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To evaluate the selectivity of supercritical carbon dioxide (scCO2) as a solvent to deacidify vegetable oils, the solubility of oleic acid and of a mixture of oleic acid and refined sunflower oil in scCO2 was measured. Sunflower oil was adopted as a pseudo-pure component and the phase equilibrium of ternary and binary systems were thermodynamically modeled by the Peng-Robinson equation of state with classical mixing rule. The values of the estimated and/or adopted critical properties in modeling thermodynamics were shown to be of great influence on the quality of data correlation. Although correlating data from binary systems is possible, the modeling was incapable of satisfactorily predicting the behavior of the phase equilibrium of the ternary system. The large deviations observed may derive from the presence of specific intermolecular interactions between the components of these systems that were not considered in this type of modeling.

Suspended particles of copaiba (Copaifera officinalis) oleoresin were produced by supercritical fluid extraction of emulsions (SFEE), using modified starch Hi-Cap 100® as core material. First, ultrasound was applied to produce oil in water (O/W) emulsions with droplet diameter of 261.7 ± 2.2 nm. In SFEE, CO2 and emulsion flow rates, and solvent extraction time were evaluated in terms of residual ethyl acetate content (REA) and β-caryophyllene recovery in the suspension. SFEE achieved 94.1% reduction of ethyl acetate and β-caryophyllene recovery of 7.3%. This REA is within the exposure limit of ethyl acetate (5000 ppm per day). The suspended nanoparticles’ size showed little variation from the emulsion droplet diameter. Finally, the suspensions were dried to obtain powder particles. Field emission scanning electron microscopy (FESEM) revealed different structures depending on the drying method (freeze-drying or spray-drying). Moreover, confocal laser scanning microscopy (CLSM) confirmed that copaiba oleoresin was encapsulated in the particles.

The oleoresin of copaiba has many pharmacological properties, such as anti-inflammatory, antiseptic, and cicatrizing, besides helping to treat skin diseases, among other applications. In order to improve its activity, copaiba oleoresin was encapsulated within polymeric particles through emulsification assisted by ultrasound followed by a drying process. Ultrasound-assisted emulsification led to the formation of kinetically stable emulsions. The emulsions with increased stability and the lowest droplet diameters (80.95 ± 2.1 nm (Hi-Cap 100®) and 71.8 ± 2.9 nm (Snow-Flake® E 6131)) were subjected to freeze-drying and spray-drying to produce dry particles. The particles were characterized in terms of moisture content, particle size distribution, encapsulation efficiency, surface oil, oxidative stability, X-ray diffraction and morphological analysis by FESEM and CLSM. Both drying techniques produced amorphous particles with different sizes and low moisture content. Furthermore, high encapsulation efficiency and high stability against thermal degradation were achieved. The analysis of the particles’ morphology indicated that the nature of the biopolymers used (Hi-Cap 100® and Snow-Flake® E 6131) did not affect their microstructure. However, as expected, the freeze-drying and spray-drying techniques produced particles with different external microstructures. SD particles were spherical, whereas FD particles presented irregular structures similar to sheets.

Rhizome of Curcuma longa L. is rich in curcumin which is also an important natural pigment and has important biological activity. In order to obtain curcumin concentrated extracts, one-step and two-step processes were employed. The one step process involves supercritical carbon dioxide (scCO 2 ) at 60 °C and 400 bar, ethanol at 25 °C and water at 60 °C, both at atmospheric pressure. Ethanol and/or water were used as solvents. In the two-step process, sequential extraction, using scCO 2, was performed followed by ethanol or water extraction. All the extracts obtained were analyzed and results were reported for global extraction yield, the total phenolic content, total flavonoids, curcumin, antimalarial activity and antioxidant activity. The two-step process showed the highest global yield (23.4%) when water is used as solvent in the second step. However, high concentrations of curcumin and high antioxidant activity were obtained when ethanol is used as solvent. The supercritical extract presents low concentration of curcumin and high antimalarial activity; which shows that extracts of different compositions and functionality can be obtained from a sequential extraction.

