928 resultados para CATIONIC GEMINI SURFACTANTS
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Combating pollution of soils is a challenge that has concerned researchers from different areas and motivated the search for technologies that aim the recovery of degraded soils. Literature shows numerous processes that have been proposed with the intent of remediating soils contaminated by oils and other by-products of the oil industry, considering that the processes available have, generally, high operating costs, this work proposes a costeffective alternative to the treatment of Diesel-contaminated soils. The washing solutions were prepared using water as aqueous phase, the saponified coconut oil (OCS) as surfactant and n-butanol as co-surfactant. In this study, the soil was characterized by physical and chemical analyses. The study of diesel desorption from the soil was held in bath, using hexane and washing solutions, which had 10 and 20 wt.% active matter (AM - co-surfactant/surfactants) respectively. The study of the influence of active matter concentration and temperature in bath agitated used an experimental planning. The experiment also developed a system of percolation in bed to wash the soil and studied the influence of the concentration of active substance and volume of washing solution using an experimental planning. The optimal times to achieve hexane extraction were 30 and 180 min, while the best results using a 10% AM was 60 min and using a 20% AM was 120 min. The results of the experimental planning on bath showed that the maximum diesel removal was obtained when at a 20 wt.% of AM and under 50 °C, removing 99.92% of the oil. As for experiments in the system of percolation soil bed, the maximum diesel removal was high when the volume of the washing solution was of 5 L and the concentration of 20% AM. This experiment concluded that the concentration of AM and the temperature were vital to bath experiments for diesel removal, while in the system of percolation soil bed only concentration of AM influenced the soil remediation
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TiTanate NanoTubes (TTNT) were synthesized by hydrothermal alkali treatment of TiO2 anatase followed by repeated washings with distinct degrees of proton exchange. TTNT samples with different sodium contents were characterized, as synthesized and after heattreatment (200-800ºC), by X-ray diffraction, scanning and transmission electron microscopy, electron diffraction, thermal analysis, nitrogen adsorption and spectroscopic techniques like FTIR and UV-Vis diffuse reflectance. It was demonstrated that TTNTs consist of trititanate structure with general formula NaxH2−xTi3O7·nH2O, retaining interlayer water in its multiwalled structure. The removal of sodium reduces the amount of water and contracts the interlayer space leading, combined with other factors, to increased specific surface area and mesopore volume. TTNTs are mesoporous materials with two main contributions: pores smaller than 10 nm due to the inner volume of nanotubes and larger pores within 5-60 nm attributed to the interparticles space. Chemical composition and crystal structure of TTNTs do not depend on the average crystal size of the precursor TiO2-anatase, but this parameter affects significantly the morphology and textural properties of the nanostructured product. Such dependence has been rationalized using a dissolution-recrystallization mechanism, which takes into account the dissolution rate of the starting anatase and its influence on the relative rates of growth and curving of intermediate nanosheets. The thermal stability of TTNT is defined by the sodium content and in a lower extent by the crystallinity of the starting anatase. It has been demonstrated that after losing interlayer water within the range 100-200ºC, TTNT transforms, at least partially, into an intermediate hexatitanate NaxH2−xTi6O13 still retaining the nanotubular morphology. Further thermal transformation of the nanostructured tri- and hexatitanates occurs at higher or lower temperature and follows different routes depending on the sodium content in the structure. At high sodium load (water washed samples) they sinter and grow towards bigger crystals of Na2Ti3O7 and Na2Ti6O13 in the form of rods and ribbons. In contrast, protonated TTNTs evolve to nanotubes of TiO2(B), which easily convert to anatase nanorods above 400ºC. Besides hydroxyls and Lewis acidity typical of titanium oxides, TTNTs show a small contribution of protonic acidity capable of coordinating with pyridine at 150ºC, which is lost after calcination and conversion into anatase. The isoeletric point of TTNTs was measured within the range 2.5-4.0, indicating behavior of a weak acid. Despite displaying semiconductor characteristics exhibiting typical absorption in the UV-Vis spectrum with estimated bandgap energy slightly higher than that of its TiO2 precursor, TTNTs showed very low performance in the photocatalytic degradation of cationic and anionic dyes. It was concluded that the basic reason resides in its layered titanate structure, which in comparison with the TiO2 form would be more prone to the so undesired electron-hole pair recombination, thus inhibiting the photooxidation reactions. After calcination of the protonated TTNT into anatase nanorods, the photocatalytic activity improved but not to the same level as that exhibited by its precursor anatase
