Effect of cosurfactant on the supramolecular structure and physicochemical properties of non-ionic biocompatible microemulsions

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

Surfactant-cosurfactant interactions and process parameters involved in the formulation of stable and small droplet-sized benznidazole-loaded soybean O/W emulsions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Reverse Microemulsion Synthesis, Structure, and Luminescence of Nanosized REPO(4):Ln(3+) (RE = La, Y, Gd, or Yb, and Ln = Eu, Tm, or Er)

A surfactant-mediated solution route for the obtainment of nanosized rare-earth orthophosphates of different compositions (LaPO(4):Eu(3+), (Y,Gd)PO(4):Eu(3+),LaPO(4):Tm(3+), YPO(4):Tm(3+), and YbPO(4):Er(3+)) is presented, and the implications of the morphology control on the solids properties are discussed. The solids are prepared in water-in-heptane microemulsions, using cetyltrimethylammonium bromide and 1-butanol as the surfactant and cosurfactant; the alteration of the starting microemulsion composition allows the obtainment of similar to 30 nm thick nanorods with variable length. The morphology and the structure of the solids were evaluated through scanning electron microscopy and through powder X-ray diffractometry; dynamic light scattering and thermal analyses were also performed. The obtained materials were also characterized through vibrational (FTIR) and luminescence spectroscopy (emission/excitation, luminescence lifetimes, chromaticity, and quantum efficiency), where the red, blue, and upconversion emissions of the prepared phosphors were evaluated.

Development and application of NMR techniques to study water-in-CO2 microemulsions

Self-assembly is a phenomenon that occurs frequently throughout the universe. In this work, two self-assembling systems were studied: the formation of reverse micelles in isooctane and in supercritical CO2 (scCO2), and the formation of gels in organic solvents. The goal was the physicochemical study of these systems and the development of an NMR methodology to study them. In this work, AOT was used as a model molecule both to comprehensively study a widely researched system water/AOT/isooctane at different water concentrations and to assess its aggregation in supercritical carbon dioxide at different pressures. In order to do so an NMR methodology was devised, in which it was possible to accurately determine hydrodynamic radius of the micelle (in agreement with DLS measurements) using diffusion ordered spectroscopy (DOSY), the micellar stability and its dynamics. This was mostly assessed by 1H NMR relaxation studies, which allowed to determine correlation times and size of correlating water molecules, which are in agreement with the size of the shell that interacts with the micellar layer. The encapsulation of differently-sized carbohydrates was also studied and allowed to understand the dynamics and stability of the aggregates in such conditions. A W/CO2 microemulsion was prepared using AOT and water in scCO2, with ethanol as cosurfactant. The behaviour of the components of the system at different pressures was assessed and it is likely that above 130 bar reverse microemulsions were achieved. The homogeneity of the system was also determined by NMR. The formation of the gel network by two small molecular organogelators in toluene-d8 was studied by DOSY. A methodology using One-shot DOSY to perform the spectra was designed and applied with success. This yielded an understanding about the role of the solvent and gelator in the aggregation process, as an estimation of the time of gelation.

Fluorinated ionic surfactant microemulsions in hydrofluorocarbon 134a (HFC 134a)

The factors influencing the formation of water-in-134a-propellant microemulsions using the fluorinated ionic surfactants ammonium perfluorooctanoate, ammonium perfluoroheptanoate, and sodium perfluorooctanoate has been determined. None of the fluorinated ionic surfactants could be used to prepare clear, one-phase systems when used as sole surfactant, but they could be when combined with a short-chain fluoro- or hydrocarbon alcohol in surfactant:cosurfactant weight-mixing ratios (K(m)) in the range 1:2 to 2:1. When hydrocarbon alcohols were used this clear region extended over a wide range of compositions and was confirmed by means of photon correlation spectroscopy (PCS) to contain microemulsion droplets in the propellant-rich part of the phase diagram. PCS studies performed in the presence of the water-soluble drug terbutaline sulfate showed that it was possible to solubilize the drug within water-in-propellant microemulsion droplets. These studies confirm for the first time that it is possible to prepare water-in-propellant 134a microemulsions using fluorinated ionic surfactants and to solubilize water-soluble drugs within these systems.