This article reports a study on the extraction and evaluation of essential oil obtained from dried flowers of Eupatorium intermedium, a plant native to southern Brazil that belongs to the Asteraceae family. The hydrodistillation achieved a maximum yield of 1.01 wt% of essential oil. Regarding the chemical composition, by a qualitative analysis, the identified substances were α-pinene, sabinene, β-pinene, limonene, caryophyllene (E), germacrene D, spathulenol and caryophyllene oxide. The antioxidant activity of the essential oil obtained was evaluated using the DPPH method, phosphomolybdenum reducing method and total phenolic content. The total phenolic content was 4.26 mg GAE/g of oil. The antioxidant activity obtained by the DPPH method was 0.82 wt%, at a concentration of 250 mg/mL. The antioxidant activity obtained through the reduction of the phosphomolybdenum complex was 1154.69 mg α-tocopherol/g of oil. Antibacterial activity assays were performed using the agar well method. The oil presented...

Extraction of bioactive compounds requires frequent changes in the extraction techniques due to the quality requirements in the food, pharmaceutical and cosmetic industries. The compounds of the polyphenolic family represent an important group of bioactive compounds in food, and are present in various types of plants, including Lippia sidoides Cham., also known as pepper-rosmarin, an aromatic plant with therapeutic properties. Thus, this study aimed to investigate the sequential extraction (in fixed bed and high pressure) of bioactive compounds from L. sidoides leaves, using supercritical carbon dioxide, ethanol, and water as solvents and, compare the global yield, total phenolics, total flavonoids, and antioxidant activity of extracts obtained from sequential extraction with the extracts obtained by one-step extraction in fixed bed (high pressure) and by conventional extraction. The results showed that the combination of extraction processes is an effective method to obtain extracts with different compositions and functionalities. Overall, the ethanolic extraction in fixed bed and the three-step sequential extraction showed the best results in terms of global yield, and content and yield of total phenolics and flavonoids. The ethanol extracts exhibited the best antioxidant activity, which may be related to the presence of phenolic compounds.

The extraction of Eupatorium intermedium flowers was evaluated using supercritical CO2 (scCO2) and compressed propane. Experiments were carried out under the following conditions using scCO2 as the solvent: 15.0, 20.0 and 25.0 MPa and at 303.15, 328.15 and 353.15 K, and the maximum extraction yield was 5.85 wt%. With propane as the solvent the conditions applied were 3.0, 6.5 and 10.0 MPa and 293.15, 313.15 and 333.15 K, and the maximum extraction yield was 9.34 wt%. When scCO2 was used the pressure had a positive effect on the extraction yield while with the use of propane both variables (pressure and temperature) had a positive effect. Gas chromatographic analysis showed that the major compounds were spathulenol, caryophyllene oxide, caryophyllene (E), germacrene D, bicyclogermacrene and carotol, for the two solvents. The highest values for antioxidant activity were found for the extracts obtained using scCO2 at 303.15 K and 15 MPa and propane at 333.15 K and 3.0 MPa, determined by the DPPH method and the phosphomolybdenum reduction method. The extract obtained using propane at 293.15 K and 3.0 MPa presented the highest phenolic content. The highest antibacterial activity was observed for the extracts obtained with scCO2 against Staphylococcus aureus and Listeria monocytogenes.

