Interfacial concentrations of chloride and bromide in zwitterionic micelles with opposite dipoles: Experimental determination by chemical trapping and a theoretical description

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The role of counterion on the thermotropic phase behavior of DODAB and DODAC vesicles

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Aggregation behavior of hydrophobically modified dextran in aqueous solution: a fluorescence probe study

Dextrans (M-W = 11.000 and M-w = 40.000) have been modified with 4-hexyl benzoyl chloride and their aggregation behavior was studied in aqueous solution employing the fluorescent probes pyrene and 1,8 anilinonaphtalene sulfonic acid sodium salt (1,8 ANS). The photophysical studies showed that above a critical concentration the derivatives tend to form aggregates having different properties, which depend on both the degree of substitution (alpha) and the molecular weight of the sample. The parameter alpha has a marked effect on the critical aggregation concentrations (CAC) and aggregate proper-ties. Hydrophobic microenvironments can be detected for substituted dextrans having alpha values varying from 0.01 to 0.19. CAC values decreased by two orders and magnitude when the molecular weight increased from 11 to 40 kDa, leading to formation of more apolar aggregates and diminishing by about 30% the polarity of the microenviromnents. Pre-aggregation was evidenced by pyrene excimer emission and intermolecular interactions were responsible by the formation of aggregates leading to solution behaviour similar to that of common surfactants. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

Morphology and Blue Photoluminescence Emission of PbMoO4 Processed in Conventional Hydrothermal

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Effects of organic and inorganic additives on flotation recovery of washed cells of Saccharomyces cerevisiae resuspended in water

Separation of microbial cells by flotation recovery is usually carried out in industrial reactors or wastewater treatment systems, which contain a complex mixture of microbial nutrients and excretion products. In the present study, the separation of yeast cells by flotation recovery was carried out using a simple flotation recovery systems containing washed yeast cells resuspended in water in order to elucidate the effects of additives (defined amounts of organic and inorganic acids, ethanol, surfactants and sodium chloride) on the cellular interactions at interfaces (cell/aqueous phase and cell/air bubble). When sodium chloride, organic acids (notably propionic, succinic and acetic acids) and organic surfactants (sodium dodecyl sulphate (SDS), cetyltrimethylammonium bromide (CTAB) and Nonidet P40) were added to the flotation recovery system, significant increases in the cell recovery of yeast hydrophobic cells (Saccharomyces cerevisiae, strain FLT-01) were observed. The association of ethanol to acetic acid solution (a minor by-product of alcoholic fermentation) in the flotation recovery system, containing washed cells of strain FLT-01 resuspended in water, leading to an increased flotation recovery at pH 5.5. Thus, the association among products of the cellular metabolism (e.g., ethanol and acetic acid) can improve yeast cell recovery by flotation recovery. (c) 2006 Elsevier B.V. All rights reserved.

Production and partial characterization of serine and metallo peptidases secreted by Aspergillus fumigatus Fresenius in submerged and solid state fermentation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

MISTURAS DE HERBICIDAS: EFEITOS DE ADJUVANTES NO CONTROLE DE PLANTAS INFESTANTES NA CULTURA da SOJA

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Comportamento fotofísico do antraceno em sistemas micro-heterogêneos argila-surfactantes-íons metálicos

Argilas constituem uma classe de complexos micro-heterogêneos e podem ser utilizados como substrato para adsorção. O seu comportamento de sorção em fase sólida intensificada pela presença de surfactantes, argilas organofílicas, é um importante fenômeno explorado pela tecnologia ambiental para a remoção de compostos orgânicos policíclicos (hidrocarbonetos aromáticos policíclicos, HPA) da água, introduzidos no ambiente por fontes antropogênicas. Este trabalho tem por objetivo estudar o comportamento fotofísico do antraceno, como modelo de HPA, em sistemas micro-heterogêneos argila-surfactantes-íons metálicos (M(II)= Cd(II), Cu(II), Hg(II), Ni(II) e Pb(II); surfactantes: CTACl; SDS; TR-X100). Os estudos foram conduzidos pelo monitoramento na mudança das propriedades de fluorescência estática e na supressão da emissão do antraceno utilizado como sonda fluorescente. Como supressores foram utilizados os cátions metálicos: Cd(II), Cu(II), Hg(II), Ni(II) e Pb(II). O perfil do espectro de fluorescência e os resultados dos ensaios de supressão da fluorescência da sonda permitiram inferir na localização do sítio de solubilização do antraceno nos sistemas micro-heterogêneos estudados e na conseqüente organização dos mesmos.

