Comparative analysis of the composition of essential oils and supercritical carbon dioxide extracts from the berries and needles of Estonian juniper (Juniperus communis L.)

The composition of the volatile oil of the common juniper (Juniperus communis L.) from Estonia was analyzed by gas chromatography (GC-FID) and gas chromatography-mass spectrometry (GC-MS). The yield and composition of the oil obtained by different methods (micro-distillation and extraction, SDE, and supercritical carbon dioxide extraction, SFE) from various parts of juniper (berries, needles) were compared. The oil yield ranged from 0.7 to 2.1%. The content of α-pinene of juniper-berry essential oil was 47.9, that of juniper needleoil, 36.4%. The oil yields and composition obtained by SDE and SFE from juniper needles were similar. The oil obtained by SFE from juniper berries contained more sesquiterpenes and high boiling compounds than that obtained by SDE.     

The effect of pressure on the characteristics of supercritical carbon dioxide extracts from Calamintha nepeta subsp. nepeta

Chemists and industrialists are continuously attempting to develop greener and more environmentally benign chemical processes to extract essential oils and bioactive metabolites of high purity, finding various applications in cosmetics, detergents, nutraceuticals and pharmaceuticals. An increase preferenced for natural products over synthetic ones has made supercritical fluid technology a primary alternative for the generation of high-value bioactive ingredients. This effective technique requires only moderate temperatures, eliminates clean-up steps and avoids the use of harmful organic solvents. In this context, our study was focused on the chemical analysis of Calamintha nepeta subsp. nepeta aromatic extracts obtained with supercritical carbon dioxide. The effect of different operating conditions on the capacity of the lipophilic solvent to extract the targeted volatile components was also studied. The process was carried out at a fairly low constant temperature of 40°C, and with varying the pressure from 90 to 300 bar. The chemical composition of the extracts was analyzed by gas chromatography–mass spectroscopy. The results showed that the composition pattern, the concentrations of individual components and the quality of the extractable analytes were affected by pressure increase. The extraction yields varied from 0.73 to 1.21 wt% at 90 and 300 bar, respectively.     

Extraction of atabron residues from cabbage with supercritical carbon dioxide

Summary In this work we present a new procedure for extraction of Atabron residues from cabbage samples using supercritical carbon dioxide. The results obtained with this procedure were compared with those obtained using traditional extraction methods for Atabron residues. The extraction yields found by both procedures are similar but SFE has several advantages, especially higher speed, greater economy, better selectivity and greater reproducibility.     

Synthesis of dimethyl carbonate from methanol and supercritical carbon dioxide

The synthesis of dimethyl carbonate (DMC) from methanol and supercritical carbon dioxide over various base catalysts has been studied. Compounds of group-I elements (Li, Na and K) were used as base catalysts. The promoter and the dehydrating agent were also used to enhance the yield of DMC. The effects of the catalysts, promoter and dehydrating agent on the yield of DMC were investigated. By-products such as dimethyl ether (DME) and C₁–C₂ hydrocarbons were formed with the DMC as a main product. The yield of DMC with different alkali metal catalysts ranked in the following order: K > Na > Li. The catalysts of the metal-CO₃ compounds were more effective than the metal-OH compounds in DMC synthesis. The maximum DMC yield reached up to about 12 mol% in the presence of K₂CO₃ (catalyst), CH₃I (promoter) and 2,2-dimethoxypropane (dehydrating agent) at 130–140°C and 200 bar. The reaction mechanism of DMC synthesis from methanol and supercritical carbon dioxide was proposed.     

Selective oxidation of alkanes with molecular oxygen and acetaldehyde in compressed (supercritical) carbon dioxide as reaction medium

The oxidation of cycloalkanes or alkylarenes with molecular oxygen and acetaldehyde as sacrificial co-reductant occurs efficiently in compressed (supercritical) carbon dioxide (scCO2) under mild multiphase conditions. No catalyst is required and high-pressure ATR-FTIR online measurements show that a radical reaction pathway is heterogeneously initiated by the stainless steel of the reactor walls. For secondary carbon atoms, high ketone to alcohol ratios are observed (3.5-7.9), most probably due to fast consecutive oxidation of alcoholic intermediates. Since C--C scission reactions are detected only to a very small extent, tertiary carbon atoms are transformed into the corresponding alcohols with high selectivity. Detailed analysis of the product distributions and other mechanistic evidence suggest that acetaldehyde acts not only as the sacrificial oxygen acceptor, but also as an efficient H-atom donor for peroxo and oxo radicals and as a crucial reductant for hydroperoxo intermediates. In comparison to other inert gases such as compressed N2 or Ar, the use of carbon dioxide was shown to increase the yields of alkane oxygenates under identical reaction conditions.     

