Supramolecular assemblies of a new class of nonplanar cationic metalloporphyrins and anionic metallophthalocyanines

The heteroaggregation behavior between a new class of nonplanar cationic beta-octabrominated meso-alkylpyridinium zinc(II)-porphyrins (beta-Br(8)(ZnP)) and anionic tetrasulfonated metallophthalocyanines (MTSPc, M = Ni(II) and Cu(II)) has been studied by UV-Vis electronic spectroscopy, in dimethylsulfoxide (DMSO) solution. The heteroaggregate stoichiometry and the association constants were determined by means of Job plots. Dimers and unexpected trimers, taking into account the existence of axially coordinated DMSO molecules to the central metal in both beta-Br(8)(ZnP) and MTSPc complexes, are formed in solution. The spectroscopic properties of the heteroaggregates are markedly different from those observed in the correspondent planar cationic derivatives, the heteroaggregates showing major changes predominantly in the beta-Br(8)(ZnP) Soret band region and minor effects in the MTSPc Q bands. The observed changes in the Soret band region (red/blue shifts, decrease in the absorption intensities) depend on the nature of the alkyl substituent attached to the meso-pyridinium group. The greater versatility of the nonplanar porphyrins accommodating the meso-substituents in out-of-plane and in-plane conformations is proposed to explain the observed stoichiometries and the differences on the heteroaggregates spectroscopic properties for each beta-Br(8)(ZnP) compound. The likely conformations assumed by the meso-substituents in these beta-Br(8)(ZnP) compounds and its spectroscopic characteristics are in accordance with the participation of the substituents as the main factor on the extent of the observed red-shifted spectra in nonplanar porphyrins. The obtained association constants (K(IP)) for the dimers and trimers are lower than those previously found for the similar planar cationic porphyrin systems, due to the lack of extensive pi-pi interactions and to the less effective approximation between the ionic groups, resulting in loosened heteroaggregates, particularly for the trimeric systems. Furthermore, the experimental results suggest that the NiTSPc is more distorted in DMSO solution than the CuTSPc derivative, favoring the interaction with the nonplanar beta-Br(8)(ZnP) compounds. (C) 2007 Elsevier B.V. All rights reserved.

Structure and Applications of a Rhamnolipid Surfactant Produced in Soybean Oil Waste

Soybean oil soapstock was utilized as an alternative carbon source for the production of rhamnolipids by Pseudomonas aeruginosa LBI strain. The chemical composition and properties of the rhamnolipid mixture obtained were determined to define its potential applications. The chemical characterization of the rhamnolipid has revealed the presence of ten different homologues. The monorhamnolipid RhaC(10)C(10) and the dirhamnolipid Rha(2)C(10)C(10) were the main components of the mixture that showed predominance of 44% and 29%, respectively, after 144-h of cultivation. The biosurfactant was able to form stable emulsions with several hydrocarbons and showed excellent emulsification for soybean oil and chicken fat (100%). The rhamnolipid removed 67% of crude oil present in sand samples and presented antimicrobial activity against Bacillus cereus and Mucor miehei at 64 mu g/mL and inhibition of Neurospora crassa, Staphylococcus aureus, and Micrococcus luteus at 256 mu g/mL. The results demonstrated that the rhamnolipid produced in soybean oil soapstock can be useful in environmental and food industry applications.

On the interaction of bovine serum albumin with ionic surfactants: Temperature induced EPR changes of a maleimide nitroxide reflect local protein dynamics and probe solvent accessibility

