Chemical composition and extraction yield of the extract of Origanum vulgare obtained from sub- and supercritical CO2

In this work sub- and supercritical CO(2) were used to obtain extracts from two origanum samples, one commercial, and another cultivated under agronomic control. The experiments were performed in the temperature range of 293-313 K and from 100 to 200 bar in pressure, employing around 26 g of origanum samples. Results show that the commercial sample provides a higher yield of extract if compared to the other sample. It is also achieved that a raise in temperature at constant pressure leads to an increase in the extraction yield despite solvent density changes. Chemical analyses were carried out in a GC-MSD, allowing the identification of around 24 compounds by use of the library of spectra of the equipment and injection of some standard compounds for both commercial and cultivated origanum samples. It was also found that the distribution of chemical components as a function of extraction time differs appreciably between the origanum species. The chromatographic analysis permitted the identification of thymol and cis-sabinene hydrate as the most prominent compounds present in commercial oregano sample and carvacrol and cis-sabinene hydrate in the cultivated Origanum vulgare.     

Chemical composition of volatiles in Sardinian myrtle (Myrtus communis L.) alcoholic extracts and essential oils

The chemical composition of the volatile fraction of myrtle (Myrtus communis L.) alcoholic extracts and essential oils from leaves and berries collected in different places in Sardinia (Italy) was studied. A simple and rapid liquid-liquid extraction method was used to isolate volatile compounds from myrtle alcoholic extracts followed by GC and GC-MS analysis allowing the detection of 24 compounds. The volatile fraction was characterized by the terpenes fraction corresponding to that of the essential oils and by a fatty acid ethyl esters fraction. The variation during extraction of the volatile fraction in alcoholic extracts of berries and leaves was evaluated. Essential oils were obtained by hydrodistillation, and the yields were on average 0.52 +/- 0.03% (v/w dried weight) and 0.02 +/- 0.00% for leaves and berries, respectively. The essential oils were analyzed by GC and GC-MS, and a total of 27 components were detected, accounting for 90.6-98.7% of the total essential oil composition. Strong chemical variability depending on the origin of the samples was observed. The major compounds in the essential oils were alpha-pinene (30.0 and 28.5%), 1,8-cineole (28.8 and 15.3%), and limonene (17.5 and 24.1%) in leaves and berries, respectively, and were characterized by the lack of myrtenyl acetate.     

Effects of supercritical carbon dioxide (SC-CO(2)) oil extraction on the cell wall composition of almond fruits.

Extraction of oil from almond fruits using supercritical carbon dioxide (SC-CO(2)) was carried out at 50 degrees C and 330 bar on three sets of almonds: raw almond seeds, raw almond kernels, and toasted almond seeds. Three different oil extraction percentages were applied on each set ranging from approximately 15 to 16%, from approximately 27 to 33%, and from approximately 49 to 64%. Although no major changes were detected in the fatty acid composition between fresh and partially defatted samples, carbohydrate analysis of partially defatted materials revealed important changes in cell wall polysaccharides from almond tissues. Thus, at low extraction percentages (up to approximately 33%), pectic polysaccharides and hemicellulosic xyloglucans were the main type of polymers affected, suggesting the modification of the cell wall matrix, although without breakage of the walls. Then, as supercritical fluid extraction (SCFE) continues and higher extraction rates are achieved (up to approximately 64%), a major disruption of the cell wall occurred as indicated by the losses of all major types of cell wall polysaccharides, including cellulose. These results suggest that, under the conditions used for oil extraction using SC-CO(2), fatty acid chains are able to exit the cells through nonbroken walls; the modification of the pectin-hemicellulose network might have increased the porosity of the wall. However, as high pressure is being applied, there is a progressive breakage of the cell walls allowing the free transfer of the fatty acid chains from inside the cells. These findings might contribute to providing the basis for the optimization of SCFE procedures based on plant food sources.     

