ABSTRACT N-Acetylcysteine (NAC) is a thiol (-SH) with a strong antioxidant activity. This compound has demonstrated positive effects on chronic kidney disease, cancer, pulmonary insufficiency and other diseases. The aim of this work was to investigate the application of the Solution Enhanced Dispersion by Supercritical Fluids (SEDS) technique in the micronization of NAC using a 23 Central Composite Design (CCD) with 3 central points, as well as to assess the influence of active compound concentration, temperature and pressure on the particle size produced. The average size of the drug before SEDS processing was verified to be 709.82 µm while the best result led to a particle size of 2.86 µm, which means a reduction of about 248 fold. It was also observed that a reduction in particle size led to an increase in the dissolution rate with 100% dissolution.

ABSTRACT Transesterification of non-edible oils using immobilized lipase is a promising process for biodiesel production. Thus, this study aimed to evaluate the enzymatic transesterification of the non-edible Jatropha curcas oil for FAEE production under ultrasound irradiation in a solvent-free system. The effects of enzyme concentration, water concentration, molar ratio of ethanol to oil and ultrasound power on the FAEE conversion have been evaluated. The results show that enzyme concentration and irradiation power have a positive significant effect on FAEE conversion, where an increase in these variables leads to higher conversions. Conversion above 54% of FAEE was achieved with 1.5 hours of reaction time using ultrasound irradiation, reducing reaction time by at least 3 times, when compared with the same experimental conditions without ultrasound irradiation. Results showed that ultrasound can improve reaction conversion mainly by enhancing the mass transfer between the constituents of the reactions.

The inconveniences of the conventional method for biodiesel production by alkaline catalysis suggests research towards alternative methods, with the non-catalytic transesterification using an alcohol at supercritical conditions proposed as a promising technique for biodiesel production. The so-called supercritical method (SCM) has powerful advantages over conventional techniques, such as fast reaction rates, feedstock flexibility, production efficiency and environmentally friendly benefits. However, application of this methodology has some limitations, like operating conditions (elevated temperature and pressure and higher amounts of alcohol), which result in high energy costs and degradation of the products generated. In this review paper the state of the art in relation to the use of the SCM for biodiesel production is reported and discussed, describing the characteristics of the method, the influence of operational parameters on the ester yield, patents available in the field and the perspectives for application of the technique.

Lipases produced by a newly isolated Sporidiobolus pararoseus strain have potential catalytic ability for esterification reactions. After production, the enzymatic extracts (conventional crude and precipitated, 'CC' and 'CP', and industrial crude and precipitated, 'IC' e 'IP') were partially characterized. The enzymes presented, in general, higher specificity for short chain alcohols and fatty acids. The precipitated extract showed a good thermal stability, higher than that for crude enzymatic extracts. The 'CC' and 'CP' enzymes presented high activities after exposure to pH 6.5 and 40 ºC. On the other hand, the 'IC' and 'IP' extracts kept their activities in a wide range of pH memory but presented preference for higher reaction temperatures. Preliminary studies of application of the crude lipase extract in the enzymatic production of geranyl propionate using geraniol and propionic acid as substrates in solvent-free system led to a reaction conversion of 42 ± 1.5%.

This work is focused on the determination of liquid-liquid equilibrium data for systems containing methyl and ethyl fatty acid esters, water, glycerol and ethanol at temperatures of 303.15 K and 318.15 K using a near-infrared spectroscopy technique (NIR). The NIR method used in this investigation provided quite satisfactory results when compared to conventional analytical techniques and hence can be used as an advantageous tool to quantify the compounds involved in the liquid-liquid equilibrium systems: i) without previous preparation of the samples; ii) with less waste generation; iii) at low cost; and iv) via a non-destructive technique, as sample analyses are made directly, showing good reproducibility and reliability of the data. The NIR method was effective in the use of different temperatures for calibration and validation of the systems under study. Besides, it is shown that extrapolation with the technique may be possible, making LLE predictions feasible for other conditions not used in the calibration procedure.