The interaction of bovine serum albumin (BSA) with the ionic surfactants sodium dodecylsulfate (SDS, anionic), cetyltrimethylammonium chloride (CTAC, cationic) and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS, zwitterionic) was studied by electron paramagnetic resonance (EPR) spectroscopy of spin label covalently bound to the single free thiol group of the protein. EPR spectra simulation allows to monitor the protein dynamics at the labeling site and to estimate the changes in standard Gibbs free energy, enthalpy and entropy for transferring the nitroxide side chain from the more motionally restricted to the less restricted component. Whereas SDS and CTAC showed similar increases in the dynamics of the protein backbone for all measured concentrations. HPS presented a smaller effect at concentrations above 1.5 mM. At 10 mM of surfactants and 0.15 mM BSA, the standard Gibbs free energy change was consistent with protein backbone conformations more expanded and exposed to the solvent as compared to the native protein, but with a less pronounced effect for HPS. In the presence of the surfactants, the enthalpy change, related to the energy required to dissociate the nitroxide side chain from the protein, was greater, suggesting a lower water activity. The nitroxide side chain also detected a higher viscosity environment in the vicinity of the paramagnetic probe induced by the addition of the surfactants. The results suggest that the surfactant-BSA interaction, at higher surfactant concentration, is affected by the affinities of the surfactant to its own micelles and micelle-like aggregates. Complementary DLS data suggests that the temperature induced changes monitored by the nitroxide probe reflects local changes in the vicinity of the single thiol group of Cys-34 BSA residue. (C) 2011 Elsevier B.V. All rights reserved.

THERMAL BEHAVIOR OF IN VITRO MINERALIZED ANIONIC COLLAGEN MATRICES

In the present study porcine skin and bovine pericardium were used as a source of type I collagen. Both were submitted to an alkaline treatment and mineralized by the alternate soaking method. Thermal stability and extent of mineralization have been investigated using DSC and TG. After alkaline hydrolysis there is a decrease in thermal stability but mineralization stabilizes collagen structure. Thermogravimetric data have shown that the amount of hydroxyapatite present in bovine pericardium matrix (45%) was greater than on porcine skin matrix (20%). Presence of hydroxyapatite was confirmed by EDX.

Estrutura e dinâmica da interação de éteres de celulose com surfactantes

As técnicas de fluorimetria, condutometria, viscosimetria, turbidimetria, espalhamento de luz e espalhamento de raios-X a baixo ângulo (SAXS) foram empregadas no estudo da agregação de diferentes surfactantes aniônicos em presença de soluções aquosas diluídas de (hidroxipropil)celulose (HPC) 0,25% m/m, (hidroxipropilmetil)celulose (HPMC) 0,20% m/m e HPMC 0,10% m/m / NaCl 0,10 mol L-1. Também foram investigadas através de SAXS soluções concentradas de HPC (30, 40 e 50% m/m). Admitindo-se uma faixa geral de concentração, entre 10-4 e 10-1 mol L-1, foram utilizados neste estudo os surfactantes colato de sódio (CS), deoxicolato de sódio (DC), derivados dos sais biliares, e o alquilsintético dodecilsulafato de sódio (SDS). Observou-se que os polímeros contribuem diferentemente no processo de agregação de cada surfactante, evidenciado pela mudança dos valores da concentração de agregação crítica (CAC) em relação à concentração micelar crítica (CMC). Os resultados condutométricos confirmaram a interação éteres de celulose/sais biliares, embora a mesma tenha se mostrado mais fraca em relação a éteres de celulose/SDS. Os dados termodinâmicos demonstraram que a formação de agregados polímero/surfactante apresenta maior estabilidade do que as próprias micelas livres. Os resultados de viscosimetria e turbidimetria evidenciaram as diferenças estruturais entre HPC e HPMC, assim como entre os surfactantes. Através do espalhamento de luz dinâmico, verificou-se a existência de dois modos de correlação, rápido e lento. O primeiro é atribuído à cadeia polimérica isolada, agregados polímero/surfactante intramoleculares ou mesmo a micelas livres. Por sua vez, o modo lento relaciona-se a clusters poliméricos ou agregados polímero/surfactante intermoleculares. Adicionalmente, as curvas de distribuição dos tempos de relaxação demonstraram a influência de cada surfactante sobre a dinâmica dos polímeros. Tal influência é percebida antes mesmo da CAC, contrariando o modelo da interação polímero/surfactante proposto por Cabane. Os resultados de SAXS acusaram a formação de domínios líquido-cristalinos em xx soluções concentradas de HPC, assim como confirmaram a presença de micelas livres a altas concentrações de surfactantes nos sistemas diluídos. Em linhas gerais, os resultados indicaram a interação dos polímeros com SDS mais efetiva do que os mesmos polímeros e os sais biliares. No que tange à natureza do polímero, a HPC mostrou uma maior estabilidade na sua interação com os surfactantes do que a HPMC.