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We report the effect of solvent on the rhodamine 6G encapsuled into channels of mesoporous silica, synthesized by two-step process that gives intermediary stable hybrid micelles. Mesoporous materials have been obtained by the method that involves surfactant micelles (mainly cationic) and inorganic precursor of the structure to be obtained. MSU-X type mesoporous silica has been synthesized with polyethylene oxide surfactant as the directing-structure agent and tetraethyl orthosilicate Si(OEt)(4) as the silica source. The influence of the solvent on the encapsulation of rhodamine dye was systematically explored, specially its influence on the luminescence properties. Rhodamine 6G encapsuled into mesoporous silica channel was characterized by UV-Vis and luminescence spectroscopies, scanning electron microscopy, small angle x ray scattering and N(2) sorption-desorption. The pore size and the solvent effects into luminescence dye encapsuled into mesoporous silica channels are observed in the visible absorption and emission spectra of rhodamine 6G. The intense photo luminescence band of rhodamine 6G dye is in 500 to 600 nm region. The observed shift of the absorption and emission bands can be assigned to the effect of the solvents dielectric constant and pore size of mesoporous silica.
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The present work aims to study the theoretical level of some processes employed in the refining of petroleum fractions and tertiary recovery of this fluid. In the third chapter, we investigate a method of hydrogenation of oil fractions by QTAIM (Quantum Theory of Atoms in Molecules) and thermodynamic parameters. The study of hydrogenation reactions, and the stability of the products formed, is directly related to product improvement in the petrochemical refining. In the fourth chapter, we study the theoretical level of intermolecular interactions that occur in the process of tertiary oil recovery, or competitive interactions involving molecules of non-ionic surfactants, oil and quartz rock where oil is accumulated. Calculations were developed using the semiempirical PM3 method (Parametric Model 3). We studied a set of ten non-ionic surfactants, natural and synthetic origin. The study of rock-surfactant interactions was performed on the surface of the quartz (001) completely hydroxylated. Results were obtained energetic and geometric orientations of various surfactants on quartz. QTAIM was obtained through the analysis of the electron density of interactions, and thus, providing details about the formation of hydrogen bonds and hydrogen-hydrogen systems studied. The results show that the adsorption of ethoxylated surfactants in the rock surface occurs through the hydrogen bonding of the type CH---O, and surfactants derivatives of polyols occurs by OH---O bonds. For structures adsorption studied, the large distance of the surfactant to the surface together with the low values of charge density, indicate that there is a very low interaction, characterizing physical adsorption in all surfactants studied. We demonstrated that surfactants with polar group comprising oxyethylene units, showed the lowest adsorption onto the surface of quartz, unlike the derivatives of polyols
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Innovative technologies using surfactant materials have applicability in several industrial fields, including petroleum and gas areas. This study seeks to investigate the use of a surfactant derived from coconut oil (SCO saponified coconut oil) in the recovery process of organic compounds that are present in oily effluents from petroleum industry. For this end, experiments were accomplished in a column of small dimension objectifying to verify the influence of the surfactant SCO in the efficiency of oil removal. This way, they were prepared emulsions with amount it fastens of oil (50, 100, 200 and 400 ppm), being determined the great concentrations of surfactant for each one of them. Some rehearsals were still accomplished with produced water of the industry of the petroleum to compare the result with the one of the emulsions. According to the experiments, it was verified that an increase of the surfactant concentration does not implicate in a greater oil removal. The separation process use gaseous bubbles formed when a gas stream pass a liquid column, when low surfactant concentrations are used, it occurs the coalescence of the dispersed oil droplets and their transport to the top of the column, forming a new continuous phase. Such surfactants lead to a gas-liquid interface saturation, depending on the used surfactant concentration, affecting the flotation process and influencing in the removal capacity of the oily dispersed phase. A porous plate filter, with pore size varying from 40 to 250 mm, was placed at the base of the column to allow a hydrodynamic stable operation. During the experimental procedures, the operating volume of phase liquid was held constant and the rate of air flow varied in each experiment. The resulting experimental of the study hydrodynamic demonstrated what the capturing of the oil was influenced by diameter of the bubbles and air flow. With the increase flow of 300 about to 900 cm3.min-1, occurred an increase in the removal of oil phase of 44% about to 66% and the removal kinetic of oil was defined as a reaction of 1° order.