In Brazil, the species Maytenus aquifolia and Maytenus ilicifolia are widely used in popular medicine in the form of teas for stomach and ulcer illness treatment. Despite the great interest in Maytenus aquifolia therapeutic properties and the fact that it is an abundant and native plant growing in Brazil, there is a lack of information in the literature concerning the extraction at high pressures. In this context, this work is focused on the mathematical modelling of the packed-bed extraction of Maytenus aquifolia with compressed CO2. Three mathematical models were used to represent the experimental data. The experiments were performed in a laboratory-scale unit, evaluating the effects of temperature (293 to 323 K), pressure (100 to 250 bar), and extraction time on the yield of the extracts. Results show that the extraction temperature and solvent density exerted a pronounced effect on yield. The mathematical model of Sovová was the most suitable to represent the experimental extraction data of M. aquifolia.

The lipase produced by a newly isolate Sporidiobolus pararoseus strain has potential catalysis ability for esterification reactions. In order to improve its synthetic activity, this work aimed at optimizing 'synthetic lipase' production by submerged fermentation of a conventional media based on peptone, yeast extract, NaCl and olive oil using experimental design technique. According to the results obtained in the first experimental design (2(4-1)), yeast extract and NaCl concentrations were tested to further optimization by response surface methodology. The maximum 'synthetic lipase' activity obtained was 26.9 U/mL in the optimized media (5.0, 6.8, 7.0 and 1.0% (wt/v) of peptone, yeast extract, NaCl and olive oil, respectively), representing a 6.36-fold increase compared to the initial medium. The time course of 'synthetic lipase' production in the optimized condition was evaluated in terms of synthetic activity, protease activity, biomass and total carbon and the maximum synthetic activity was observed during the stationary phase of growth.

The aim of this work is to report the performance of different supports for the immobilization of commercial porcine pancreatic lipase. The immobilization tests were carried out in several types of Accurel, activated alumina, kaolin, montmorillonite, ion exchange resins and zeolites. The characterization of the supports showed differences in terms of specific area and morphology. The characteristics of the supports influenced the amount of enzyme adsorbed, yield of immobilization and esterification activity of the resulting immobilized catalyst. The clays KSF and natural and pillared montmorillonites presented potential for use as support for lipase immobilization in terms of yield and esterification activity. Yields of immobilization of 76.32 and 52.01% were achieved for clays KSF and natural montmorillonite, respectively. Esterification activities of 754.03, 595.51, 591.88 and 515.71 U.g-1 were obtained for lipases immobilized in Accurel MP-100, Amberlite XAD-2, mordenite and pillared montmorillonite, respectively.

The main focus of this work was to investigate the residual esterification activity and the product conversion after 10 successive cycles of utilization of a commercial lipase in three systems: esterification of 2-ethyl hexanol and palmitic acid in a solvent-free system; esterification of ascorbic acid and palmitic acid in tert-butanol; and transesterification of glycerol and methyl benzoate in 2-propanol. These systems were chosen based on previous results by our research group in terms of product conversion. Before scale-up, there is a need for evaluating several cycles of utilization of the biocatalyst. The esterification of 2-ethyl hexanol showed that after 10 cycles the enzyme retained 90% of its activity. The system consisting of ascorbic acid, palmitic acid, Novozym 435 and tert-butanol showed that a reduction in enzyme activity was accompanied by a reduction in reaction conversion; the same behavior was not observed for the third system.

This work reports high-pressure cloud point data for the quaternary system glycerol + olive oil + n-butane + AOT surfactant. The static synthetic method, using a variable-volume view cell, was employed for obtaining the experimental data at pressures up to 27 MPa. The effects of glycerol/olive oil concentration and surfactant addition on the pressure transition values were evaluated in the temperature range from 303 K to 343 K. For the system investigated, vapor-liquid (VLE), liquid-liquid (LLE) and vapor-liquid-liquid (VLLE) equilibrium were recorded. It was experimentally observed that, at a given temperature and surfactant content, an increase in the concentration of glycerol/oil ratio led to a pronounced increase in the slope of the liquid-liquid coexistence curve. A comparison with results reported for the same system but using propane as solvent showed that much lower pressure transition values are obtained when using n-butane.