On the interaction of bovine serum albumin with ionic surfactants: Temperature induced EPR changes of a maleimide nitroxide reflect local protein dynamics and probe solvent accessibility

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

THE EFFECT of ANIONIC SORPTION on THE METAKAOLINITE

This paper reports an investigation on the effect of thermal activation of kaolinite. It is well known that during calcinations (400-650 degrees C), kaolinite loses the OH lattice water and is transformed into metakaolinite or amorphous material. Arsenic is trace element that is toxic to animals including humans. The adsorption of arsenic on kaolinite was investigated at varying pH and thermal pretreatment. Calcination of sample is carried out at 650 degrees C for 3 h. The decomposition of kaolinite is recorded using methods of thermal analysis. The resultant product is identified by XRD. Laboratory experiments were conducted examining the effect of arsenic by thermally modified kaolinite. The Langmuir isotherm was used to describe arsenite and arsenate sorption by the calcined kaolinite. The equilibrium parameters used were based on experimental data obtained for the dynamic adsorption process of arsenic. Removal of arsenate using natural kaolinite was satisfactory, whereas arsenic was not removed by adsorption with thermally modified kaolinite. Moreover, the adsorption of arsenic by kaolinite and metakaolinite decreases with increasing pH.

Selection of surfactant compounds to enhance the dispersion of Beauveria bassiana

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Remoção conjugada de metais e óleo de água produzida

Petroleum can be associated or not with natural gas, but in both cases water is always present in its formation. The presence of water causes several problems, such as the difficulty of removing the petroleum from the reservoir rock and the formation of waterin-oil and oil-in-water emulsions. The produced water causes environmental problems, which should be solved to reduce the effect of petroleum industry in the environment. The main objective of this work is to remove simultaneously from the produced water the dispersed petroleum and dissolved metals. The process is made possible through the use of anionic surfactants that with its hydrophilic heads interacts with ionized metals and with its lipophilic tails interacts with the oil. The studied metals were: calcium, magnesium, barium, and cadmium. The surfactants used in this research were derived from: soy oil, sunflower oil, coconut oil, and a soap obtained from a mixture of 5wt.% coconut oil and 95wt.% animal fat. It was used a sample of produced water from Terminal de São Sebastião, São Paulo. As the concentration of the studied metals in produced water presented values close to 300 mg/L, it was decided to use this concentration as reference for the development of this research. Molecular absorption and atomic absorption spectroscopy were used to determine petroleum and metals concentrations in the water sample, respectively. A constant pressure filtration system was used to promote the separation of solid and liquid phases. To represent the behavior of the studied systems it was developed an equilibrium model and a mathematical one. The obtained results showed that all used surfactants presented similar behavior with relation to metals extraction, being selected the surfactant derived from soy oil for this purpose. The values of the partition coefficients between the solid and liquid phases " D " for the studied metals varied from 0.2 to 1.1, while the coefficients for equilibrium model " K " varied from 0.0002 and 0.0009. The removal percentile for oil with all metals associated was near 100%, showing the efficiency of the process

Síntese e caracterização de tensoativos e estudo de equilíbrio de fase dos sistemas CnH2n+2/H2O/CnH2n+1COONa/But-OH