Formation of fluorinated nonionic surfactant microemulsions in hydrofluorocarbon 134a (HFC 134a)

A structurally related series of fluorinated nonionic oxyethylene glycol surfactants of the type C(m)F(2m+1)(CH(2))(n)O[(CH(2)CH(2)O)(p)H], denoted C(m.n)E(p) (where m=4, 6, or 7, m=1 or 2, and p=4 or 6) were synthesized and their surface behavior in aqueous solution was characterized. The ability of these surfactants to form water-in-hydrofluorocarbon (HFC) propellant 134a microemulsions suitable for use in the aerosolized delivery of water-soluble drugs has been investigated. Phase studies showed that, regardless of the composition used, clear one-phase systems could not be prepared if a fluorinated nonionic surfactant was used alone, or in combination with a short or medium fluorocarbon alcohol cosurfactant. Clear one-phase systems could, however, be prepared if a short-chain hydrocarbon alcohol, such as ethanol, n-propanol, or n-pentanol, was used as cosurfactant, with the extent of the one-phase region increasing with decreased chain length of the alcohol cosurfactant. Light-scattering studies on a number of the hydrocarbon-alcoholcontaining systems in the propellant-rich part of the phase diagram showed that only systems prepared with C(4.2)E(6) and propanol contained microemulsion droplets (all other systems investigated were considered to be cosolvent systems).

Investigations into the formation and characterization of phospholipid microemulsions. IV. Pseudo-ternary phase diagrams of systems containing water-lecithin-alcohol and oil; The influence of oil

Phase studies have been performed for quaternary systems composed of egg lecithin, cosurfactant, water and oil. The lecithin used was the commercially available egg lecithin Ovothin 200 (which comprises ≥ 92% phosphatidylcholine). The cosurfactants employed were propanol and butanol, and these were used at lecithin/cosurfactant mixing ratios (Km) of 1:1 and 1.94:1 (weight basis). Six polar oils were investigated, including the alkanoic acids, octanoic and oleic, their corresponding ethyl esters and the medium and long chain triglycerides, Miglyol 812 and soybean oil. All oils, irrespective of the alcohol and the Km used, gave rise to systems that produced a stable isotropic region along the surfactant/oil axis (designated as a reverse microemulsion system). In addition, the systems incorporating propanol at both Km and butanol at a Km of 1.94: 1, generally gave rise to a liquid crystalline region and, in some cases, a second isotropic non-birefingent area (designated as a normal microemulsion system). The phase behaviour observed was largely dependent upon the alcohol and Km used and the size and the polarity of the oil present.

Mixture of changing uniaxial micellar forms in lyotropic biaxial nematics

Lyotropic nematics consisting of surfactant-cosurfactant water solutions may present a biaxial phase or direct U(+) <-> U(-) transitions, in different regions of the temperature-relative concentration phase diagram, for different systems and compositions. We propose that these may be related to changes of uniaxial micellar form, which may occur either smoothly or abruptly. Smooth change of cylinder-like into disc-like shapes requires a distribution of Maier-Saupe interaction constants and we consider two limiting cases for the distribution of forms: a single Gaussian and a double Gaussian. Alternatively, an abrupt change of form is described by a discontinuous distribution of interaction constants. Our results show that the dispersive distributions yield a biaxial phase, while an abrupt change of shape leads to coexistence of uniaxial phases. Fitting the theory to the experiment for the ternary system KL/decanol/D2O leads to transition lines in very good agreement with experimental results. In order to rationalise the results of the comparison, we analyse temperature and concentration form dependence, which connects micellar and experimental macroscopic parameters. Physically consistent variations of micellar asymmetry, amphiphile partitioning and volume are obtained. To the best of the authors` knowledge, this is the first truly statistical microscopic approach that is able to model experimentally observed lyotropic biaxial nematic phases.

