Supercritical CO2 extraction of phenolic compounds from Baccharis dracunculifolia

Extracts from Baccharis dracunculifolia leaves were obtained using the following solvents: supercritical carbon dioxide (SC-CO2), ethanol and methanol. Supercritical extraction was carried out at temperatures of 40, 50 and 60 degrees C and pressures of 20, 30 and 40 MPa. Four phenolic compounds were analysed in the extracts by high-performance liquid chromatography: 3,5-diprenyl-4-hydroxycinnamic acid (DHCA or artepillin C); 3-prenyl-4-hydroxycinnamic acid (PHCA); 4-hydroxycinnamic acid (p-coumaric acid) and 4-methoxy-3,5,7-trihydroxyflavone (kaempferide). The global extraction yields (X-0) obtained by the conventional methods with ethanol and methanol were higher than those obtained by SC-CO2. However on analysing the components of interest extracted at 60 degrees C and 40 MPa, the extraction yields of kaempferide, DHCA and PHCA were 156%, 98% and 64% higher, respectively, than in the ethanolic extracts. Only the p-coumaric acid extraction yield was better when extracted using the conventional method. (C) 2008 Elsevier B.V. All rights reserved.

Enzyme Microheterogeneous Hydration and Stabilization in Supercritical Carbon Dioxide

Supercritical carbon dioxide is a promising green-chemistry solvent for many enzyme-catalyzed chemical reactions, yet the striking stability of some enzymes in such unconventional environments is not well understood. Here, we investigate the stabilization of the Candida antarctica Lipase B (CALB) in supercritical carbon dioxide-water biphasic systems using molecular dynamics simulations. The preservation of the enzyme structure and optimal activity depend on the presence of small amounts of water in the supercritical dispersing medium. When the protein is at least partially hydrated, water molecules bind to specific sites on the enzyme surface and prevent carbon dioxide from penetrating its catalytic core. Strikingly, water and supercritical carbon dioxide cover the protein surface quite heterogeneously. In the first solvation layer, the hydrophilic residues at the surface of the protein are able to pin down patches of water, whereas carbon dioxide solvates preferentially hydrophobic surface residues. In the outer solvation shells, water molecules tend to cluster predominantly on top of the larger water patches of the first solvation layer instead of spreading evenly around the remainder of the protein surface. For CALB, this exposes the substrate-binding region of the enzyme to carbon dioxide, possibly facilitating diffusion of nonpolar substrates into the catalytic funnel. Therefore, by means of microheterogeneous solvation, enhanced accessibility of hydrophobic substrates to the active site can be achieved, while preserving the functional structure of the enzyme. Our results provide a molecular picture on the nature of the stability of proteins in nonaqueous media.

Chemical evaluation and thermal behavior of Brazil nut oil obtained by different extraction processes

Brazil nut richness has been widely studied aiming at finding transformation models that increase its yield, keep its quality, reduce costs, and increase its productivity. The objective of this study is to evaluate the spectroscopic profile and the chemical and thermal behavior of Brazil nut oil obtained by different extraction processes. Lipid soxhlet extractions with petroleum ether and hexane, and using hydraulic pressing and supercritical carbon dioxide (CO2) were performed. The physicochemical analyses showed an acidity index with significant differences between the samples obtained by hydraulic pressing and supercritical CO2. The peroxide index presented significant difference for the oil obtained by hydraulic pressing compared to that obtained by the other extraction processes. The fatty acid profiles showed a relevant presence of the omega series (w-3, w-6, and w-9) with significant differences for the extraction processes evaluated. The results of the thermogravimetric and differential analyses did not indicate changes in mass loss and presented predominantly exothermic behavior. The spectroscopic profiles indicate that the extraction processes do not change the spectral profile of the oils. (c) 2011 Elsevier Ltd. All rights reserved.

Linear parameter varying control design for rotating systems supported by journal bearings

Linear parameter varying (LPV) control is a model-based control technique that takes into account time-varying parameters of the plant. In the case of rotating systems supported by lubricated bearings, the dynamic characteristics of the bearings change in time as a function of the rotating speed. Hence, LPV control can tackle the problem of run-up and run-down operational conditions when dynamic characteristics of the rotating system change significantly in time due to the bearings and high vibration levels occur. In this work, the LPV control design for a flexible shaft supported by plain journal bearings is presented. The model used in the LPV control design is updated from unbalance response experimental results and dynamic coefficients for the entire range of rotating speeds are obtained by numerical optimization. Experimental implementation of the designed LPV control resulted in strong reduction of vibration amplitudes when crossing the critical speed, without affecting system behavior in sub- or supercritical speeds. (C) 2012 Elsevier Ltd. All rights reserved.