The growing utilization of surfactants in several different areas of industry has led to an increase on the studies involving solutions containing this type of molecules. Due to its amphiphilic nature, its molecule presents one polar part and one nonpolar end, which easily interacts with other molecules, being able to modify the media properties. When the concentration in which its monomers are saturated, the airliquid system interface is reached, causing a decrease in interfacial tension. The surfactants from pure fatty acids containing C8, C12 and C16 carbonic chains were synthesized in an alcoholic media using sodium hydroxide. They were characterized via thermal analysis (DTA and DTG) and via infrared spectroscopy, with the intention of observing their purity. Physical and chemical properties such as superficial tension, critical micelle concentration (c.m.c), surfactant excess on surface and Gibbs free energy of micellization were determined in order to understand the behaviour of these molecules with an aqueous media. Pseudo-ternary phase diagrams were obtained aiming to limit the Windsor equilibria conditions so it could be possible to understand how the surfactants carbonic chain size contributes to the microemulsion region. Solutions with known concentrations were prepared to study how the surfactants can influence the dynamic light scattering spectroscopy (DLS) and how the diffusion coefficient is influenced when the media concentration is altered. The results showed the variation on the chain size of the studied surfactant lipophilic part allows the conception of surfactants with similar interfacial properties, but dependent on the size of the lipophilic part of the surfactant. This variation causes the surfactant to have less tendency of microemulsionate oil in water. Another observed result is that the n-alcanes molecule size promoted a decrease on the microemulsion region on the obtained phase diagrams

Electrical properties of polymer/metal interface in polymer light-emitting devices: electron injection barrier suppression

The electrical characterization of a high efficient multilayer polymer light emitting diode using poly[(2-methoxy-5-hexyloxy)-p-phenylenevinylene] as the emissive layer and an anionic fluorinated surfactant as the electron transport layer was performed. For the sake of comparison, a conventional single layer device was fabricated. The density current vs. voltage measurements revealed that the conventional device has a higher threshold voltage and lower current compared to the surfactant modified device. The effective barrier height for electron injection was suppressed. The influence of the interfaces and bulk contributions to the dc and high frequencies conductivities of the devices was also discussed. (c) 2006 Springer Science + Business Media, Inc.

Enhanced stabilization of aerosol-OT surfactant monolayer upon interaction with small amounts of bovine serum albumin at the air-water interface

An investigation is made of the influence from small amounts of the protein bovine serum albumin (BSA) on the lateral organization of low molecular weight surfactant sodium bis-2-ethylhexyl sulfosuccinate (AOT) at the air-water interface. Surface pressure (pi - A), surface potential (DeltaV - A) and Brewster angle microscopy (BAM) experiments were carried out, with particular emphasis on the monolayer stability under successive compression-expansion cycles. AOT monolayer is not stable at the air-water interface, which means that the majority of AOT molecules go into the aqueous subphase as monomers and/or normal micelles. When a waiting time elapses between spreading and compression, the surfactant monolayer tends to reorganize partially at the air-water interface, with a monolayer expansion being observed for waiting times as large as 12 h. The incorporation of very small amount of BSA (10(-9) M) at the interface, also inferred from BAM, increases the monolayer stability as revealed by pi - A and DeltaV - A results. For a waiting time of circa 3 h, the mixed monolayer reaches its maximum stability. This must be related to protein (and/or protein-surfactant complexes) adsorbed onto the AOT monolayer, thus altering the BSA conformation to accommodate its hydrophobic/hydrophilic residues. Furthermore, the effects from such small amounts of BSA in the monolayer formation and stabilization mean that the AOT monolayer responds cooperatively to BSA. (C) 2004 Elsevier B.V. All rights reserved.

Rheological, Mechanical and Adhesive Properties of Surfactant-Containing Systems Designed as a Potential Platform for Topical Drug Delivery

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

Structural Properties Induced by the Composition of Biocompatible Phospholipid-Based Microemulsion and Amphotericin B Association

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

Development and In Vitro Evaluation of Surfactant Systems for Controlled Release of Zidovudine

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)