Chemical composition of the essential oil and supercritical CO2 extract of Commiphora myrrha (Nees) Engl. and of Acorus calamus L

Volatile concentrates from the oleo-gum resin of Commiphora myrrha (Nees) Engl. and from the rhizomes of Acorus calamus were isolated by supercritical extraction with carbon dioxide. The volatile oil of myrrh was obtained at 9.0 MPa and 50 degrees C and at a CO2 flow of 1.5 kg/h. Acorus calamus was extracted at 9.0 MPa and 45 degrees C and at a CO2 flow of 1.6 kg/h. In both cases, an oil devoid of cuticular waxes was obtained with a single depressurization stage. The SFE myrrh oil had a yield, Y, of 3.2%. Its main components, identified and quantified by GC/MS, were furanoeudesma-1,3-diene, 34.9%; lindestrene, 12.9%; curzerene, 8.5%; and germacrone, 5.8%. The essential oils from the same starting material by hydrodistillation, HD, (Y = 2.8%) and by steam distillation, SD, (Y = 0.4%) were quite similar to the SFE extract. The main components of the SFE oil of A. calamus (Y = 3.5%) were acorenone, 13.4%; iso-acorone, 11.6%; (Z)-sesquilavandulol, 11.0%; dehydroxy isocalamendiol, 7.7%; and beta-asarone, 5.5%. The comparison with hydrodistilled (Y = 1.8%) and steam distilled (Y = 1.0%) oils revealed large differences in the content of iso-acorone and crypto-acorone.     

Chemical composition of volatile extract and biological activities of volatile and less-volatile extracts of juniper berry (Juniperus drupacea L.) fruit

Volatile chemicals in a dichloromethane extract from a steam distillate of juniper berry fruit (Juniperus drupacea L.) and its two column chromatographic fractions (eluted with hexane and ethyl ether) were analyzed by gas chromatography/mass spectrometry. The major compounds in the dichloromethane extract were alpha-pinene (23.73%), thymol methyl ether (17.32%), and camphor (10.12%). A fraction eluted with hexane contained alpha-pinene (44.24%) as the major constituent. A fraction eluted with ethyl ether had thymol methyl ether (22.27%) and camphor (19.65%) as the main components. Three samples prepared from the distillate and two additional samples prepared by petroleum ether and ethanol extraction directly from juniper berry fruits exhibited clear antioxidant activities with dose response in both 1,2-diphenyl picrylhydrazyl and beta-carotene assays. All samples except the hexane fraction showed comparable activities to that of the synthetic antioxidant t-butyl hydroquinone at a level of 200 microg/mL in the two testing systems. The extracts of dichloromethane, petroleum ether, and ethanol exhibited appreciable antimicrobial activities against six microorganisms with minimum inhibitory concentrations ranging from 0.5 mg/mL (volatile extract against Candida albicans ) to 1.2 mg/mL (ethanol extract against Aspergillus niger ). The results of the present study suggest that this fruit could be a natural antioxidant supplement for foods and beverages.     

超声强化超临界CO2萃取人参皂苷的研究

为了探讨超声波对超临界CO2萃取(SCE)的影响,考察了在不同萃取温度、萃取压力、萃取时间和流体流量下,有、无超声时超临界CO2萃取人参皂苷的萃取率.试验结果发现,超声强化超临界CO2萃取(USCE)的合适萃取温度比没加超声(SCE)时的低10℃;在各自合适的萃取压力下,USCE的皂苷萃取率是SCE的1.64倍;CO2流体的流量大更有利于USCE.在SCE中,超声的加入能明显提高产物的萃取率和生产效率,降低生产能耗和节约生产成本.     

Improvement of the composition of Tunisian myrtle berries (Myrtus communis L.) alcohol extracts

Different extracts from myrtle berries were obtained using alcohol-water mixtures as an extraction medium in the range of 60-90% (v/v) to study the extraction efficiency in the preparation of myrtle liqueur. Flavonoids and anthocyanins were identified by high-performance liquid chromatography (HPLC) coupled with electrospray mass spectrometry and quantified during the maceration period by HPLC coupled with ultraviolet/visible detection. The antioxidant activity was tested by the 2,2-diphenyl-1-picrylhydrazyl assay. Dry matter, pH, and color parameters (L, a, b) were also analyzed. At the end of the maceration period, EE80 showed better anthocyanins stability and the highest total antioxidant activity (87.5%). These results suggest that the use of ethanol 80% provides the extract with the best characteristics for liqueur preparation. The present study contributes significantly to increase the marketing appeal of myrtle berries.     

超临界CO2流体萃取杏仁油工艺研究

该研究以单因素试验和正交试验相结合的方法对苦杏仁脂肪油的超临界CO2萃取工艺进行了研究.确定了超临界CO2萃取杏仁油的最佳工艺为:萃取压力35 MPa、萃取温度50 ℃、CO2流量24 L/h、粒径60目、萃取时间2 h.各因素影响杏仁的得率的顺序为:粒径＞时间＞萃取压力＞CO2流量＞萃取温度.最佳工艺验证试验的杏仁油的得率为52.98%.本研究的结果为下一步综合、无毒、高效地开发利用苦杏仁奠定了基础.     

