O consumo de tensoativos vem aumentando em função do crescimento da população, da melhoria geral das condições de vida e maior disponibilidade nos países menos desenvolvidos. Juntamente com o aumento de consumo, crescem os problemas no tocante às matérias-primas, resíduos e sua eliminação para o meio ambiente. A maioria dos tensoativos existentes no mercado é obtida a partir de matéria graxa. As fontes graxas convencionais incluem os óleos ou triglicerídeos de côco, babaçu, palma ou ainda os seus respectivos ácidos graxos. O Brasil possui grandes vantagens para produção de óleos vegetais, pois apresenta geografia favorável, e situa-se em uma região tropical. Além disso, a produção de oleaginosas em lavouras familiares torna-se uma importante alternativa de renda. Assim esse trabalho se propôs a desenvolver dois tensoativos anfóteros a partir de produtos da biodiversidade brasileira e estudar as suas propriedades físico-químicas. Tensoativos anfóteros são compostos que quando em solução aquosa ionizam-se produzindo ânions ou cátions, dependendo do pH. Em meio básico comportam-se como tensoativos aniônicos e, em meio ácido como catiônicos. Estes tensoativos têm alta compatibilidade com a pele e mucosas. Neste trabalho, foi efetuada uma comparação de desempenho entre os principais tensoativos comerciais do segmento de higiene e cuidado pessoal, e novos tipos de tensoativos. Este estudo foi realizado por meio da avaliação das propriedades de tensão superficial, espuma e detergência, destes tensoativos. Os resultados obtidos, dentro das condições experimentais utilizadas, indicaram que o caráter iônico do tensoativo possui pouca influência nas propriedades avaliadas, sendo o tamanho da porção apolar da molécula o fator de maior importância. A comparação entre a eficiência obtida pelos novos tipos de tensoativos com aqueles já consolidados no mercado indicou que estes se ajustam bem ao mercado. / The consumption of surfactants is increasing due to population growth, the general improvement of living conditions and greater availability in less developed countries. Along with the increase in consumption has led to increasing problems with regard to raw materials, residues and their disposal into the environment. Most of the surfactants on the market are made from fatty sources. The sources include conventional greases oils or triglycerides, coconut, babassu, palm or their respective fatty acids. Brazil has great advantages for vegetable production, because it shows favorable geography, is located in a tropical area. Furthermore, the oilseed production in family farms becomes an important alternative source of income. Thus, this study proposes to develop two amphoteric surfactants produced from the Brazilian biodiversity and study their physicochemical properties. Amphoteric surfactants are compounds that when in aqueous solution producing ionized anions or cations, depending on the pH. In basic medium behave as anionic and cationic in acid like. These surfactants have high compatibility with skin and mucous membranes. In this study, a comparison was made between the surfactants commonly used by industry of hygiene and personal care, and new types of surfactants. This study was conducted by evaluating the properties of surface tension, foam, and detergency of surfactants. The results obtained in the experimental conditions used, indicated that the ionic character of the surfactant has little influence on the properties evaluated, and the size of the nonpolar portion of the molecule the most important factor. The comparison between the efficiency of the new types of surfactants with those already established in the market indicated that they are well adjusted to the market.