Espectro de gotas de pontas de pulverização com adjuvantes de uso agrícola

O sucesso de uma boa aplicação de produtos fitossanitários depende da sinergia entre fatores como tamanho de gota, tipo de ponta, pressão, volume e composição da calda e características do alvo. Assim, o objetivo deste trabalho foi avaliar o espectro de gotas produzidas por pontas de jato plano defletor (TT 11002) e jato plano defletor com indução de ar (TTI 11002), com diferentes adjuvantes adicionados à calda de pulverização, pela técnica de difração de raio laser. O experimento foi conduzido em delineamento inteiramente casualizado, com quatro repetições, em esquema fatorial 2 x 5, ou seja, duas pontas de aplicação (jato plano defletor e jato plano defletor com indução de ar) e cinco composições de calda (água e água mais quatro adjuvantes: fosfatidilcoline+ácido propiônico, éter poliglicólico de monilfenol, ésteres de ácidos graxos e nonil-fenol etoxilado+óxido de etileno). em ambiente controlado, avaliou-se o espectro de gotas, por meio de um analisador a laser de gotas em tempo real, na pressão de 276 kPa. O efeito dos adjuvantes no espectro de gotas mostrou-se dependente da ponta de pulverização empregada. A adição dos adjuvantes à calda não alterou o risco potencial de deriva, expresso pela porcentagem do volume em gotas com diâmetro inferior a 100 µm, porém o adjuvante fosfatidilcoline+ácido propiônico reduziu o diâmetro da mediana volumétrica das gotas produzidas pela ponta de jato plano defletor com indução de ar, em relação à avaliação feita somente com água.

Droplet deposition during spray and leaf pH in aquatic weed control

A diversidade morfológica da superfície foliar existente entre as espécies de plantas e a presença de estruturas foliares como tricomas, estômatos, cutícula e ceras podem exercer grande influência na aderência e deposição das gotas de pulverização, assim como na absorção do herbicida. Desta forma, o objetivo do presente trabalho foi estudar, em quatro espécies de plantas daninhas aquáticas (Enhydra anagallis, Eichhornia crassipes, Heteranthera reniformis e Typha subulata), a área de molhamento de gotas de pulverização nas superfícies foliares adaxial e abaxial, bem como o pH foliar. O experimento foi realizado em Botucatu-SP. As plantas foram cultivadas em caixas d'água sob condições de campo, e quando atingiram seu pleno desenvolvimento (antes do florescimento), foram realizadas as avaliações de pH foliar e da área de molhamento de gotas de pulverização. As tensões superficiais das gotas aplicadas (0,5 mL), apresentadas pelas soluções de glyphosate aplicado isolado a 5,0% v v-1 (Rodeo 480 g L-1 e.a. produto comercial), glyphosate + Aterbane BR (5,0% + 0,5% v v-1), glyphosate + Silwet L-77 (5,0% + 0,05% v v-1), além das soluções com os adjuvantes isolados, Aterbane BR (0,5% v v-1) e Silwet L-77 (0,05% v v-1) foram respectivamente 72,1; 28,7; 23,3; 37,3 e 22,1 mN m-1. As médias obtidas de pH foliar variaram entre 5,50 e 7,50, destacando-se a espécie E. anagallis com valores de 6,68 e 7,02 para as faces adaxial e abaxial, respectivamente. Dentre as plantas daninhas aquáticas avaliadas T. subulata foi a espécie que apresentou as maiores médias de área de molhamento nas faces adaxial e abaxial da folha, proporcionada pelas as soluções de glyphosate + Aterbane BR, glyphosate + Silwet L-77 e Silwet L-77, com valores de 12,99-7,03; 20,04-17,95 e 31,81-25,91 mm², respectivamente.

Mixed micelles of the anionic surfactant sodium dodecyl sulfate and the nonionic pentaethylene glycol mono-n-dodecyl ether in solution

Dynamic light scattering, surface tension, and clouding temperature have been monitored to elucidate the solution properties of mixed micelles formed between the anionic surfactant sodium dodecyl sulfate (SDS) and the nonionic surfactant pentaethylene glycol mono-n-dodecyl ether (C12E5) over a wide range of surfactant concentration and temperature. Addition of 0.1 M NaCl shifts the relaxational modes to higher frequency and lowers the clouding temperature (T-c) of the nonionic surfactant solution by about 1 degrees C compared to the salt-free system. T-c for the mixed surfactant solutions is higher than that of the binary C12E5 solutions and depends sensitively on the concentration of the two surfactants but increases only slightly when the total surfactant concentration is increased at a given molar C12E5/SDS concentration ratio. With C12E5/SDS = 5.7, for example, T-c is 46.0 and 47.5 degrees C, respectively, at 5 and 70 mM of C12E5 the mixed solutions are homogeneous and stable and contain nonspherical micelles, which are close to monodisperse over a range of surfactant concentrations and temperature. The mixed system has a lower Krafft point than binary SDS solutions and shows an approximately ideal behavior in contrast to the binary C12E5 solution. The hydrodynamic radius (RH) of the mixed micelle increases with temperature as do C12E5 micelles in the binary solutions and also with increasing C12E5/SDS ratio. At 25 degrees C, the critical micelle concentration of the mixed solution lies between those of the individual surfactants and decreases as the C12E5/SDS ratio is increased.