Rheology of polydimethylsiloxane swollen with supercritical carbon dioxide

Viscosity curves were measured for polydimethyl siloxane (PDMS) melts swollen with dissolved carbon dioxide at 50 and 80°C for shear rates ranging from 40 to 2300 s⁻¹, and for carbon dioxide contents ranging from 0 to 21 wt %. The measurements were performed with a capillary extrusion rheometer modified for sealed, high-pressure operation to prevent degassing of the melt during extrusion. The concentration-dependent viscosity curves for these systems are self-similar in shape, exhibiting low-shear rate Newtonian plateau regions followed by shear-thinning “power-law” regions. Considerable reduction of viscosity is observed as the carbon dioxide content is increased. Classical viscoelastic scaling methods, employing a composition-dependent shift factor to scale both viscosity and shear rate, were used to reduce the viscosity data to a master curve at each temperature. The dependence of the shift factors on polymer chain density and free volume were investigated by comparing the shift factors for PDMS-CO₂ systems to those obtained by iso-free volume dilutions of high molecular weight PDMS. This comparison suggests that the free volume added to PDMS upon swelling with dissolved carbon dioxide is the predominant mechanism for viscosity reduction in those systems. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 523–534, 1997     

Lewis acids catalyzed ring-opening reactions of methylenecyclopropanes and epoxides in supercritical carbon dioxide or modified supercritical carbon dioxide with perfluorocarbon

The reactions of methylenecyclopropanes (MCPs) and epoxides with alcohols and aromatic amines can be carried out in supercritical carbon dioxide (scCO₂) or modified scCO₂ with perfluorocarbon which offer a way to synthesize various alcohols, amino-alcohols, homoallylic ethers, and amines under an environmentally benign condition.     

Isolation of Crithmum maritimum L. volatile oil by supercritical carbon dioxide extraction and biological assays

The chemical composition of the volatile concentrate obtained by supercritical CO2 extraction of aerial parts of Crithmum maritimum L. growing spontaneously in one area of Mediterranean coast (Buggerru, Sardinia Island, Italy) and in two areas of the Atlantic coast (Figueira da Foz and S. Pedro de Moel, Portugal) was investigated by GC and GC-MS. The major oil components identified were p-cymene, beta-phellandrene, gamma-terpinene, thymol methyl ether and dillapiole. The results showed the presence of two chemotypes of C. maritimum with different dillapiole contents, ranging from 0.2 to 64.2% in Portuguese and Italian plants, respectively. The minimal inhibitory concentration (MIC) and the minimal lethal concentration (MLC) were used to evaluate the antifungal activity of the oils against yeasts and dermatophyte strains. All the oils exhibited significant antifungal activity against dermatophyte strains. The oil with the higher amount of dillapiole (64.2%) was the most active with MIC values ranging from 0.08-0.32 microL mL(-1).     

Selective extraction of strontium with supercritical fluid carbon dioxide

Strontium (Sr(2+)) can be selectively extracted from aqueous solutions into supercritical fluid CO(2) at 60 °C and 100 atm with dicyclohexano-18-crown-6 (DC18C6) using CF(3)(CF(2))(6)CO(2) (-) (PFOA(-)) or CF(3)(CF(2))(6)CF(2)SO(3) (-) (PFOSA(-)) as a counter anion; at a mole ratio of Sr(2+) : DC18C6 : PFOA(-) = 1:10:50, the extraction of Sr (5.6 × 10(-5) M) from water at pH 3 is near quantitative whereas Ca(2+) and Mg(2+) at equal concentration are only extracted to a level of 7 and 1%, respectively; PFOSA(-) is an effective counter anion for selective extraction of Sr(2+) from 1.3 M HNO(3) with DC18C6 in supercritical CO(2).     

Simultaneous extraction of norflurazon and oxadixyl residues from food crops with supercritical carbon dioxide

Summary Norflurazon and Oxadixyl residues have been analysed by HRGC-ECD after extraction from field-treated sugar cane and grapes using classical solid-liquid extraction or supercritical fluid extraction. The extraction techniques were compared; the results indicate the advantages of SFE as an alternative method for analysis of pesticides in these samples.     

薤白挥发油成分的超临界CO2萃取及GC-MS分析

采取超临界CO2萃取和水蒸气蒸馏两种方法提取薤白中的挥发油,比较了两种提取方法得到的挥发油的理化性质,并利用GC-MS对它们进行了定性、定量分析。两种方法的主要提取物均为含硫化合物,但超临界CO2萃取法得到的含硫化合物的数量和质量都高于水蒸气蒸馏法得到的提取物。采用水蒸气蒸馏法提取8 h得到的萃取率为1.72%。通过设计的超临界CO2萃取的正交实验,得到了最佳萃取工艺条件为:压力25 MPa,温度40℃,CO2流量为25L/h。最佳萃取时间为120 min,萃取率为4.41%,是水蒸气蒸馏法萃取率的2.8倍。实验结果表明,超临界CO2萃取法简单易行,可以较快速、有效地提取薤白中的挥发油。     

Adsorption of eicosane and 1,2-hexanediol from supercritical carbon dioxide on activated carbon and chromosorb

Supercritical adsorption isotherms were measured for eicosane and 1,2-hexanediol on activated carbon and chromosorb 101 at 324.2 K and 11.45 MPa. Adsorption isotherms of both solutes on activated carbon have typical shapes and can be modelled by Langmuir or Freundlich equations. For chromosorb 101 the equilibrium loadings are a linear function of the concentration of the solute in the fluid phase. These results suggest that for chromosorb 101 a partition of the solute between two immiscible phases rather than adsorption occurs.     