Le couplage entre processus physico-chimiques et le transfert de matière ou de chaleur peuvent donner lieu à des structures spatio-temporelles induites par des flux convectifs. Ces flux peuvent résulter de gradients de densité ou de tension superficielle et sont l'expression de la conversion d'énergie chimique en énergie mécanique. Quand la tension superficielle est à l'origine de ces mouvements, les effets correspondants sont connus sous le nom d'effet Marangoni. Ils jouent un rôle dans de nombreuses applications comme les procédés industriels d'extraction en amplifiant notablement la vitesse des processus de transfert. Les systèmes réels, trop complexes, doit être simplifiés par le développement de systèmes modèles afin d'établir au niveau fondamental la théorie sous-jacente à de telles dynamiques. Une succession de régimes dynamiques est observée lors de la dissolution d'une goutte de dichlorométhane (DCM) déposée sur une solution aqueuse de tensioactif (bromure de céthytriméthylammonium, CTAB). La succession remarquable de formes et de mouvements induits est déterminée par la concentration du tensioactif qui joue le rôle de paramètre de contrôle. A faible concentration en CTAB, un mouvement de translation ou des pulsations. Aux concentrations plus élevées, la goutte entre en rotation ou forme des structures polygonales. Bien que chimiquement simple, le système est complexe et implique plusieurs processus physico-chimiques : évaporation, solubilisation, transfert de tensioactifs, adsorption aux interfaces et agrégation. Les effets thermiques et de transport qui en résultent sont à l'origine des variations locales de tension interfaciale donnant lieu aux effets Marangoni. Nous nous sommes concentrés sur le comportement de la goutte quand la concentration en tensioactif conduit au régime de pulsation. Nous avons tout d'abord analysé le comportement de la goutte pendant la période d'induction qui précède le régime instable. L'analyse de la forme de la goutte corrélée à des mesures d'Imagerie par Vélocimétrie de Particules (PIV), ont montré que les flux créés par la dissolution du DCM limitent dans un premier temps l'adsorption du CTAB à l'interface eau/huile. L'instabilité ne démarre que lorsque la dissolution est réduite et que l'adsorption devient effective. La phase d'induction apparait comme une transition lente entre un coefficient d'étalement négatif (goutte ayant la forme d'une lentille) vers un coefficient d'étalement positif qui entraine l'expansion du film et les pulsations suivantes. Ces pulsations sont accompagnées par l'éjection de gouttelettes qui se forment à partir d'un bourrelet apparaissant au bord du film pendant la phase d'expansion. La rupture de ce bourrelet ressemble au phénomène connu sous le nom d'instabilité de Rayleigh-Plateau (RP). Cependant, la longueur d'onde caractéristique de formation des gouttelettes est deux fois plus faible que celle attendue dans le cas d'une instabilité de RP classique. L'origine de cet écart réside dans la modulation du bourrelet avant sa rupture. Cette modulation est en fait déterminée par des ondulations apparaissant à la surface du film et formant des rides en direction radiale. Ces rides pourraient être attribuées à un effet Marangoni thermique connu sous le nom d'instabilité de Bénard-Marangoni. Elles jouent également un rôle important dans la formation de la structure de démouillage hautement organisée décrite dans le dernier chapitre. L'ajout de CTAB dans la phase organique (goutte) donne lieu à des oscillations plus rapides qui, après une phase d'expansion de grande amplitude et l'éjection d'une couronne parfaite de gouttelettes, résultent lors de la phase de démouillage en une structure dont la forme rappelle une fleur. Une interprétation qualitative permettant d'identifier les principaux processus à l'œuvre et basée sur des mesures indépendantes de tension interfaciale apporte une explication des pulsations observées et de l'auto-organisation induite. / Far-from-equilibrium systems exhibit a wide variety of spatial and temporal patterns known as dissipative structures. The interplay between physico-chemical processes and mass or heat transfer can give rise to spatio-temporal structures induced by convective flows. These flows may result from density or surface tension gradients. They are the expression of the conversion from chemical into mechanical energy. When surface tension is the driving force, the corresponding effects are known as Marangoni effects. They are at play in numerous applications as extraction processes, oil recovery, and chemical reactors at all scales and noticeably modify transfer rates. The complexity of real systems deserves the development of model systems, essentials to settle, on a fundamental level, the theory governing the related dynamics. A succession of dynamical regimes is observed during the dissolution of a dichloromethane drop deposited on aqueous solutions of a cationic surfactant (cetyltrimethylammonium bromide, CTAB). The remarkable range of shapes and motion patterns that emerges is related to the surfactant concentration, which is used as a control parameter. For low surfactant concentrations, we observe translational motion and pulsations of the drop. At intermediate concentrations the drop transforms and starts to rotate. At higher concentrations polygonal shapes are observed. Although chemically simple and of easy implementation, the system is relatively complex and involves several processes: evaporation, solubilization, surfactant mass transfer, interfacial adsorption and self-aggregation. Thermal and transport effects induced are at the origin of local variations of interfacial tension leading to the Marangoni flows. In this thesis, we focused on the behavior of the dichloromethane drop when the aqueous surfactant concentration (0.5 mM) leads to the pulsating regime. At this concentration, we have first analyzed the behavior of the drop during the induction period that precedes the instable regime. Drop shape analysis, correlated to Particle Image Velocimetry (PIV) measurements, showed that dissolution flows initially hinder adsorption of CTAB at the water/oil interface. The instability is only triggered when dissolution is reduced and water/oil adsorption becomes effective. The induction period appears as a slow transition from an initial negative spreading coefficient (a lens shape drop) towards a positive spreading coefficient that triggers film expansion and following pulsations. These pulsations are accompanied by the ejection of smaller droplets which are formed from a toroidal rim that is created during the expanding phase of the drop. The break-up of this toroidal rim, resembles to what is known as the Rayleigh-Plateau (RP) instability. Nevertheless, the observed characteristic wavelength is a factor of 2 too small in respect to the classical RP instability. We have found the origin of this discrepancy in the fact that modulations that appear on the rim before it transforms into droplets are settled by deformations arising at the surface of the expanding film. They appear as wrinkles that form in the film and may be related to thermal Marangoni effects known as Benard-Marangoni instability. These wrinkles play an important part in the highly organized dewetting structure described in the last chapter of the thesis. The addition of CTAB also in the organic (drop) phase leads to faster pulsations which, after a very high amplitude expanding stage and the ejection of a perfect crown of droplets, result during the film receding stage in the formation of a pattern which symmetry is reminiscent of a flower. A qualitative interpretation aimed at identifying the main processes at play and based on independent surface tension data gives a consistent explanation of the observed pulsations and related self-organized patterns.