Melia azedarach L. is a plant with wide use in folk medicine since it contains many bioactive compounds of interest. The present study aimed to extract bioactive compounds from M. azedarach fruits by a sequential process in fixed bed using various solvent mixtures. Extractions were performed at 50 °C and 300 bar in four sequential steps using supercritical CO 2 (scCO 2 ), scCO 2 /ethanol, pure ethanol, and ethanol/water mixture as solvents, respectively. The efficacy of the extraction process was evaluated by extraction yield and kinetics, and analysis of extracts by: (1) thin layer chromatography (TLC), (2) phenolics content, (3) reduction of surface tension of water, (4) gas chromatography (GC–MS), (5) electrospray ionization mass spectrometry (ESI–MS) and (6) antiviral activity. The overall extraction yield reached 45% and TLC analysis showed extracts with different composition. extract obtained from CO 2 /ethanol mixture (SCEE) exhibited the greatest ability to reduce surface tension of water from 72.4 mN m −1 [1] of pure water to 26.9 mN m −1 of an aqueous solution of 40 g L −1 . The highest phenolics contents were observed in both the hydroalcoholic extract and scCO 2 /ethanolic extract. Volatile oils were not detected in the supercritical extracts by GC–MS. MS analyses identified the fatty acids: linoleic, palmitic and myristic acid in the supercritical extract (SCE), and the phenolics: caffeic acid and malic acid in the other extracts. In addition, SCE and SCEE extracts showed significant inhibition percentage against Herpes Simplex Virus Type 1. The extraction process proposed in the present study produced extracts with significant potential for application in food and pharmaceutical industries.

Saponins are surfactants that reduce the surface tension of aqueous solutions, besides having pharmacological actions. In order to extract and fractionate saponins from Pfaffia glomerata roots and Hebanthe eriantha roots using supercritical technology, fractionated extracts were obtained from a sequential process in fixed bed using supercritical CO 2 (scCO 2 ), ethanol, and water as solvents. All extractions were carried out in four sequential steps, at 50 °C and 300 bar. In the first step, pure scCO 2 was used as solvent, while (a) scCO 2 /etanol (70:30, w/w); (b) ethanol, and (c) ethanol/water (70:30, v/v) were used as solvents in the three subsequent steps. The extracts were analyzed by thin layer chromatography (TLC) and surface tension. The extraction yields of the four steps were 0.16, 0.55, 1.00, and 6.90% for P. glomerata roots, and 0.17, 0.58, 0.89, and 28% for H. eriantha roots, showing a predominance of high polarity compounds in these species. TLC analysis showed that the extraction process was selective according to the polarity of the solvent, and provided extracts containing different saponins, except for scCO 2 extraction. The extracts from the extraction using ethanol + scCO 2 (Step 2) showed the greatest ability to reduce the surface tension of water from 72 mN m −1 (pure water) to 25 mN m −1 , suggesting that this step was the best for extraction of less polar saponins in the extracts. The critical micelle concentration (CMC) values were approximately 2 and 8 g L −1 for P. glomerata and H. Eriantha , respectively. These results confirmed the efficacy of the extraction process under study.

Baccharis dracunculifolia is a shrub native to Brazil and an important botanical source for propolis production. The essential oil from the leaves of B. dracunculifolia DC (Asteraceae), popularly known as broom oil, presents pharmacological activities and is a raw material in the perfumery and cosmetics industries. The isolation of its major constituent, nerolidol, to a high purity (92.5–93.7%) was possible through the countercurrent chromatography technique. The countercurrent chromatography biphasic solvent system chosen was a mixture of hexane:methanol:water (5:4:1, v/v/v). Isocratic elution was conducted in a tail-to-head manner.

With the goal of maximizing the extraction yield of phenolic compounds from pitanga leaves (Eugenia uniflora L.), a sequential extraction in fixed bed was carried out in three steps at 60 °C and 400 bar, using supercritical CO2 (non-polar) as solvent in a first step, followed by ethanol (polarity: 5.2) and water (polarity: 9.0) in a second and third steps, respectively. All extracts were evaluated for global extraction yield, concentration and yield of both polyphenols and total flavonoids and antioxidant activity by DPPH method (in terms of EC50). The nature of the solvent significantly influenced the process, since the extraction yield increased with solvent polarity. The aqueous extracts presented higher global extraction yield (22%), followed by ethanolic (16%) and supercritical extracts (5%). The study pointed out that the sequential extraction process is the most effective in terms of global extraction yield and yield of polyphenols and total flavonoids, because it produced the more concentrated extracts on phenolic compounds, since the supercritical ethanolic extract presented the highest phenolics content (240.5 mg GAE/g extract) and antioxidant capacity (EC50 = 9.15 μg/mL). The most volatile fraction from the supercritical extract, which is similar to the essential oils obtained by steam distillation or hydrodistillation, presented as major compounds the germacrenos D and B + bicyclogermacrene (40.75%), selina-1,3,7(11)-trien-8-one + selina-1,3,7(11)-trien-8-one epoxide (27.7%) and trans-caryophyllene (14.18%).