裸大麦中生育三烯酚的超临界CO2流体萃取工艺

采用四元二次通用旋转设计研究了裸大麦中生育三烯酚的超临界CO2流体萃取工艺.结果表明:萃取温度对生育三烯酚提取率有显著影响,乙醇添加量和萃取时间对生育三烯酚提取率有极显著影响,而萃取压力对生育三烯酚提取率无显著影响,但萃取压力和乙醇添加量的交互项对生育三烯酚提取率有显著影响;在本实验条件下,生育三烯酚最佳超临界CO2萃取条件为:萃取温度51.8℃、萃取压力34.7 MPa、乙醇添加量9%、萃取时间120 min.     

Antimutagenicity of supercritical CO2 extracts of Terminalia catappa leaves and cytotoxicity of the extracts to human hepatoma cells

Natural antimutagens may prevent cancer and are therefore of great interest to oncologists and the public at large. Phytochemicals are potent antimutagen candidates. When the Ames test was applied to examine the antimutagenic potency of supercritical carbon dioxide (SC-CO(2)) extracts of Terminalia catappa leaves at a dose of 0.5 mg/plate, toxicity and mutagenicity were not detected. The antimutagenic activity of SC-CO(2) extracts increased with decreases of temperature (60, 50, and 40 degrees C) and pressure (4000, 3000, and 2000 psi) used for extraction. The most potent antimutagenicity was observed in extracts obtained at 40 degrees C and 2000 psi. At a dose of 0.5 mg of extract/plate, approximately 80% of the mutagenicity of benzo[a]pyrene (B[a]P, with S-9) and 46% of the mutagenicity of N-methyl-N '-nitroguanidine (MNNG, without S-9) were inhibited. Media supplemented with SC-CO(2) extracts at a range of 0-500 microg/mL were used to cultivate human hepatoma (Huh 7) and normal liver (Chang liver) cells. The viability of the cells was assayed by measuring cellular acid phosphatase activity. A dose-dependent growth inhibition of both types of cells was observed. The SC-CO(2) extracts were more cytotoxic to Huh 7 cells than to Chang liver cells. The observation that SC-CO(2) extracts of T. catappa leaves did not induce mutagenicity at the doses tested while exhibiting potent antimutagenicity and were more cytotoxic to human hepatoma cells than to normal liver cells is of merit and warrants further investigation.     

压力、温度对穿心莲内酯超临界CO2萃取-结晶的影响

以穿心莲浸膏为原料,进行了穿心莲内酯的超临界CO2萃取结晶分离纯化.考察了单因素参数压力、温度对穿心莲内酯纯度、结晶量等的影响.结果表明:超临界CO2萃取结晶穿心莲内酯的纯度在结晶板上呈梯度分布;在25 MPa以下,压力升高,结晶板上部晶体纯度升高,而结晶量先增后减;在结晶板下部穿心莲内酯的纯度和结晶量都是先升高后降低;温度在一定范围内能提高晶体纯度,且有利于缩短萃取结晶时间.     

超临界CO2萃取毛竹笋油的工艺及产品成分

为优化超临界CO2萃取毛竹笋油的工艺参数,该研究通过单因素试验和正交试验考察了萃取压力、萃取温度、萃取时间和CO2流量等因素对毛竹笋油得率的影响,并利用气质联用（GC-MS）对毛竹笋油进行成分分析。研究确定超临界CO2萃取毛竹笋油的较佳工艺为：萃取压力25 MPa、萃取温度55℃、萃取时间2.5 h和CO2流量15 L/h,较佳工艺条件下笋油得率为5.74%;GC-MS分析毛竹笋油,共鉴定出17种组分,其中β-谷甾醇、9,12-十八碳二烯酸和9,12,15-十八碳三烯酸的相对含量分别为26.00%、10.50%和9.83%。     