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Among the new drugs launched into the market since 1980, up to 30% of them belong to the class of natural products or they have semisynthetic origin. Between 40-70% of the new chemical entities (or lead compounds) possess poor water solubility, which may impair their commercial use. An alternative for administration of poorly water-soluble drugs is their vehiculation into drug delivery systems like micelles, microemulsions, nanoparticles, liposomes, and cyclodextrin systems. In this work, microemulsion-based drug delivery systems were obtained using pharmaceutically acceptable components: a mixture Tween 80 and Span 20 in ratio 3:1 as surfactant, isopropyl mirystate or oleic acid as oil, bidistilled water, and ethanol, in some formulations, as cosurfactants. Self-Microemulsifying Drug Delivery Systems (SMEDDS) were also obtained using propylene glycol or sorbitol as cosurfactant. All formulations were characterized for rheological behavior, droplet size and electrical conductivity. The bioactive natural product trans-dehydrocrotonin, as well some extracts and fractions from Croton cajucara Benth (Euphorbiaceae), Anacardium occidentale L. (Anacardiaceae) e Phyllanthus amarus Schum. & Thonn. (Euphorbiaceae) specimens, were satisfactorily solubilized into microemulsions formulations. Meanwhile, two other natural products from Croton cajucara, trans-crotonin and acetyl aleuritolic acid, showed poor solubility in these formulations. The evaluation of the antioxidant capacity, by DPPH method, of plant extracts loaded into microemulsions evidenced the antioxidant activity of Phyllanthus amarus and Anacardium occidentale extracts. For Phyllanthus amarus extract, the use of microemulsions duplicated its antioxidant efficiency. A hydroalcoholic extract from Croton cajucara incorporated into a SMEDDS formulation showed bacteriostatic activity against colonies of Bacillus cereus and Escherichia coli bacteria. Additionally, Molecular Dynamics simulations were performed using micellar systems, for drug delivery systems, containing sugar-based surfactants, N-dodecylamino-1-deoxylactitol and N-dodecyl-D-lactosylamine. The computational simulations indicated that micellization process for N-dodecylamino-1- deoxylactitol is more favorable than N-dodecyl-D-lactosylamine system.
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Corrosion usually occurs in pipelines, so that it is necessary to develop new surface treatments to control it. Surfactants have played an outstanding role in this field due to its capacity of adsorbing on metal surfaces, resulting in interfaces with structures that protect the metal at low surfactant concentrations. The appearance of new surfactants is a contribution to the area, as they increase the possibility of corrosion control at specific conditions that a particular oil field presents. The aim of this work is to synthesize the surfactants sodium 12 hydroxyocadecenoate (SAR), sodium 9,10-epoxy-12 hydroxyocadecanoate (SEAR), and sodium 9,10:12,13-diepoxy-octadecanoate (SEAL) and apply them as corrosion inhibitors, studying their action in environments with different salinities and at different temperatures. The conditions used in this work were chosen in order to reproduce oil field reality. The study of the micellization of these surfactants in the liquid-gas interface was carried out using surface tensiometry. It was observed that cmc increased as salt concentration was increased, and temperature and pH were decreased, while cmc decreased with the addition of two epoxy groups in the molecule. Using the values of cmc and the Gibbs equation, the values of Gibbs free energy of adsorption, area per adsorbed molecule, and surface excess were calculated. The surface excess increases as salt concentration and temperature decreases, increasing as pH is increased. The area per adsorbed molecule and the free energy of adsorption decrease with salt concentration, temperature, and pH increase. SAXS results showed that the addition of epoxy group in surfactant structure results in a decrease in the repulsion between the micelles, favoring the formation of more oblong micellar structures, ensuring a better efficiency of metal coverage. The increase in salt and surfactant concentrations provides an increase in micellar diameter. It was shown that the increase in temperature does not influence micellar structure, indicating thermal stability that is advantageous for use as corrosion inhibitor. The results of inhibition efficiency for the surfactants SEAR and SEAL were considered the best ones. Above cmc, adsorption occurred by the migration of micelles from the bulk of the solution to the metal surface, while at concentrations below cmc film formation must be due to the adsorption of semi-micellar and monomeric structures, certainly due to the presence of the epoxy group, which allows side interactions of the molecule with the metal surface. The metal resistance to corrosion presented values of 90% of efficiency. The application of Langmuir and Frumkin isotherms showed that the later gives a better description of adsorption because the model takes into account side interactions from the adsorbing molecules. Wettability results showed that micelle formation on the solid surface occurs at concentrations in the magnitude of 10-3 M, which isthe value found in the cmc study. This value also justifies the maximum efficiencies obtained for the measurements of corrosion resistance at this concentration. The values of contact angle as a function of time suggest that adsorption increases with time, due to the formation of micellar structures on metal surface