Extraction of carotenoids and chlorophyll from microalgae with supercritical carbon dioxide and ethanol as cosolvent

The extraction of carotenoids and chlorophylls using carbon dioxide modified with ethanol as a cosolvent is an alternative to solvent extraction because it provides a high-speed extraction process. In the study described here, carotenoid and chlorophyll extraction with supercritical CO(2 )+ ethanol was explored using freeze-dried powders of three microalgae (Nannochloropsis gaditana, Synechococcus sp. and Dunaliella salina) as the raw materials. The operation conditions were as follows: pressures of 200, 300, 400 and 500 bar, temperatures of 40, 50 and 60 degrees C. Analysis of the extracts was performed by measuring the absorbance and by using empirical correlations. The results demonstrate that it is necessary to work at a temperature of 50-60 degrees C and a pressure range of 300-500 bar, depending on the type of microalgae, in order to obtain the highest yield of pigments. The best carotenoid/chlorophyll ratios were obtained by using supercritical fluid extraction + cosolvent instead of using conventional extraction. The higher selectivity of the former process should facilitate the separation and purification of the two extracted pigments.     

Copolymerization of vinylidene difluoride with hexafluoropropene in supercritical carbon dioxide

Vinylidene difluoride and hexafluoropropene are copolymerized in supercritical carbon dioxide at 280 bar and 50 °C by means of free radical copolymerization, initiated by diethyl peroxydicarbonate. The first stages of the reaction were monitored by turbidity measurements and the time/conversion curve was followed gravimetrically to measure the initial rates of polymerization. The obtained copolymers possessed bimodal molecular weight distributions, their average comonomer composition was well described by the Lewis‐Mayo equation with the copolymerization parameters r_VDF = 4.8 and r_HFP = 0. The glass transition and melting temperatures of the copolymers are similar to that of the materials resulting from aqueous emulsion polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1299–1316, 2006     

Photoactivity of titanium dioxide/carbon felt composites prepared with the assistance of supercritical carbon dioxide: Effects of calcination temperature and supercritical conditions

TiO2-coated carbon felt(TCF)composite catalysts have been prepared via a supercritical treatment of titanium tetraisopropoxide(TTIP)as the precursor.The physical properties of the catalysts were characterized by means of thermogravimetric and differential thermal analysis(TG–DTA),X-ray diffraction(XRD),fluorescence spectroscopy,scanning electron microscopy (SEM),and BET surface areas techniques.The photocatalytic activities of the materials were evaluated using the degradation of Congo red(CR)as a probe rea...     

Extraction of essential oil from Pimpinella anisum using supercritical carbon dioxide and comparison with hydrodistillation

Supercritical fluid extraction (SFE) of essential oil from Pimpinella anisum, using carbon dioxide as a solvent is presented in this work. An orthogonal array design OA9 (3(4)) was applied to select the optimum extraction condition. The effects of pressure, temperature, dynamic extraction time and methanol volume on the extraction efficiency were investigated by the three-level orthogonal array design. Results show that pressure has a significant effect on the extraction efficiency. The extract obtained from P. anisum by using supercritical fluid extraction was compared with the essential oil obtained by hydrodistillation, considering both quantity and quality of the product. SFE products were found to be of markedly different composition, compared with the corresponding hydrodistilated oil. The total amount of extractable substances obtained in SFE (7.5%) is higher than that obtained by hydrodistillation (3.1%) and SFE is faster than hydrodistillation method.     

Extraction of volatile oil from aromatic plants with supercritical carbon dioxide: experiments and modeling

An overview of the studies carried out in our laboratories on supercritical fluid extraction (SFE) of volatile oils from seven aromatic plants: pennyroyal (Mentha pulegium L.), fennel seeds (Foeniculum vulgare Mill.), coriander (Coriandrum sativum L.), savory (Satureja fruticosa Béguinot), winter savory (Satureja montana L.), cotton lavender (Santolina chamaecyparisus) and thyme (Thymus vulgaris), is presented. A flow apparatus with a 1 L extractor and two 0.27 L separators was built to perform studies at temperatures ranging from 298 to 353 K and pressures up to 30.0 MPa. The best compromise between yield and composition compared with hydrodistillation (HD) was achieved selecting the optimum experimental conditions of extraction and fractionation. The major differences between HD and SFE oils is the presence of a small percentage of cuticular waxes and the relative amount of thymoquinone, an oxygenated monoterpene with important biological properties, which is present in the oils from thyme and winter savory. On the other hand, the modeling of our data on supercritical extraction of volatile oil from pennyroyal is discussed using Sovová's models. These models have been applied successfully to the other volatile oil extractions. Furthermore, other experimental studies involving supercritical CO₂ carried out in our laboratories are also mentioned.