Medicinal plants are well known for their use in traditional folk medicine as treatments for many diseases including infectious diseases.Six Brazilian medicinal plant species were subjected to an antiviral screening bioassay to investigate and evaluate their biological activities against five viruses: bovine herpesvirus type 5 (BHV-5), avian metapneumovirus (aMPV), murine hepatitis virus type 3, porcine parvovirus and bovine respiratory syncytial virus.The antiviral activity was determined by a titration technique that depends on the ability of plant extract dilutions (25 or 2.5 µg/mL) to inhibit the viral induced cytopathic effect and the extracts' inhibition percentage (IP).Two medicinal plant species showed potential antiviral activity. The Aniba rosaeodora Ducke (Lauraceae) extract had the best results, with 90% inhibition of viral growth at 2.5 µg/mL when the extract was added during the replication period of the aMPV infection cycle. The Maytenus ilicifolia (Schrad.) Planch. (Celastraceae) extracts at a concentration of 2.5 µg/mL exhibited antiviral activity during the attachment phase of BHV-5 (IP = 100%).The biomonitored fractionation of the active extracts from M. ilicifolia and A. rosaeodora could be a potential tool for identifying their active compounds and determining the exact mechanism of action.

One and two step extraction processes were used to obtain extracts from two samples of alecrim do campo leaves ( Baccharis dracunculifolia L.). In the one step process, supercritical carbon dioxide (scCO 2 ), ethanol and water were used as solvents. In the two step process, scCO 2 was used as a solvent in the first step followed by ethanol or water as the solvent in a second step on the residue resulting from scCO 2 extraction. Extraction yields, total polyphenol, total flavonoid and Artepillin C contents, antioxidant activity by DPPH radical scavenging and β-carotene bleaching methods were measured in all extracts. The supercritical extract showed a higher concentration and yield of Artepillin C, low antioxidant activity by the DPPH method and high antioxidant activity by the β-carotene method. In general the aqueous and ethanol extracts were more concentrated in polyphenol compounds and a second extraction step produced high yields with high concentrations of phenolic compounds.

Venturi easy ambient sonic spray ionization mass spectrometry in both itsliquid(VL-EASI-MS) and solid sample modes (VS-EASI-MS) is shown to provide nearly immediate and secure typification of woods, as demonstrated for Mahogany, an endangered and mostvaluabletypeoftropical wood. Thisreddishwood displaysuniquephytochemical markers(phragmalin-typelimonoids) which are rapidly detected from the wood surface by VS-EASI-MS or from a simple methanol extract of a tiny wood chip by VL-EASI-MS. Unique profiles were obtained for Mahogany (Swietenia macrophylla) whereas genuine samples of six other similar types of woods, which are commonly falsified by artificial coloring and commercialized as Mahogany, display also typical but dissimilar pythochemical profiles as compared to that of the authentic wood. Variable and atypical chemical profiles were observed for artificially colored woods. Secure chemical characterization via VS-EASI-MS or Vs-EASI-MS fingerprints of Mahogany and other types of woods with similar appearance should help to control the illegal logging and trade of this and other endangered woods and their falsification, and to create certified standards. Copyright © 2012 John Wiley & Sons, Ltd.

Conchocarpus fontanesianus (A. St.-Hill.) Kallunki & Pirani, Rutaceae, popularly known as pitaguará, is a native and endemic tree from São Paulo and Rio de Janeiro States, Brazil. Based in the information that anticholinesterasic derivatives could act as new prototypes to treatment of Alzheimer disease, this work describes the fractionation guided by evaluation of the anticholinesterase activity of the ethanolic stems extract from C. fontanesianus. This procedure afforded the alkaloids dictamnine (1), γ-fagarine (2), skimianine (3), and 2-phenyl-1-methyl-4-quinolone (4), as well as the coumarin marmesin (5).