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During the storage of oil, sludge is formed in the bottoms of tanks, due to decantation, since the sludge is composed of a large quantity of oil (heavy petroleum fractions), water and solids. The oil sludge is a complex viscous mixture which is considered as a hazardous waste. It is then necessary to develop methods and technologies that optimize the cleaning process, oil extraction and applications in industry. Therefore, this study aimed to determine the composition of the oil sludge, to obtain and characterize microemulsion systems (MES), and to study their applications in the treatment of sludge. In this context, the Soxhlet extraction of crude oil sludge and aged sludge was carried out, and allowing to quantify the oil (43.9 % and 84.7 % - 13 ºAPI), water (38.7 % and 9.15 %) and solid (17.3 % and 6.15 %) contents, respectively. The residues were characterized using the techniques of X-ray fluorescence (XRF), Xray diffraction (XRD) and transmission Infrared (FT-IR). The XRF technique determined the presence of iron and sulfur in higher proportions, confirming by XRD the presence of the following minerals: Pyrite (FeS2), Pyrrhotite (FeS) and Magnetite (Fe3O4). The FT-IR showed the presence of heavy oil fractions. In parallel, twelve MES were prepared, combining the following constituents: two nonionic surfactants (Unitol L90 and Renex 110 - S), three cosurfactants (butanol, sec-butanol and isoamyl alcohol - C), three aqueous phase (tap water - ADT, acidic solution 6 % HCl, and saline solution - 3.5 % NaCl - AP) and an oil phase (kerosene - OP). From the obtained systems, a common point was chosen belonging to the microemulsion region (25 % [C+S] 5 % OP and AP 70 %), which was characterized at room temperature (25°C) by viscosity (Haake Rheometer Mars), particle diameter (Zeta Plus) and thermal stability. Mixtures with this composition were applied to oil sludge solubilization under agitation at a ratio of 1:4, by varying time and temperature. The efficiencies of solubilization were obtained excluding the solids, which ranged between 73.5 % and 95 %. Thus, two particular systems were selected for use in storage tanks, with efficiencies of oil sludge solubilization over 90 %, which proved the effectiveness of the MES. The factorial design delimited within the domain showed how the MES constituents affect the solubilization of aged oil sludge, as predictive models. The MES A was chosen as the best system, which solubilized a high amount of aged crude oil sludge (~ 151.7 g / L per MES)
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Alkyl polyethoxylates are surfactants widely used in vastly different fields, from oil exploitation to pharmaceutical applications. One of the most interesting characteristics of these surfactants is their ability to form micellar systems with specific geometry, the so-called wormlike micelle. In this work, microemulsions with three distinct compositions (C/T = 40 %, 30 % and 25 %) was used with contain UNITOL / butanol / water / xylene, cosurfactant / surfactante (C/S) ratio equal to 0,5. The microemulsion was characterized by dynamic light scattering (DLS), capillary viscometry, torque rheometry and surface tensiometry experiments carried out with systems based on xylene, water, butanol (cosurfactant) and nonaethyleneglycolmonododecyl ether (surfactant), with fixed surfactant:cosurfactant:oil composition (with and without oil phase) and varying the overall concentration of the microemulsion. The results showed that a transition from wormlike micelles to nanodrops was characterized by maximum relative viscosity (depending on how relative viscosity was defined), which was connected to maximum effective diameter, determined by DLS. Surface tension suggested that adsorption at the air water interface had a Langmuir character and that the limiting value of the surfactant surface excess was independent of the presence of cosurfactant and xylene. The results of the solubilization of oil sludge and oil recovery with the microemulsion: C/S = 40%, 30% and 25% proved to be quite effective in solubilization of oil sludge, with the percentage of solubilization (%solubilization) as high as 92.37% and enhanced oil recovery rates up to 90.22% for the point with the highest concentration of active material (surfactant), that is, 40%.