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.

Não consta Resumo na publicação. / Abstract not available

Neste estudo foi caracterizado o processo de solubilização de solutos neutros em sistemas micelares compostos de surfactantes não iônicos da família de alcoóis secundários etoxilados com o mesmo grupo hidrofóbico e graus diferentes de etoxilação, variando de 5 a 30 subunidades de oxido de etileno. Para isso, foram utilizadas as Relações Lineares de Energias Livres de Solvatação (LSER) como modelo preditivo para a eficiência de incorporação de solutos. As análises de regressão múltipla e as validações apresentadas tiveram por base a constante de incorporação micelar KS como variável dependente e os descritores de soluto de Abraham como as variáveis independentes. A metodologia utilizada para a determinação de KS baseou-se em técnicas fotofísicas (supressão de fluorescência), medidas de solubilização (solubilização em saturação via espectrofotometria de UV-VIS) e técnicas de cromatografia líquida (Cromatografia Micelar) e gasosa (Cromatografia por Análise de Fase Vapor ou Headspace). A determinação realizada forneceu as seguintes LSERs: 15-S-5: Log KS = 0,054 - 0,227A - 1,197B - 0,600S + 0,938E + 1,854V 15-S-7: Log KS = + 0,267 + 0,435A - 1,475B - 0,831S + 1,045E + 1,805V 15-S-15: Log KS = -0,047 + 0,314A - 1,265B - 0,487S + 0,823E + 2,107V 15-S-30: Log KS = - 0,345 + 0,366A - 1,114B - 0,430S + 0,858E + 2,310V Como é típico para sistemas micelares, constatou-se que a partição dos solutos entre os agregados micelares e a fase aquosa é dominada pelas propriedades de volume molar (V) e capacidade receptora de pontes de hidrogênio ou basicidade (B) do soluto, com contribuições secundárias de dipolaridade (S) e refração molar em excesso (E) do soluto. O aumento do tamanho da cabeça hidrofílica de oligômeros de oxietileno (OE) torna a micela menos coesa, facilitando a acomodação de solutos e favorecendo também a penetração de moléculas de água de hidratação que formam pontes de hidrogênio com as unidades de OE. Isto é indicado pelas variações observadas nos coeficientes de B e V. As variações dos coeficientes de S respondem também ao tamanho da cadeia e ao grau de hidratação, o que foi verificado pelos espectros de bandas vibrônicas de fluorescência de pireno e por alterações de deslocamentos químicos de RMN-1H. Anomalias observadas para surfactante 15-S-5 provavelmente deveram-se à presença de isopropanol utilizado como aditivo para solubilizá-lo em meio aquoso. O conjunto de dados obtidos demonstra que o tamanho da cadeia de OE e da micela responde melhor ao modo do que à extensão de solubilização dos solutos analisados, uma vez que a variável KS não responde de maneira linear ao grau de etoxilação para o conjunto de detergentes estudados. / This study has characterized the solubilization of neutral solutes in micellar systems composed of nonionic surfactants belonging to the family of ethoxylated secondary alcohols with the same hydrophobic group and different degrees of ethoxylation ranging from 5 to 30 ethylene oxide units. Linear Solvation Energy Relationships (LSER) was used as a predictive model for the efficiency of incorporation of solutes. The multiple regression analysis and the validations presented were based on the micellar incorporation constant KS as the dependent variable and Abraham solute descriptors as the independent variables. The methodologies utilized to determine the KS values included photophysical techniques (fluorescence quenching), measurements of solubility at saturation (via UV-VIs spectrophotometry), micellar liquid chromatography and gas chromatography (Headspace analysis of the vapor phase above micellar solutions). This study provided the following LSERs: 15-S-5: Log KS = - 0,054 - 0,227A - 1,197B - 0,600S + 0,938E + 1,854V 15-S-7: Log KS = + 0,267 + 0,435A - 1,475B - 0,831S + 1,045E + 1,805V 15-S-15: Log KS = - 0,047 + 0,314A - 1,265B - 0,487S + 0,823E + 2,107V 15-S-30: Log KS = - 0,345 + 0,366A - 1,114B - 0,430S + 0,858E + 2,310V As typically observed for micellar systems, the partitioning of solutes between micellar aggregates and the aqueous phase is dominated by the properties of molar volume (V) and hydrogen bond basicity (B) of the solute, with secondary contributions from the dipolarity (S) and excess molar refraction (E) of the solute. The increase in the size of the hydrophilic oxyethylene (OE) headgroup decreases the cohesion of the micelle, facilitating the accommodation of solutes and also favoring the penetration of waters of hydration