超临界CO_2萃取脱皮菜籽饼粕油脂的可行性

为提高脱皮双低菜籽低温压榨饼的附加值,采用Box-Behnken响应面设计优化超临界CO2萃取脱皮双低菜籽低温压榨饼中油脂的工艺,研究萃取压力、温度和时间对油脂提取率的影响,并对萃取得到的油和粕的品质进行检测。结果表明:萃取温度对油脂提取率的影响显著(P0.05);萃取压力和时间对油脂提取率的影响极显著(P0.001),且交互作用非常显著(P0.01);最佳工艺参数为萃取温度40℃、压力28 MPa和时间120 min,此条件下菜籽油的提取率为95.08%。超临界萃取的油色泽较浅,酸价与过氧化值都优于正已烷工艺,磷脂质量分数为0.051 mg/g约是正已烷工艺的1/32,维生素E和总酚含量较高;超临界萃取的脱脂粕蛋白溶解度高,颜色较浅,硫甙含量较少,品质明显优于正已烷脱脂粕。研究结果可为脱皮双低菜籽低温压榨饼的高值化利用提供数据参考。     

Beta-carotene isomer composition of sub- and supercritical carbon dioxide extracts. Antioxidant activity measurement

In the present work sub- and supercritical extraction conditions using carbon dioxide were studied in order to obtain extracts with different compositions from the green microalgae Dunaliella salina. Different compositions of beta-carotene isomers were identified in the extracts by using HPLC-DAD. Also, antioxidant activity of the extracts was measured using a TEAC assay. An experimental design was applied considering two factors, extraction pressure and temperature, in a wide range of values, trying to maximize the extraction yield. Higher yields were obtained at high pressures and low temperatures, that is, at higher CO2 densities. Attempts were made to correlate the antioxidant activity of the extracts with their chemical composition by means of principal component analysis. A certain relationship was found between their antioxidant activity and the isomeric composition of beta-carotenes. As a result, an original equation is proposed to predict the antioxidant activity of extracts from D. salina in terms of the ratio 9-cis-beta-carotene/all-trans-beta-carotene, the concentration of alpha-carotene, and, especially, the concentration of 9-cis-beta-carotene.     

The effects of temperature and pressure on the characteristics of the extracts from high-pressure CO(2) extraction of Majorana hortensis Moench

The aim of this work is to assess the influence of temperature and pressure (solvent density) on the characteristics of the essential oil obtained from high-pressure carbon dioxide extraction of marjoram (commercial marjoram samples available in the free market and Majorana hortensis Moench, cultivated in South Brazil under rigorous agronomic conditions). The extracts were analyzed in terms of the liquid yield (extract/raw material, wt/wt) and distribution of volatile chemical components. The experiments were performed in a laboratory-scale unit using the dynamic method in the temperature range of 293.15-313.15 K, from 100 to 200 bar in pressure. Chemical analyses were carried out in a GC/MSD. Results show that an increase in temperature leads to a rise in the extract liquid yield despite large changes in solvent density. Chromatographic analyses permitted the identification of cis-sabinene hydrate, terpineol-4, alpha-terpineol, and cis-sabinene hydrate acetate as the main volatile compounds present in both commercial and cultivated samples.     

Flavonoids and biflavonoids in Tuscan berries of Juniperus communis L.: detection and quantitation by HPLC/DAD/ESI/MS

The aim of the present work was to develop a quali-quantitative investigation, using HPLC/DAD and HPLC/ESI/MS techniques, of the phenolic composition of berries collected from wild Tuscan plants of Juniperus communis L. and grown in three different geographical zones. The applied chromatographic elution method made it possible to well separate up to 16 different compounds belonging to flavonoids, such as isoscutellarein and 8-hydroxyluteolin or hypolaetin glycosides, and six biflavonoids, among them amentoflavone, hynokiflavone, cupressoflavone, and methyl-biflavones. To the best of the authors' knowledge this is the first report on the presence of these compounds in juniper berries. The flavonoidic content in the analyzed berries ranged between 1.46 and 3.79 mg/g of fresh pulp, whereas the amount of the biflavonoids was always lower, varying between 0.14 and 1.38 mg/g of fresh weight.     

