio de experimentos de RFM dependente da variação de temperatura, que confirmaram o comportamento superparamagnético das NOSF. / In this work, we made use of the Electron Paramagnetic Resonance (EPR) spectroscopy along with the so-called reporter group technique and extensive spectral simulations by means of the software NLSL to investigate the interaction of nicotine with model membranes. Besides that we also employed Ferromagnetic Resonance (FMR), which is a technique similar in many aspects to EPR, to investigate stem cells labeled with superparamagnetic nanoparticles of iron oxide (NSOF) previously made at the Nanotechnology Laboratory of the Instituto Israelita de Ensino e Pesquisa Albert Einstein (IIEPAE). The results concerning the first part of our work showed that nicotine in acidic pH value interacts with the polar headgroup region of the phospholipids under investigation, whereas it penetrates the model membrane in alkaline pH value. Also, the interaction of nicotine with DPPC resulted in destabilization of the phospholipid gel phase. This fact could be related to some of the effects of nicotine in respiratory diseases since DPPC is the major constituent of the pulmonary surfactant complex. In the second part of our work, we were able to successfully label stem cells with the superparamagnetic nanoparticles and also quantify that labeling by calculating the area under the double integrated NSOF FMR spectra. We also performed a characterization of the nanoparticles by means of temperature-variation FMR experiments, which showed that the iron oxide nanoparticled indeed had a superparamagnetic behavior.

Em trabalhos anteriores nós apresentamos um sensor sólido de óxido nítrico (NO) preparado pelo método sol-gel utilizando como aprisionadores complexos de Fe 2+ -DETC. Neste trabalho, reportamos o efeito de alguns surfactantes (CTAB-catiônico, SDS-aniônico, Triton X100-neutro e o plurônico F127) sobre o sensor. A ressonância paramagnética eletrônica (RPE) foi usada para quantificar o número de moléculas de NO-Fe 2+ -DETC. A presença dos surfactantes aumenta a resistência mecânica dos sensores sólidos, sendo mais pronunciada nos sensores contendo CTAB e Triton. Sem os surfactantes não há sinal do complexo NO-Fe 2+ - DETC. O tempo de secagem foi otimizado para 30 min. O sinal mais intenso foi obtido com os sensores contendo os surfactantes a 12 mM. Os surfactantes de um modo geral aumentam a quantidade de NO aprisionado. A difusão do NO foi estimada através do tempo de aprisionamento do NO sendo maior na presença do F127 e SDS. A saturação do sinal de NO nos sensores acontece em 10 min. Uma maior mobilidade dos complexos NO-Fe 2+ -DETC foi encontrada nos sensores contendo SDS e F127 e foi estimada pela forma de linha. Para os sensores no estado sólido o limite de detecção foi de 2 µM utilizando o F127 como aditivo, para o SDS, CTAB e Triton o limite foi de 6 µM, 8 µM e 10 µM respectivamente. Na solução coloidal a menor quantidade detectada foi de 0,1µM também com o F127. A sensibilidade dos sensores aumenta em pelo menos 5 vezes nos sensores sólidos preparados com o F127 em detrimento aos demais e pode ser melhorada utilizando surfactantes mistos. / In previous work we present a solid sensor for nitric oxide (NO) prepared by sol-gel method using the trapped complex of Fe 2+ -DETC. In this work, we report the effect of some surfactants (CTAB, cationic, anionic, SDS, Triton-X100 and neutral pluronic F127) on the sensor. The electron paramagnetic resonance (EPR) was used to quantify the number of molecules of NO-Fe 2+ -DETC. The use of surfactant increases the mechanical strength of solid sensors, being more pronounced in sensors containing CTAB and Triton. Without the surfactant no EPR signal of the complex NO-Fe 2+ -DETC was observed. The drying time was optimized to 30 min. The strongest EPR signal was obtained with the sensors containing the surfactant to 12 mM. The surfactants in general increase the amount of NO trapped. The diffusion of NO was estimated by the time of trapping of the NO that it was higher in the presence of F127 and SDS. The signal saturation of the NO sensors occurs in 10 min. A higher mobility of the complex NO-Fe 2+ -DETC was found in sensors containing SDS and F127 and was estimated by lineshapes. For the solid state sensors the detection limit was 2 µM using the F127 as additive and for the SDS, CTAB and Triton the limit was 6 µM, 8 µM and 10 µM respectively. In the colloidal solution the least amount detected was 0.1 µM also with the F127. The sensitivity of the sensors increases at least 5 times in the solid sensors prepared with the F127 in detriment to the other and can be improved by using mixed surfactants.