Minimization of Gibbs free energy using activity coefficient models and nonlinear equation solution techniques is commonly applied to phase stability problems. However, when conventional techniques, such as the Newton-Raphson method, are employed, serious convergence problems may arise. Due to the existence of multiple solutions, several problems can be found in modeling liquid-liquid equilibrium of multicomponent systems, which are highly dependent on the initial guess. In this work phase stability analysis of liquid-liquid equilibrium is investigated using the NRTL model. For this purpose, two distinct stochastic numerical algorithms are employed to minimize the tangent plane distance of Gibbs free energy: a subdivision algorithm that can find all roots of nonlinear equations for liquid-liquid stability analysis and the Simulated Annealing method. Results obtained in this work for the two stochastic algorithms are compared with those of the Interval Newton method from the literature. Several different binary and multicomponent systems from the literature were successfully investigated.

This work reports the effects of temperature (20 to 50ºC) and pressure (100 to 250 bar) on the extraction yield, chemical characteristics and antimicrobial activity of extracts of Peumus boldus Molina obtained by compressed carbon dioxide extraction. Results showed that the extraction variables affect the extraction yield and the chemical distribution of the major compounds present in the extracts. The extracts were chemically analyzed with regard to 1,8-cineole, trans-sabinene, pinocarveol, pinocarvone, 4-terpineol, ascaridole, piperitone oxide, limonene dioxide and n-eicosane in a GC/MSD. Antimicrobial tests demonstrated that the high-pressure CO2 extracts had activity against 13 bacteria and that better action was verified with extracts obtained at a lower CO2 extraction density and a higher temperature.

There are numerous examples of the importance of small molecule migration in polymeric materials, such as in drying polymeric packing, controlled drug delivery, formation of films, and membrane separation, etc. The Chapman-Enskog kinetic theory of hard-sphere fluids with the Weeks-Chandler-Andersen effective hard-sphere diameter (Enskog-WCA) has been the most fruitful in diffusion studies of simple fluids and mixtures. In this work, the ability of the Enskog-WCA model to describe the temperature and concentration dependence of the mutual diffusion coefficient, D, for a polystyrene-toluene system was evaluated. Using experimental diffusion data, two polymer model approaches and three mixing rules for the effective hard-sphere diameter were tested. Some procedures tested resulted in models that are capable of correlating the experimental data with the refereed system well for a solvent mass fraction greater than 0.3.

Recently, there has been a growing interest in fractionating orange peel oil by the use of supercritical carbon dioxide (SCCO2). However, progress in this area has been hindered by the lack of more comprehensive work concerning the phase equilibrium behavior of the SCCO2-orange peel oil system. In this context, the aim of this work is to provide new phase equilibrium data for this system over a wide range of temperatures and pressures, permitting the construction of coexistence PT-xy curves as well as the P-T diagram. The experiments were performed in a high-pressure variable-volume view cell in the temperature range of 50-70ºC from 70 to 135 atm and in the CO2 mass fraction composition range of 0.35-0.98. Based on the experimental phase equilibrium results, appropriate operating conditions can be set for high-pressure fractionation purposes.

In this work the Enskog solution of the Boltzmann equation, as corrected by Speedy, together with the Weeks-Chandler-Andersen (WCA) perturbation theory of liquids is employed in correlating and predicting self-diffusivities of dense fluids. Afterwards this theory is used to estimate mutual diffusion coefficients of solutes at infinite dilution in sub and supercritical solvents. We have also investigated the behavior of Fick diffusion coefficients in the proximity of a binary vapor-liquid critical point since this subject is of great interest for extraction purposes. The approach presented here, which makes use of a density and temperature dependent hard-sphere diameter, is shown to be excellent for predicting diffusivities in dense pure fluids and fluid mixtures. The calculations involved highly nonideal mixtures as well as systems with high molecular asymmetry. The predicted diffusivities are in good agreement with the experimental data for the pure and binary systems. The methodology proposed here makes only use of pure component information and density of mixtures. The simple algebraic relations are proposed without any binary adjustable parameters and can be readily used for estimating diffusivities in multicomponent mixtures.