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The construction of wells is one of the most important activities of the oil industry. The drilling process is the set of activities and operations to design, program and perform the opening thereof. During this process, the cuttings are removed by the drilling fluid, or mud, and carted to the surface. This fluid is injected into the drill string and returns to the surface through the annular space between the well walls and the drill string. After the descent of the column casing, the annular space between the casing string and the walls of the borehole is filled with cement so as to secure the spine and prevent any migration of fluids between the various permeable zones traversed by the well behind of the coating. To ensure the good quality of the cementation scrubbers are used mattresses which are pumped ahead of the cement slurry so as to avoid contamination of the drilling fluid paste, or vice versa, and assist in the removal of plaster, formed by drilling fluid of the borehole walls, thus enabling a better cement bond to the well. Within this context, this work aims to evaluate the efficiency of mattresses scrubbers, the basis of ionic and nonionic surfactants, on the removal of nonaqueous drilling fluid, based on n-paraffin in oil wells, and the compatibility between the Mattress relations washer / drilling fluid bed scrubber / cement paste mattress washer / cement slurry / drilling fluid and the drilling fluid / cement slurry using laboratory tests rheology, thickening time and compressive strength. Also technique was performed X-ray diffraction (XRD) for a more detailed analysis of these mixtures with hydrated cement paste. In compatibility tests the conditions of temperature and pressure used in the same laboratory procedure simulating the conditions of oil wells, the well is considered the depth of 800 m. The results showed that the compositions of the mattress washer nonionic, KMS obtained a 100% efficient in removing the non-aqueous drilling fluid, and the best formulation showed good results with respect to compliance testing
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A catalyst of great interest to the scientific community tries to unite the structure of ordered pore diameter from mesoporous materials with the properties of stability and acid activity to microporous zeolites. Thus a large number of materials was developed in the past decades, which although being reported as zeolites intrinsically they fail to comply with some relevant characteristics to zeolites, and recently were named zeolitic materials of high accessibility. Among the various synthesis strategies employed, the present research approaches the synthesis methods of crystallization of silanized protozeolitic units and the method of protozeolitic units molded around surfactant micelles, in order for get materials defined as hierarchical zeolites and micro-mesoporous hybrid materials, respectively. As goal BEA/MCM-41 hybrid catalysts with bimodal pore structure formed by nuclei of zeolite Beta and cationic surfactant cetyltrimethylammonium were developed. As also was successfully synthesized the hierarchical Beta zeolite having a secondary porosity, in addition to the typical and uniform zeolite micropores. Both catalysts were applied in reactions of catalytic cracking of high density polyethylene (HDPE), to evaluate its properties in catalytic activity, aiming at the recycling of waste plastics to obtain high value-added raw materials and fuels. The BEA/MCM-41 hybrid materials with 0 days of pre-crystallization did not show enough properties for use in catalytic cracking reactions, but they showed superior catalytic properties compared to those ordered mesoporous materials of Al-MCM-41 type. The structure of Beta zeolite with hierarchical porosity leads the accessibility of HDPE bulky molecules to active centers, due to high external area. And provides higher conversion to hydrocarbons in the gasoline range, especially olefins which have great interest in the petrochemical industry