Aggregation behaviour of hydrophobically modified poly(allylammonium) chloride

The behaviour of hydrophobically modified poly(allylammonium) chloride having octyl, decyl, dodecyl and hexadecyl side chains has been studied in aqueous solution using fluorescence emission techniques. Micropolarity studies using the I-1/I-3 ratio of the vibronic bands of pyrene show that the formation of hydrophobic microdomains depends on both the length of the side chain and the polymer concentration. The I-1/I-3 ratio of the polymers with low hydrophobe content (less than 5% mel) changes substantially when reaching a certain concentration. These changes are assigned to aggregation originating from interchain interactions. This behaviour is also confirmed by the behaviour of the monomer/excimer emission intensities of pyrene- dodecanoic acid used as a probe. For polymers having dodecyl side chains and hydrophobe contents higher than 10%, aggregates are formed independently of the polymer concentration. Anisotropy measurements show that microdomains resulting from the inter- and/or intramolecular interactions are similar to those observed for cationic surfactants. Viscosity measurements show that the coil dimensions are substantially decreased for the polymers having high hydrophobe contents, indicating intramolecular associations.

Formation and characterization of soy bean oil/surfactant/water microemulsions

Pseudoternary phase diagrams, at 25 degrees C, were constructed for the systems soy bean oil (SBO)/surfactant/water, with single anionic sodium bis(2-ethylhexyl)sulfosuccinate (AOT), nonionic monoolein (MO) and mixtures of these surfactants, showing the isotropic phase of W/O microemulsions (MEs). The area of ME formation in the phase diagrams was shown to be dependent of the relative amount of surfactants, being larger for MO:AOT equals to 2:1. Rheological and dynamic light scattering (DLS) studies indicated that the viscosity of the isotropic ME phase exhibited two different behaviors depending on composition. The viscosity of dry MEs initially decreased with increasing amount of water following a dilution line in the phase diagram, i.e., a constant surfactant:SBO percentage ratio. As the water content increased the relative viscosity attained a minimum and then increased. This minimum could be related to the transition between two ME regions, L-2 and L'(2), having different characteristics. DLS measurements confirm the existence of ordinary W/O ME droplets in the L-2 region and suggest the existence of another structure in the L'(2) region. The size of the MEs droplets in L-2 phase ranges from 3.6 to 16.5 nm, depending on composition of SBO, surfactant and water. Small angle X-ray scattering (SAXS) also indicates the existence of structures with different characteristics, for the SAXS curves exhibit a typical micelle asymmetrical peak at low scattering vector q for MEs in L-2 but a symmetrical correlation peak at higher q vector in L'(2). (c) 2006 Elsevier B.V. All rights reserved.

beta-ZnMoO4 microcrystals synthesized by the surfactant-assisted hydrothermal method: Growth process and photoluminescence properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Highly swollen liquid crystals as new reactors for the synthesis of nanomaterials

Synthesis and self-assembly of nanomaterials can be controlled by the properties of soft matter. on one hand, dedicated nanoreactors such as reverse microemulsions or miniemulsions can be designed. on the other hand, direct shape control can be provided by the topology of liquid crystals that confine the reacting medium within a specific geometry. In the first case, the preparation of micro- or miniemulsions generally requires energetic mechanical stirring. The second approach uses thermodynamically stable systems, but it remains usually limited to binary (water + surfactant) systems. We report the preparation of different families of materials in highly ordered quaternary mediums that exhibit a liquid crystal structure with a high cell parameter. They were prepared with the proper ratios of salted water, nonpolar solvent, surfactant. and cosurfactants that form spontaneously swollen hexagonal phases. These swollen liquid crystals can be prepared from all classes of surfactants (cationic, anionic, and nonionic). They contain a regular network of parallel cylinders, whose diameters can be swollen with a nonpolar solvent, that are regularly spaced in a continuous aqueous salt solution. We demonstrate in the present report that both aqueous and organic phases can be used as nanoreactors for the preparation of materials. This property is illustrated by various examples such as the synthesis of platinum nanorods prepared in the aqueous phase or zirconia needles or the photo- or gamma-ray-induced polymerization of polydiacetylene in the organic phase. In all cases, materials can be easily extracted and their final shapes are directed by the structure-directing effect imposed by the liquid crystal.