FundaÃÃo de Amparo à Pesquisa do Estado do Cearà / Lipases (glycerol ester hydrolases, EC3.1.1.3) are versatile catalysts with broad and diverse possibilities of industrial applications. Its main application is essentially catalyze the hydrolysis of triglycerides. However, in micro-aqueous environments these enzymes have the ability to catalyze the reverse reaction of esterification. These enzymes do not require cofactors, have relatively low cost, are regioespecific, enantioselectives and may act on a broad range of temperature and pH. This work aimed to develop alternative technologies using enzymatic routes mediated by lipase from Rhizomucor miehei (RmL) immobilized on chitosan support in the presence of some classes of surfactants for the production of methyl butyrate and ethyl butyrate, two esters widely used in cosmetic and food industries. In this study two immobilization strategies were evaluated. In the first, the enzymes were immobilized in the presence of selected surfactants on chitosan supports previously activated with glutaraldehyde. In the second immobilization strategy, chitosan was crosslinked with glutaraldehyde after prior adsorption of the enzymes in the presence of surfactants. Among the immobilization procedures studied, the best results were achived when the enzyme was immobilized onto chitosan support in the presence of the surfactant sodium dodecyl sulphate SDS (0.23% m v-1) for 1 h at 4  C and 220 rpm, followed by crosslinking with 0.6% glutaraldehyde (v v-1) for 1 h at 25  C. In esterification experiments conducted with the best derivative, a detailed study of the parameters that affect the reaction rates were performed. The best yields were obtained when the reactions were conducted at 25  C, 6h and 150 rpm using n-heptane as a solvent. For methyl butyrate maximum esterification yield was 89% and for ethyl butyrate the maximum conversion observed was 92%. The results were comparable to yields observed when the esterification reactions were carried out with the commercial enzyme Lipozyme and the soluble enzyme under the same reaction conditions. / Lipases (glicerol Ãster hidrolases, E.C.3.1.1.3) sÃo catalisadores versÃteis com amplas e diversificadas possibilidades de aplicaÃÃo industrial. Sua principal aplicaÃÃo à essencialmente catalisar a hidrÃlise de triglicerÃdeos. Entretanto, em ambientes micro-aquosos estas enzimas possuem a habilidade de catalisar a reaÃÃo reversa de esterificaÃÃo. Estas enzimas nÃo requerem cofatores, possuem custo relativamente baixo, sÃo regioespecÃficas, enantiosseletivas, alÃm de atuarem em uma larga faixa de temperatura e pH. Neste contexto, este trabalho teve por objetivo desenvolver tecnologias alternativas utilizando rotas enzimÃticas mediadas por lipase de Rhizomucor miehei (RmL) imobilizada em suporte quitosana na presenÃa de algumas classes de surfactantes para a produÃÃo de butirato de metila e butirato de etila, dois Ãsteres amplamente utilizados na indÃstria de cosmÃticos e de alimentos. Neste estudo, duas estratÃgias de imobilizaÃÃo foram avaliadas. Na primeira, a enzima foi imobilizada na presenÃa dos surfactantes selecionados em suporte quitosana previamente reticulado com glutaraldeÃdo. Na segunda estratÃgia de imobilizaÃÃo, o suporte utilizado foi reticulado com glutaraldeÃdo apÃs prÃvia adsorÃÃo da enzima na presenÃa dos surfactantes. Dentre os procedimentos de imobilizaÃÃo estudados, os melhores resultados foram obtidos quando a enzima foi previamente adsorvida no suporte quitosana na presenÃa do surfactante dodecil sulfato de sÃdio (0,23% m.v-1) por 1h a 4ÂC e 220 rpm, seguido de reticulaÃÃo com glutaraldeÃdo 0,6% (v.v-1) por 1h a 25ÂC. Nos ensaios de esterificaÃÃo utilizando o melhor derivado obtido, foi efetuado um estudo detalhado dos parÃmetros que afetam as taxas de conversÃo. Os melhores rendimentos foram obtidos quando as reaÃÃes foram conduzidas a 25ÂC, 6h e 150 rpm utilizando n-heptano como solvente. Para o butirato de metila, o rendimento mÃximo de esterificaÃÃo foi de 89% e para o butirato de etila a maior conversÃo observada foi de 92%. Os resultados obtidos foram comparÃveis aos rendimentos de esterificaÃÃo observados quando foi utilizada a enzima comercial Lipozyme nas mesmas condiÃÃes reacionais.