This study aimed to evaluate the chemical composition of Baccharis dracunculifolia essential oil and the water soluble oil obtained by steam distillation that were analyzed by GC and GC/MS. In the first hour of distillation B. dracunculifolia aerial parts yielded 0.08% oil and in the second hour, 0.27%. The oil recovered from the distillate water yielded 0.18 g/L in the first hour and 0.44 g/L in the second hour of distillation. The main volatile compounds identified in the distillate water were aromatic compounds and sesquiterpene alcohols.

RESUMO – Esse trabalho objetivou, atraves da combinacao de processos de extracao, a obtencao de extratos naturais a partir de folhas de alecrim-pimenta (Lippia sidoides Cham.). Extratos foram obtidos por extracao sequencial em leito fixo a 60 oC e 400 bar, primeiro atraves de extracao com dioxido de carbono supercritico (scCO2), seguida por extracao com etanol e por ultimo, extracao com agua. Todos os extratos foram avaliados quanto ao teor de fenois e flavonoides totais. Para efeito de comparacao, mais dois tipos de extratos etanolicos e aquosos foram obtidos: 1) Extratos em etapa unica a partir das folhas, com etanol e com agua em leito fixo a 60 °C e 400 bar sem previa extracao com scCO2 e 2) Extratos convencionais utilizando um sistema a baixa pressao e 60 oC. A analise dos resultados mostrou que o carater do solvente empregado influenciou significativamente no processo de obtencao dos extratos, pois o rendimento apresentou tendencia de aumento com o aumento da polaridade do solvente. Os resultados apontaram a extracao sequencial como a mais eficiente quanto ao rendimento global e rendimento de fenois e a extracao etanolica (1 etapa) em leito fixo com as maiores concentracoes de fenois e flavonoides totais e com o melhor rendimento de flavonoides.

Bacillus subtilis experiments for surface tension evaluation were accomplished with culture medium containing 0.4% nitrate ions and 4% glucose basic nutrient in the presence of crude oil. Surfactin production was observed by surface tension reduction of the culture broth. Surfactin was isolated from Bacillus subtilis fermented broth, by acid-precipitation followed by extraction with chloroform-methanol. Evaluation of the linear alkanes composition was performed by capillary gas chromatography. We observed a significant reduction of the surface tension of the fermented broth indicating that the biosurfactant production was not inhibited by the crude oil presence, and that the light paraffins might have been consumed.

An easy methodology for triterpene isolation is shown. Evaluation in rats for antiulcer activity of friedelan-3beta-ol 1 and friedelin 2. The two triterpenes isolated from the leaves of Maytenus ilicifolia, did not decrease gastric ulcers when tested on indometacine induced ulcer model in rats.

Synthesis of several (±)-[4S-(4β,4aβ,8aα)]-1,6-dimethyl-4-(1 methylethyl)-1,2,3,4,5,8,8a-octahydro-1-naphthalenol derivatives (cadinanol derivatives) provided the necessary evidence for the identification of three novel cadinane derivatives [(±)-[1S-(1β, 4β, 4aβ, 8aα)]-1,6-dimethyl-4-(1-methylethyl)-1,2,3,4,4a,5,8,8a-octahydro-1-naphthalenol 11a, (±)-[1S-(1β, 4β, 4aβ, 4aβ, 6α, 7α, 8aα)]-6, 7-epoxide-1,6-dimethyl-4-(1-methylethyl)-1,2,3,4,4a,5,6,7,8,8a-decahydro-1- naphthalenol 14 and (±)-[1S-(1β,4β,4aβ,6β,8aα)]-1,6-dimethyl-4-(1-methylethyl-1,2,3,4,4a,5,6,7,8,8a-decahydro-1,6-naphthalenediol 15] detected, in the essential oils of, B. platipoda. Compound 14 was also detected in B. tridentata. The synthetic compounds were characterized by one and two dimensional 1H and 13C NMR. The identification was obtained by coinjection of the oils with the synthetic standards and fragmentation pattern comparison.