that hydrogen bond with the OE units. This is indicated by the changes observed in the coefficients of B and V. The changes observed for S also respond to the size of the OE chain, as reflected in the vibronic bands of the fluorescence spectra of pyrene and changes of proton chemical shifts in 1H-NMR spectra. Anomalies for the surfactant 15-S-5 were probably due to the necessity to include isopropanol as an additive to solubilize it in water. The data show that the OE chain and micelle sizes respond better to the mode than to the extent of solubilization for the solutes analyzed, since the predictor variable KS does not respond consistently to the degree of ethoxylation for the micellar systems studied.

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.

O CO2 supercrítico (CO2-sc) é um bom solvente para substâncias apolares e pouco polares de baixa massa molecular. A fim de tornar este meio um melhor solvente para uma gama maior de substâncias, desenvolvemos 8 novos tensoativos, sendo seis derivados de açúcares (N-metil-D-glucamina, 2-D-Glucosamina e Sorbitano) e três derivados de óleos vegetais (linhaça e palma). Os tensoativos possuem como grupos CO2-fílicos, o acetato (peracetilados) ou o t-butil-glicidil-éter, e como grupo CO2-fóbico o dodecanoato, que pode proporcionar um ambiente \"apolar\" em eventuais agregados formados em CO2-sc. A solubilidade e o comportamento de fase destes novos tensoativos em CO2-sc foram investigados, mostrando-se bastante solúveis e apresentando pontos de névoa comparáveis a outros tensoativos fluorados (mais agressivos, do ponto de vista ambiental). A polaridade que estes tensoativos agregam ao meio foi verificada através de análises de solvatocromismo, utilizando o corante de Reichardt (Betaína-30) e fluorescência de pireno, as quais mostraram resultados bastante promissores, obtendo-se polaridades baixas e médias (similares a álcoois de cadeia média ou solventes clorados). / Supercritical CO2 (sc-CO2) is a good solvent for non-polar or almost non-polar substances with low molecular mass. In order to turn this medium into a better solvent for a wider range of substances, we developed 8 new surfactants, six of them sugar derivatives (N-methyl-D-glucamine, 2-D-Glucosamine and Sorbitan), and three of them vegetable oil derivatives (palm and linseed). The surfactants have either acetate (peracetylated) or t-butyl-glycidyl ether as CO2-philic groups, and as CO2-phobic group, dodecanoate, that can provide an \"apolar\" environment in aggregates that might be formed in sc-CO2. The solubility and phase behavior of these new surfactants in sc-CO2 were investigated, and they showed to be very soluble presenting low cloud pressures comparable to fluorinated surfactants (that are more aggressive from an environmental perspective). The polarity that these new surfactants brought to the medium was verified through the solvatochromic analysis, using the Reichardt\'s dye (Betaine-30) and pyrene fluorescence, which showed promising results, with polarities similar to medium chain alcohols or chlorinated solvents

O óleo diesel é um dos derivados do petróleo mais consumidos no Brasil e responsável com grande número de áreas contaminadas. Enquanto há técnicas consagradas para a remoção do óleo diesel nas fases livre, vapor e dissolvida, as soluções para a remoção da fase residual ainda carecem de maior eficiência e/ou menor custo. Este trabalho mostra os resultados de uma investigação laboratorial da remoção de HPA de amostras indeformadas de um solo contaminado com óleo diesel por meio de ensaios de lavagem com soluções do surfactante Lauril Sulfato de Sódio (LSS) nas concentrações de 0,6, 1,5 e 3 CMC (concentração micelar crítica), seguido de um ensaio de respirometria para avaliar a capacidade de biodegradação aeróbia. Um equipamento foi desenvolvido especialmente para a realização dos ensaios de coluna utilizando os próprios anéis de amostragem. Os resultados mostraram que apenas na concentração de 3 CMC foi possível remover HPA em concentrações acima do limite de detecção da técnica analítica, e que essa remoção foi inferior a 7,6 % da massa residual no solo. Os resultados de respirometria mostraram que o solo sem a adição de surfactante degradou em média 1% do contaminante inicial, por semana. A influência da lavagem na biodegradação não demonstrou um comportamento regular e durou aproximadamente duas semanas. A biodegradação posterior ao período de influência do surfactante apresentou alta correlação linear com a concentração inicial de contaminante. / Diesel