Extração de boro de água produzida sintética por sistema microemulsionado

Boron is a semi-metal present in certain types of soils and natural waters. It is essential to the healthy development of plants and non-toxic to humans, depending on its concentration. It is used in various industries and it s present in water production coming from oil production. More specifically in Rio Grande do Norte, one of the largest oil producers on shore of Brazil, the relationship water/oil in some fields becomes more than 90%. The most common destination of this produced water is disposal in open sea after processing to meet the legal specification. In this context, this research proposes to study the extraction of boron in water produced by microemulsion systems for industrial utilization. It was taken into account the efficiency of extraction of boron related to surfactant (DDA and OCS, both characterized by FT-IR), cosurfactant (butanol and isoamyl alcohol), organic phase (kerosene and heptanes) and aqueous phase (solution of boron 3.6 ppm in alkaline pH). The ratio cosurfactant/ surfactant used was four and the percentage of organic phases for all points of study was set at 5%. It was chosen points with the highest percentage of aqueous phase. Each system was designed for three points of different compositions in relation to the constituents of a pseudoternary diagram. These points were chosen according to studies of phase behavior in pseudoternary diagrams made in previous studies. For this research, points were chosen in the Winsor II region. The excess aqueous solution obtained in these systems was separated and analyzed by ICP OES. For the data set obtained, the better efficiency in the extraction of boron was obtained using the system with DAC, isoamyl alcohol and heptanes, which extracted 49% in a single step. OCS was not viable to the extraction of boron by microemulsion system in the conditions defined in this study

Extração de metais (K, Mg, Ba, Ca, Cr, Mn, Li, Fe) de água produzida utilizando sistema microemulsionado

The produced water is a byproduct formed due to production of petroleum and carries with it a high amount of contaminants such as oil particles in suspension, organic compounds and metals. Thus, these latter pollutants are very difficult to treat because of its high solubility in water. The objective of this work is to use and evaluate a microemulsioned system to remove metals ( K , Mg , Ba , Ca , Cr , Mn , Li , Fe ) of synthetic produced water. For the extraction of metals, it was used a pseudoternary diagram containing the following phases: synthetic produced water as the aqueous phase (AP), hexane as organic phase (OP), and a cosurfactant/surfactant ratio equal to four (C/S = 4) as the third phase, where the OCS (saponified coconut oil) was used as surfactant and n-butanol as cosurfactant. The synthetic produced water was prepared in a bench scale and the region of interest in the diagram for the removal of metals was determined by experimental design called. Ten points located in the phase Winsor II were selected in an area with a large amount of water and small amounts of reagents. The samples were analyzed in atomic absorption spectrometer, and the results were evaluated through a statistical assesment, allowing the efficiency analysis of the effects and their interactions. The results showed percentages of extraction above 90% for the metals manganese, iron, chromium, calcium, barium and magnesium, and around 45% for metals lithium and potassium. The optimal point for the simultaneous removal of metals was calculated using statistical artifact multiple response function (MR). This calculation showed that the point of greatest extraction of metals occurs was the J point, with the composition [72% AP, 9% OP, 19% C/S], obtaining a global extraction percentage about 80%. Considering the aspects analyzed, the microemulsioned system has shown itself to be an effective alternative in the extraction of metals on synthetic produced water remediation

Extração de ferro da cera de carnaúba utilizando sistemas microemulsionados

The constant search for biodegradable materials for applications in several fields shows that carnauba wax can be a viable alternative in the manufacturing of biolubricants. Carnauba wax is the unique among the natural waxes to have a combination of properties of great importance. In previous studies it was verified the presence of metals in wax composition that can harm the oxidative stability of lubricants. Considering these factors, it was decided to develop a research to evaluate iron removal from carnauba wax, using microemulsion systems (Me) and perform the optimization of parameters, such as: extraction pH, temperature, extraction time, among others. Iron concentration was determined by atomic absorption and, to perform this analysis, sample digestion in microwave oven was used, showing that this process was very efficient. It was performed some analysis in order to characterize the wax sample, such as: attenuated total reflectance infrared spectroscopy (ATR-IR), thermogravimetry (TG), differential scanning calorimetry (DSC), energy dispersive X-ray fluorescence (EDXRF), scanning electron microscopy (SEM) and melting point (FP). The microemulsion systems were composed by: coconut oil as surfactant, n-butanol as cosurfactant, kerosene and/or heptanes as oil phase, distilled water as water phase. The pH chosen for this study was 4.5 and the metal extraction was performed in finite experiments. To evaluate Me extraction it was performed a factorial design for systems with heptane and kerosene as oil phase, also investigating the influence of temperature time and wax/Me ratio, that showed an statistically significant answer for iron extraction at 95% confidence level. The best result was obtained at 60°C, 10 hours contact time and 1: 10 wax/Me ratio, in both systems with kerosene and heptanes as oil phase. The best extraction occurred with kerosene as oil phase, with 54% iron removal

Estudo de sistemas microemulsionados utilizando água do mar na recuperação avançada de petróleo