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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The molecular distillation is show as an alternative for separation and purification of various kinds of materials. The process is a special case of evaporation at high vacuum, in the order from 0.001 to 0.0001 mmHg and therefore occurs at relatively lower temperatures, preserves the material to be purified. In Brazil, molecular distillation is very applied in the separation of petroleum fractions. However, most studies evaluated the temperature of the evaporator, condenser temperature and flow such variables of the molecular distillation oil. Then, to increase the degree of recovery of the fraction of the distillate obtained in the process of the molecular distillation was evaluated the use nonionic surfactants of the class of nonylphenol ethoxylate, molecules able to interact in the liquid-liquid and liquid-vapor interface various systems. In this context, the aim of this work was to verify the influence of commercial surfactant (Ultranex-18 an Ultranex-18-50) in the molecular distillation of a crude oil. The physicochemical characterization of the oil was realized and the petroleum shown an API gravity of 42°, a light oil. Initially, studied the molecular distillation without surfactant using star design experimental (2H ± ) evaluated two variables (evaporator temperature and condenser temperature) and answer variable was the percentage in distillate obtained in the process (D%). The best experimental condition to molecular distillation oil (38% distillate) was obtained at evaporator and condenser temperatures of 120 °C and 10 ° C, respectively. Subsequently, to determine the range of surfactant concentration to be applied in the process, was determined the critical micellar concentration by the technique of scattering X-ray small angle (SAXS). The surfactants Ultranex-18 an Ultranex-18-50 shown the critical micelle concentration in the range of 10-2 mol/L in the hydrocarbons studied. Then, was applied in the study of distillation a concentration range from 0.01 to 0.15 mol/L of the surfactants (Ultranex- 18 and 50). The use of the nonionic surfactant increased the percentage of hydrocarbons in the range from 5 to 9 carbons in comparison to the process carried out without surfactant, and in some experimental conditions the fraction of light compounds in the distilled was over 700% compared to the conventional process. The study showed that increasing the degree of ethoxylation of Ultranex18 to Ultranex-50, the compounds in the range of C5 to C9 reduced the percentage in the distilled, since the increase of the hydrophilic part of the surfactant reduces its solubility in the oil. Finally, was obtained an increase in the degree of recovery of light hydrocarbons, comparing processes with and without surfactant, obtained an increase of 10% and 4% with Ultranex-18 and Ultranex-50, respectively. Thus, it is concluded that the Ultranex- 18 surfactant showed a higher capacity to distillation compared with Ultranex-50 and the application of surfactant on the molecular distillation from petroleum allowed for a greater recovery of light compounds in distillate
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The pharmacokinetics of enrofloxacin (ENRO), a fluoroquinolone antimicrobial agent, was studied in male broiler chickens (Cobb) after single oral administration of 10 mg of ENRO/kg b.w. A high-performance liquid chromatography-photodiode array detector (DAD) (HPLC-DAD) method was developed and validated and used for quantitation of ENRO and its major metabolite ciprofloxacin in plasma. The HPLC analyses were carried out using a cationic-octadecyl mixed column and 0.05 mol/L phosphate buffer (pH 2.5)/acetonitrile as mobile phase. The sample preparation of plasma consisted of the precipitation of proteins followed by solid phase extraction on cationic-octadecyl mixed cartridges. The method was validated considering linear range, linearity, selectivity, sensitivity, limit of detection (LOD), limit of quantitation (LOQ), intra- and inter-day precisions and accuracy. The LOD and LOQ for both fluoroquinolones were 60 and 200 ng/mL for plasma. The plasma concentration vs. time graph was characteristic of a two-compartment open model. The maximal plasma concentration of 1.5 +/- 0.2 mg/mL was achieved at 9 +/- 2 h. The elimination half-life and the mean residence time of ENRO were 1.5 +/- 0.2 and 15.64 h, respectively. The area under the concentration-time curve was calculated as 35 +/- 4 mg(.)h/mL.
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)