fuel is one of the most petroleum derivates consumed in Brazil and responsible with large numbers of contaminated areas. While there are consecrated techniques for the removal of diesel oil-free phases, vapor and dissolved, the solutions to remove the residual phase still need greater efficiency and/or lower cost. This work shows the results of a laboratory investigation of the removal of PAH undisturbed samples of soil contaminated with diesel oil by soil flushing tests with solutions of surfactant Sodium Lauryl Sulfate (SLS) at concentrations of 0,6, 1,5 and 3 CMC (critical micelle concentration), followed by a respirometric test to assess the ability of aerobic biodegradation. A device was developed specifically for the test column using their own sampling rings. The results showed that only the solution with 3 CMC concentration was able to remove PAH concentrations above the detection limit of the analytical technique, and that this removal was less than 7.6% of residual mass in the soil. The results showed in the soil respirometry without the addition of surfactant biodegraded on average 1% per week of the initial contaminant. The influence of flushing on the biodegradation has not established a regular pattern and lasted about two weeks. The biodegradation after the period of influence of the surfactant was highly correlated linearly with the initial concentration of contaminant.

A poluição dos rios brasileiros é, atualmente, um grande problema para as autoridades governamentais já que a demanda dos recursos hídricos vem crescendo nos últimos anos. Os rios Tietê, Pinheiros e Tamanduateí foram de grande importância para a cidade de São Paulo em seu período de industrialização, contudo o próprio desenvolvimento industrial impactou permanentemente os mesmos. Preocupados com a saúde ambiental, órgãos fiscalizadores estaduais iniciaram forte fiscalização para coibir e responsabilizar os principais culpados. Esta política pública resultou em uma diminuição das concentrações de poluentes orgânicos e inorgânicos, porém muito pouco foi efetivamente feito com relação ao esgoto doméstico, e, como consequência, a toxicidade das águas dos rios permanece elevada. Os estudos de Avaliação e identificação da toxicidade englobam diversas metodologias reunidas em três documentos pela USEPA - Agência de Proteção Ambiental dos Estados Unidos, onde método físico-químico e testes toxicológicos são usados para identificar substâncias tóxicas, ou grupo de substâncias tóxicas que contribuem efetivamente para a toxicidade total de uma amostra. A abordagem rotineiramente utilizada baseia-se no fracionamento da amostra de acordo com suas propriedades físico-químicas: volatilidade, solubilidade e capacidade de formar complexos, ou de ser reduzida, oxidada, ionizada, entre outras. Em conjunto com os ensaios químicos, os ensaios toxicológicos, em especial o Sistema Microtox®, contribuem na investigação da toxicidade para os rios metropolitanos Tietê, Pinheiros e Tamanduateí, que se mostrou eficaz na determinação dos grupos de compostos, sendo os compostos orgânicos apolares, orgânicos voláteis, tensoativos e as partículas, as principais fontes da toxicidade para esses rios. Embora muitas informações sobre a toxicidade tenham sido descobertas, a identificação dos compostos só pode ser realizada por análises químicas mais robustas uma vez que um grande número de substâncias, metabólitos e subprodutos de degradação são facilmente encontrados neste tipo de amostra. Mesmo sofrendo algumas modificações, deve-se incentivar o uso desta metodologia para outros rios a fim de determinar os principais toxicantes responsáveis pela toxicidade. / Pollution of Brazilian rivers is currently a major problem for government authorities as demand for water resources has been increasing in recent years. Tietê, Pinheiros and Tamanduateí rivers were of great importance for the city of São Paulo during its industrialization period, however, the industrial development itself permanently impacted them. Concerned about environmental health, state supervisory bodies have begun strong enforcement to curb and hold the main culprits accountable. This public policy has resulted in a decrease in concentrations of organic and inorganic chemicals, but very little has been done in relation to domestic sewage, and as a consequence, the toxicity of the rivers remains high. The Toxicology Assessment and Identification studies encompass various methodologies gathered in three documents by the USEPA, where physico-chemical method and toxicological tests are