Petroleum exists in the nature in certain underground formations where it is adsorbed into the rocks pores. For the conventional recovery methods usually only 30% of the oil is extracted and this can be credited, basically, to three aspects: high viscosity of the oil, geology of the formation and high interfacial tensions between the reservoir s fluids. The enhanced recovery methods use the injection of a fluid or fluids mixture in a reservoir to act in points where the conventional process didn't reach the recovery rates. Microemulsion flooding, considered an enhanced method, has the purpose to desorb the oil from the rock formation and to attain an efficient displacement of the oil emulsion. With this in mind, this work was accomplished with two main objectives: the study of the parameters effect that influence a microemulsified system (surfactant and cosurfactant types, C/S rate and salinity) and the evaluation of displacement efficiency with the microemulsions that showed stability in the rich aqueous area. For the analyzed parameters it was chose the microemulsions composition used in the recovery stage: 25% water, 5% kerosene, 46.7% of butanol as cosurfactant and 23.3% of BC or SCO cosurfactant. The core plugs of Assu and Botucatu sandstones were appraised in porosity and permeability tests and then submitted to the steps of saturation with seawater and oil, conventional recovery with water and enhanced recovery with the selected microemulsions. The Botucatu sandstone presented better recovery parameters, and the microemulsion composed with BS surfactant had larger recovery efficiency (26.88%)

Sistemas microemulsionados aplicados à remoção da cor de efluente têxtil

Effluent color resulting from textile dyeing processes has been one of the biggest environmental problems faced by the textile industry. In particular, reactive dyes are highly resistant to conventional wastewater treatment methods. New technologies have been contemplated, some of which have been applied in industrial treatment plants, but color removal has not been efficiently attained. Since microemulsion systems provide good results in heavy metals and proteins extraction processes, their use in dyes extraction has been suggested and investigated. In this work, a real textile wastewater from an exhaustion dyebath has been treated, which contains the following reactive dyes: Procion Yellow H-E4R (CI Reactive Yellow 84), Procion Blue H-ERD (CI Reactive Blue 160) and Procion Red H-E3B (CI Reactive Red 120), in addition to auxiliary compounds normally found in dyeing processes with reactive dyes. The dyes Remazol Blue RR and Remazol Turquoise Blue G (Reactive Blue 21) have also been examined in view of the presence of heavy metals in these molecules. The microemulsion system comprised dodecyl ammonium chloride (as a cationic surfactant), water or wastewater as aqueous phase, kerosene as oil phase, and one of the following alcohols as cosurfactant: isoamyl alcohol, n-butyl alcohol and n-octyl alcohol. The pseudo-ternary diagrams were constructed in order to define Winsor s equilibrium regions. The influence of parameters such as pH, C/S (cosurfactant/surfactant) ratio, distribution coefficient, initial dye concentration, salinity, temperature, phases relative amounts, loading capacity of the microemulsion phase and dye reextraction rate has also been investigated. An experimental planning (Scheffé Net) was used to optimize the extraction process. The removal of color and metals reached levels as high as 99%

Estudo da influência de tensoativos em sistemas microemulsionados na extração de gálio e alumínio

Gallium is an important material used in the electronic industry whose demand in the world market is increasing in view of its potential applications. A selective technique is required to allow for the production of the metal, separated from aluminium. Due to the fact that microemulsions constitute an attractive alternative to metal extraction procedures, microemulsified systems have been employed as gallium-selective extraction agents. Two surfactants have been synthesized: sodium 12-N,N-diethylamino-9,10-dihydroxyestearate (AMINE) and saponified coconut oil (SCO), both produced from raw materials readily available in Northeastern Brazil. Also, the commercial extraction agent KELEX-100, conventionally used with the same purpose, has been used in this work for comparison. The optimization of the extraction process with microemulsions was carried out by investigating the influence of some parameters, namely the type of cosurfactant, the cosurfactant/surfactant (C/S) ratio, the pH and concentration of metals in the aqueous phase. Pseudoternary diagrams, which are representative of the microemulsified systems under study, have been constructed in order to establish the boundaries of the regions where the several Winsor systems are formed. An experimental planning methodology (Scheffé Net) has been used to optimize the extraction. The extraction percentage values were as high as 100% for gallium and 99.99% for aluminium for the system with KELEX-100; 96.6% for gallium and 98.8% for aluminium for the system containing AMINE; and 88% for gallium and 85% for aluminium for the system with SCO. The microemulsified system chosen for presenting the best results in gallium extraction was composed by SCO/isoamyl alcohol/kerosene/Bayer licquor with a C/S ratio of 28 and pH of the original aqueous phase of 6.0. The selectivity that has not been observed in the extraction stage was accomplished in the reextraction process using HCl. For the KELEX-100 system, gallium was reextracted at 100% with 6M HCl and aluminium was reextracted at 100% with 0.8M HCl. For the AMINE system, the reextraction percentages were also 100% for both metals, using 6M HCl for gallium and 0.5M HCl for aluminium. On the other hand, the reextraction percentages for the system with SCO were as high as 84% for gallium and 92% for aluminium, with HCl in the same concentrations as those used in the AMINE system. Finally, an optimized system was applied in the gallium extraction process employing a reciprocating perforated-plates extractor. As a result, the metal content was extracted at a recovery rate of 95% for gallium and 97% for aluminium