Venturi easy ambient sonic spray ionization mass spectrometry in both its liquid (V(L) -EASI-MS) and solid sample modes (V(S) -EASI-MS) is shown to provide nearly immediate and secure typification of woods, as demonstrated for Mahogany, an endangered and most valuable type of tropical wood. This reddish wood displays unique phytochemical markers (phragmalin-type limonoids) which are rapidly detected from the wood surface by V(S) -EASI-MS or from a simple methanol extract of a tiny wood chip by V(L) -EASI-MS. Unique profiles were obtained for Mahogany (Swietenia macrophylla) whereas genuine samples of six other similar types of woods, which are commonly falsified by artificial coloring and commercialized as Mahogany, display also typical but dissimilar pythochemical profiles as compared to that of the authentic wood. Variable and atypical chemical profiles were observed for artificially colored woods. Secure chemical characterization via V(S) -EASI-MS or V(s) -EASI-MS fingerprints of Mahogany and other types of woods with similar appearance should help to control the illegal logging and trade of this and other endangered woods and their falsification, and to create certified standards.

Synthesis of several (±)-[4S-(4β,4aβ,8aα)]-1,6-dimethyl-4-(1 methylethyl)-1,2,3,4,5,8,8a-octahydro-1-naphthalenol derivatives (cadinanol derivatives) provided the necessary evidence for the identification of three novel cadinane derivatives [(±)-[1S-(1β, 4β, 4aβ, 8aα)]-1,6-dimethyl-4-(1-methylethyl)-1,2,3,4,4a,5,8,8a-octahydro-1-naphthalenol 11a, (±)-[1S-(1β, 4β, 4aβ, 4aβ, 6α, 7α, 8aα)]-6, 7-epoxide-1,6-dimethyl-4-(1-methylethyl)-1,2,3,4,4a,5,6,7,8,8a-decahydro-1- naphthalenol 14 and (±)-[1S-(1β,4β,4aβ,6β,8aα)]-1,6-dimethyl-4-(1-methylethyl-1,2,3,4,4a,5,6,7,8,8a-decahydro-1,6-naphthalenediol 15] detected, in the essential oils of, B. platipoda. Compound 14 was also detected in B. tridentata. The synthetic compounds were characterized by one and two dimensional 1H and 13C NMR. The identification was obtained by coinjection of the oils with the synthetic standards and fragmentation pattern comparison.

Extratos etanolicos e oleos essenciais de propolis verde do sudeste brasileiro e gemas de sua origem botânica (Baccharis dracunculifolia) foram analisados por CLAE-FR (Cromatografia Liquida de Alta Eficiencia em Fase Reversa), CCDAE (Cromatografia em Camada Delgada de Alta Eficiencia) e CG-EM (Cromatografia Gasosa acoplada a Espectrometria de Massas). Os oleos essenciais foram obtidos por hidro destilacao. Extratos etanolicos e oleos essenciais de Baccharis dracunculifolia e de propolis mostraram perfis cromatograficos similares entre si. Treze flavonoides foram identificados por CLAE-FR e CCDAE em ambas as amostras. Vinte e tres compostos volateis foram identificados por CG EM, sendo dezessete deles presentes em ambos os oleos essenciais. Artepillin C foi o flavonoide encontrado em maiores concentracoes em ambas as amostras, enquanto nerolidol foi o volatil majoritario em ambos os oleos essenciais. Os compostos majoritarios identificados neste trabalho podem ser utilizados como marcadores quimicos para classificar de forma pratica e identificar origens botânicas de propolis.

The oil of the leaves of Bursera aloexylon was found to contain a high linalool level (96.7 %). The antimicrobial activity tests indicated that the oil was effective against Rhodococcus equi (0.60 mg/ml) and Staphylococcus epidermides (0.15 mg/ml).