used to identify toxic substances, or group of toxic substances that effectively contribute to the total toxicity of a sample. The routinely used approach is based on fractionation of the sample according to its physicochemical properties: volatility, solubility and chemical properties such as the ability to form complexes, or to be reduced, oxidized, ionized, among others. In conjunction with the chemical tests, the toxicological tests in particular the Microtox® System contribute to the investigation of the toxicity to the metropolitan rivers, Tietê, Pinheiros and Tamanduateí, which proved to be effective in the determination of the groups of compounds, the organic compounds being apolar, organic volatiles, surfactants and particulates, the main sources of toxicity for the studied rivers. Although much information on toxicity has been discovered, the identification of compounds can only be performed by more robust chemical analyzes since a large number of substances, metabolites, degradation byproducts are readily found in this type of sample. Even with some modifications, it is necessary to encourage the use of this methodology for other rivers in order to determine the main xenobiotics responsible for toxicity.

Bacteria produce a range of surface-active compounds called biosurfactants that reduce the surface tension of liquid and exhibit different oil-water behaviours. These are used in various biotechnological applications including agriculture, cosmetics, medical and food. A recent study has predicted a limit to bacterial surface tension-reducing ability. If this limit exists, it has strong negative consequences in surveys for more active compounds. In this work, the aim is to (i) investigate this prediction more robustly by using chemical media and (ii) study the diversity amongst the best-performing surfactants produced by Pseudomonas spp. with the intention of finding novel surfactants that could be used in different biotechnological applications. A total of 251 Pseudomonas spp. were isolated from soil. Strains were first screened for liquid surface tension-reducing ability (LSTRA) using qualitative drop-collapse assay before quantitative surface tension measurement. Of the 58 LSTRA strains, only 46 significantly reduced the surface tension of sterile media. Individual Distribution Identification (IDI) analysis was used to determine the predicted limit for surfactant activity in KB* and M9Glu media, and results were found to be in agreement with earlier studies. To investigate the chemical structural diversity amongst the best performing surfactants, a collection of 25 key strains producing a limited range of very low surface tension in liquid culture media (~24 – 26 mN/m) were examined. Initial phenotypic characterisation including biochemical, metabolic profiling and 16S rDNA sequencing confirmed strains were a diverse collection of Pseudomonas spp. A series of behaviour assays including emulsion formation, foam stabilisation and oil displacement assays to investigate behavioural diversity among surfactants expressed by the key strains were then undertaken. For the oil displacement, diesel, mineral, vegetable, and used lubricating oils were tested with the underlying aqueous layer containing 0 or 200 mM NaCl at pH 6.0 or 8.0 to reflect a range of biotechnological applications and conditions. Analysis of variance of the emulsion indices, foam stabilisation and oil displacement data showed significant difference in surfactant behaviour among the key surfactant-expressing strains (P < 0.001). Moreover, Hierarchical Cluster Analysis (HCA) was used to produce a constellation dendrogram in which isolates were grouped according to similarities in phenotype and surfactant behaviour. Critically, this resulted in more groups (≥ 5 groups) than could be explained by statistically significant differences in mean surface tensions (previously determined by ANOVA and Tukey-Kramer HSD, alpha = 0.05). These findings provide strong evidence that the key strains were expressing structurally more than one type of surfactant with differing air-water and oil-water behaviours. Similarly, in vitro surfactant characterisation within a range of pH and salt concentrations confirmed diversity among strains (P < 0.001). Investigating surfactant potential by a two-way behaviour cluster dendrogram resulted in more diversity among oil types than the conditions used. These findings indicate that bioprospecting surfactants by screening only the more active compounds is likely to reveal a range of functionalities.