Comparison of the chemical composition of extracts from Scutellaria lateriflora using accelerated solvent extraction and supercritical fluid extraction versus standard hot water or 70% ethanol extraction

The aqueous extract of American skullcap (Scutellaria lateriflora L. (S. lateriflora), Lamiaceae) has been traditionally used by North American Indians as a nerve tonic and for its sedative and diuretic properties. Recent reports stated that flavonoids and possibly amino acids are responsible for the anxiolytic activity. As a part of our search for environmentally friendly solvents to extract the active components from medicinal plants, we used S. lateriflora in a comparison of accelerated solvent extraction (ASE) using water, and supercritical fluid extraction (SFE) using CO2 and 10% EtOH as modifier, at different temperatures. Flavonoids and amino acids were quantified by HPLC-UV and HPLC-MS, respectively. The flavonoid content was compared with conventional extraction methods (hot water extraction and 70% ethanol). The use of ASE at 85 degrees C with water as solvent gave the best results for flavonoid glycosides and amino acids, whereas SFE gave higher yields of flavonoid aglycones. However, the results obtained for total flavonoids were not significatively superior to hot water extraction or 70% aqueous EtOH extract.     

响应曲面法建立超临界CO2萃取结晶穿心莲内酯工艺模型

以穿心莲内酯含量为30%的穿心莲浸膏为试验原料,采用响应曲面分析法(Response Surface Methodology,RSM)建立了超临界CO2萃取结晶穿心莲内酯结晶率的二次多项数学模型,验证了数学模型的有效性,并探讨了萃取结晶压力、温度、时间对结晶率的作用规律.根据该模型进行了工艺参数的优选,以结晶率为指标,试验所得穿心莲内酯超临界CO2萃取结晶优化工艺条件为:压力20.88 MPa,温度50.27℃,时间97.02 min,该条件下结晶率高达74.77%.     

Antioxidant activity of extracts of black sesame seed (Sesamum indicum L.) by supercritical carbon dioxide extraction

Antioxidant activities of extracts derived from sesame seed by supercritical carbon dioxide (SC-CO(2)) extraction and by n-hexane were determined using alpha,alpha-diphenyl-beta-picylhydrazyl (DPPH) radical scavenging and linoleic acid system methods. The highest extracted yield was given at 35 degrees C, 40 MPa, and a CO(2) flow rate of 2.5 mL min(-1) by an orthogonal experiment. The yields of extracts increased with increasing pressure, and yields at 40 and 30 MPa were higher than that by solvent extraction at 46.50%. Results from the linoleic acid system showed that the antioxidant activity follows the order: extract at 35 degrees C, 20 MPa > BHT > extract at 55 degrees C, 40 MPa > extract at 55 degrees C, 30 MPa > Trolox > solvent extraction > alpha-tocopherol. The SC-CO(2) extracts exhibited significantly higher antioxidant activities comparable to that by n-hexane extraction. The extracts at 30 MPa presented the highest antioxidant activities assessed in the DPPH method. At 20 MPa, the EC(50) increased with temperature, which indicated that the antioxidant activity was decreased in a temperature-dependent manner. The significant differences of antioxidant activities were found between the extracts by SC-CO(2) extraction and n-hexane. However, no significant differences were exhibited among the extracts by SC-CO(2) extraction. The vitamin E concentrations were also significantly higher in SC-CO(2) extracts than in n-hexane extracts, and its concentrations in extracts corresponded with the antioxidant activity of extracts.     

Stimulatory effect on pea of Typha Angustifolia L. extracts and their chemical composition

In this study, the influence of aqueous and organic extracts of different plant parts (flowers, leaves, and stems) of Typha angustifolia on the germination and early seedling growth of field pea (Pisum sativum L.) was evaluated. Chemical composition of extracts of different plant parts of Typha was also determined. Aqueous (20, 40, 60, 80, and 100 g L^?1) and organic extracts (at 0.5, 1, and 2 mg mL^?1) were applied to the seeds of two pea cultivars, Douce de Provence and Lincoln, placed in Petri dishes. Application of extracts had a beneficial effect on germination and early seedling growth of both pea cultivars. However, aqueous extract of leaves showed the most beneficial effect at 60 and 40 g L^?1 for the cultivars Douce de Provence and Lincoln, respectively. The effect could be attributed to the allelochemicals present in the aqueous extracts. Petroleum ether and chloroform extracts of leaves had the most stimulating effect on the germination and early seedling growth of pea. Analysis of Typha extracts indicated the presence of vitamin E in leaves, which could be responsible forthis stimulation. Moreover, Typha leaves also had substantial amount of flavonoids. In conclusion, the allelopathic activity of of Typha was dependent on the plant part, the solvent nature, the concentration of the extracts tested, and on the pea cultivar. Application of leaf extract was the most effective in improving the germination rate and early seedling growth of pea.