Glycerol as a by-product of biodiesel production in Brazil: Alternatives for the use of unrefined glycerol

On January 1 2008, Brazil included yet another element into its energy matrix: biodiesel. The predominant biodiesel production process involves a phase of transesterification that yields glycerol as a by-product. The use of this glycerol is limited since it is considered an unrefined raw material that must be refined for its various types of use. Several studies have addressed identification of possible uses for unrefined glycerol. Given the diversity of uses, an overview is necessary. The purpose of this work is to present alternatives currently being considered for the use of unrefined glycerol as a by-product of biodiesel production, aiming to contribute to the sustainable consolidation of the biofuel market. Exploratory research was carried out to identify these viable alternatives for the use of this by-product. The possibilities include the production of chemical products, fuel additives, production of hydrogen, development of fuel cells, ethanol or methanol production, animal feed, co-digestion and co-gasification, and waste treatment among others. The present research reveals that there are promising possibilities for the use of unrefined glycerol, which may help consolidate the sustainability of the biofuel market. (C) 2012 Elsevier Ltd. All rights reserved.

Fractionation of lemon essential oil by solvent extraction: Phase equilibrium for model systems at T=298.2 K

The fractioning of lemon essential oil can be performed by liquid-liquid extraction using hydrous ethanol as a solvent. A quaternary mixture composed of limonene, gamma-terpinene, beta-pinene, and citral was used to simulate lemon essential oil. In this paper, we present (liquid + liquid) equilibrium data that were experimentally determined for systems containing essential oil compounds, ethanol, and water at T = 298.2 K. The experimental data were correlated using the NRTL and UNIQUAC models, and the mean deviations between calculated and experimental data were less than 0.0053 in all systems, indicating the accuracy of these molecular models in describing our systems. The results show that as the water content in the solvent phase increased, the values of the distribution coefficients decreased, regardless of the type of compound studied. However, the oxygenated compound always showed the highest distribution coefficient among the components of the essential oil, thus making deterpenation of the lemon essential oil a feasible process. (C) 2012 Elsevier Ltd. All rights reserved.

Bifurcation analysis of an aeroelastic system with concentrated nonlinearities

Analytical and numerical analyses of the nonlinear response of a three-degree-of-freedom nonlinear aeroelastic system are performed. Particularly, the effects of concentrated structural nonlinearities on the different motions are determined. The concentrated nonlinearities are introduced in the pitch, plunge, and flap springs by adding cubic stiffness in each of them. Quasi-steady approximation and the Duhamel formulation are used to model the aerodynamic loads. Using the quasi-steady approach, we derive the normal form of the Hopf bifurcation associated with the system's instability. Using the nonlinear form, three configurations including supercritical and subcritical aeroelastic systems are defined and analyzed numerically. The characteristics of these different configurations in terms of stability and motions are evaluated. The usefulness of the two aerodynamic formulations in the prediction of the different motions beyond the bifurcation is discussed.

Engineering Active Pharmaceutical Ingredients by Spray Drying: Effects on Physical Properties and In Vitro Dissolution

Active pharmaceutical ingredients have very strict quality requirements; minor changes in the physical and chemical properties of pharmaceuticals can adversely affect the dissolution rate and therefore the bioavailability of a given drug. Accordingly, the aim of the present study was to investigate the effect of spray drying on the physical and in vitro dissolution properties of four different active pharmaceutical ingredients, namely carbamazepine, indomethacin, piroxicam, and nifedipine. Each drug was dispersed in a solution of ethanol and water (70:30) and subjected to single-step spray drying using similar operational conditions. A complete characterization of the spray-dried drugs was performed via differential scanning calorimetry (DSC), scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), particle size distribution analysis, solubility analysis, and an in vitro dissolution study. The results from the thermal analysis and X-ray diffraction showed that, except for carbamazepine, no chemical modifications occurred as a result of spray drying. Moreover, the particle size distribution of all the spray-dried drugs significantly decreased. In addition, SEM images showed that most of the particles had an irregular shape. There was no significant improvement in the solubility of the spray-dried drugs compared with the unprocessed compounds; however, in general, the dissolution rates of the spray-dried drugs showed a remarkable improvement over their non-spray-dried counterparts. Therefore, the results from this study demonstrate that a single spray-drying step may lead to changes in the physical properties and dissolution characteristics of drugs and thus improve their therapeutic action.