Novas alternativas de remoção de enxofre do óleo diesel utilizando tensoativos e microemulsões

The diesel combustion form sulfur oxides that can be discharged into the atmosphere as particulates and primary pollutants, SO2and SO3, causing great damage to the environment and to human health. These products can be transformed into acids in the combustion chamber, causing damage to the engines. The worldwide concern with a clean and healthy environment has led to more restrictive laws and regulations regulating the emission levels of pollutants in the air, establishing sulfur levels increasingly low on fuels. The conventional methods for sulfur removal from diesel are expensive and do not produce a zero-level sulfur fuel. This work aims to develop new methods of removing sulfur from commercial diesel using surfactants and microemulsion systems. Its main purpose is to create new technologies and add economic viability to the process. First, a preliminary study using as extracting agent a Winsor I microemulsion system with dodecyl ammonium chloride (DDACl) and nonyl phenol ethoxylated (RNX95) as surfactant was performed to choose the surfactant. The RNX95 was chosen to be used as surfactant in microemulsioned systems for adsorbent surface modification and as an extracting agent in liquid-liquid extraction. Vermiculite was evaluated as adsorbent. The microemulsion systems applied for vermiculite surface modification were composed by RNX95 (surfactant), n-butanol (cosurfactant), n-hexane (oil phase), and different aqueous phases, including: distilled water (aqueous phase),20ppm CaCl2solution, and 1500ppm CaCl2solution. Batch and column adsorption tests were carried out to estimate the ability of vermiculite to adsorb sulfur from diesel. It was used in the experiments a commercial diesel fuel with 1,233ppm initial sulfur concentration. The batch experiments were performed according to a factorial design (23). Two experimental sets were accomplished: the first one applying 1:2 vermiculite to diesel ratio and the second one using 1:5 vermiculite to diesel ratio. It was evaluated the effects of temperature (25°C and 60°C), concentration of CaCl2in the aqueous phase (20ppm and 1500ppm), and vermiculite granule size (65 and 100 mesh). The experimental response was the ability of vermiculite to adsorb sulfur. The best results for both 1:5 and 1:2 ratios were obtained using 60°C, 1500ppm CaCl2solution, and 65 mesh. The best adsorption capacities for 1:5 ratio and for 1:2 ratio were 4.24 mg sulfur/g adsorbent and 2.87 mg sulfur/g adsorbent, respectively. It was verified that the most significant factor was the concentration of the CaCl2 solution. Liquid-liquid extraction experiments were performed in two and six steps using the same surfactant to diesel ratio. It was obtained 46.8% sulfur removal in two-step experiment and 73.15% in six-step one. An alternative study, for comparison purposes, was made using bentonite and diatomite asadsorbents. The batch experiments were done using microemulsion systems with the same aqueous phases evaluated in vermiculite study and also 20ppm and 1500 ppm BaCl2 solutions. For bentonite, the best adsorption capacity was 7.53mg sulfur/g adsorbent with distilled water as aqueous phase of the microemulsion system and for diatomite the best result was 17.04 mg sulfur/g adsorbent using a 20ppm CaCl2solution. The accomplishment of this study allowed us to conclude that, among the alternatives tested, the adsorption process using adsorbents modified by microemulsion systems was considered the best process for sulfur removal from diesel fuel. The optimization and scale upof the process constitutes a viable alternative to achieve the needs of the market