Optimization of extraction of evodiamine and rutaecarpine from fruit of Evodia rutaecarpa using modified supercritical CO(2)

Evodiamine and rutaecarpine have been intensively studied due to their pharmacological actions and clinical applications. In this report, supercritical fluid was used to extract evodiamine and rutaecarpine from the unripe fruit of Evodia rutaecarpa. Response surface methodology using Box-Behnken experimental design was utilized to optimize parameters for supercritical carbon dioxide extraction with methanol as co-solvent. The effect of various values of dynamic extraction time (30-90min), temperature (50-70°C) and pressure (200-400bar) on extraction yields of the two compounds was evaluated. Determinations of the extracts were performed by high-performance liquid chromatography. The experimental data obtained were fitted to second-order polynomial equations and analyzed by analysis of variance. The highest yields predicted were 1.217mg/g for evodiamine and 0.969mg/g for rutaecarpine at the optimal values (time 78min, temperature 62°C, pressure 280bar and co-solvent flow rate 0.4mL/min), based on the selected range of experimental conditions.     

Assay of free ferulic acid and total ferulic acid for quality assessment of Angelica sinensis

Activity of Chinese Danggui (DG), the processed root of Angelica sinensis (Oliv.) Diels, is linked to the ferulic acid content but the stability of ferulic acid during extraction for medicinal use is not known. The stabilities of ferulic acid and coniferyl ferulate were evaluated in the extracts of DG using a variety of extraction solvents. These included various combinations and proportions of methanol, water, formic acid, 1 M aqueous hydrochloric acid and 2% sodium hydrogen carbonate (NaHCO3) in water. Coniferyl ferulate was found liable to hydrolyze into ferulic acid in neutral, strongly acidic and basic solvents, where heat and water could facilitate this hydrolysis. However, the hydrolysis was relatively resisted in weakly organic acid. Based on the stability evaluation, two new terms, namely: free ferulic acid and total ferulic acid, were suggested and defined. Free ferulic acid refers to the natural content of ferulic acid in herbs. Total ferulic acid means the sum of free ferulic acid plus the amount of related hydrolyzed components. Meanwhile, the high-performance liquid chromatographic (HPLC) method was developed to assay free ferulic acid and total ferulic acid in DG using methanol-formic acid (95:5) and methanol-2% NaHCO3 in water (95:5) as extraction solvents, respectively. Ten DG samples were investigated on their contents of free and total ferulic acid. The results indicated that the amount variety of free ferulic acid was larger than that of their counterparts, and the ratio of total ferulic acid to free ferulic acid was 4.07 +/- 2.73 (mean +/- SD, n = 10). The chemical assay of DG using total ferulic acid content would be a better choice to assess the herbal quality and was recommended.     

Supercritical Fluid Extraction of Phenolic Compounds from Mango (Mangifera indica L.) Seed Kernels and Their Application as an Antioxidant in an Edible Oil

Phenolic compounds from mango (M. indica) seed kernels (MSK) var. Sugar were obtained using supercritical CO₂ and EtOH as an extraction solvent. For this purpose, a central composite design was carried out to evaluate the effect of extraction pressure (11–21 MPa), temperature (40–60 °C), and co-solvent contribution (5–15% w/w EtOH) on (i) extraction yield, (ii) oxidative stability (OS) of sunflower edible oil (SEO) with added extract using the Rancimat method, (iii) total phenolics content, (iv) total flavonoids content, and (v) DPPH radical assay. The most influential variable of the supercritical fluid extraction (SFE) process was the concentration of the co-solvent. The best OS of SEO was reached with the extract obtained at 21.0 MPa, 60 °C and 15% EtOH. Under these conditions, the extract increased the OS of SEO by up to 6.1 ± 0.2 h (OS of SEO without antioxidant, Control, was 3.5 h). The composition of the extract influenced the oxidative stability of the sunflower edible oil. By SFE it was possible to obtain extracts from mango seed kernels (MSK) var. Sugar that transfer OS to the SEO. These promissory extracts could be applied to foods and other products.     

Effects of different extraction methods and conditions on the phenolic composition of mate tea extracts

A simple and rapid HPLC method for determination of chlorogenic acid (5-O-caffeoylquinic acid) in mate tea extracts was developed and validated. The chromatography used isocratic elution with a mobile phase of aqueous 1.5% acetic acid-methanol (85:15, v/v). The flow rate was 0.8 mL/min and detection by UV at 325 nm. The method showed good selectivity, accuracy, repeatability and robustness, with detection limit of 0.26 mg/L and recovery of 97.76%. The developed method was applied for the determination of chlorogenic acid in mate tea extracts obtained by ethanol extraction and liquid carbon dioxide extraction with ethanol as co-solvent. Different ethanol concentrations were used (40, 50 and 60%, v/v) and liquid CO? extraction was performed at different pressures (50 and 100 bar) and constant temperature (27 ± 1 °C). Significant influence of extraction methods, conditions and solvent polarity on chlorogenic acid content, antioxidant activity and total phenolic and flavonoid content of mate tea extracts was established. The most efficient extraction solvent was liquid CO? with aqueous ethanol (40%) as co-solvent using an extraction pressure of 100 bar.     

Essential oil composition of Valeriana officinalis L. roots cultivated in Iran. Comparative analysis between supercritical CO2 extraction and hydrodistillation

The composition of essential oil extracted from Valeriana officinalis L. roots growing wild in Iran was studied by hydrodistillation and supercritical CO2 extraction. Forty-seven components representing 89.3% and 35 constituents varying from 86.1% to 95.1% of the oil obtained by hydrodistillation and supercritical CO2 were identified, respectively. The major components in the extracted oil from supercritical CO2 were isovaleric acid (18.7-41.8%), valerenic acid (8.2-11.8%), acetoxyvaleranone (5.6-9.6%), (Z)-valernyl acetate (4.5-6.5%), bornyl acetate (2.3-7.7%) and valerenol (3.7-5.2%), whereas by hydrodistillation were bornyl acetate (11.6%), valerenic acid (8.0%), (Z)-valernyl acetate (7.9%) and acetoxyvaleranone (7.6%). The analysis of the extracts was performed by capillary GC and GC/MS.     

固定化脂质体色谱研究中药复方的细胞膜通透性成分及其质量控制

提出了固定化脂质体色谱(immobilized liposome chromatography,ILC)研究中药复方的细胞膜通透性成分及其质量控制的方法。以当归补血汤及其组分为例,考察了它们在ILC色谱柱上的分离效果;当归补血汤水提取液和75％乙醇提取液在ILC色谱柱上各有8个保留峰,当归水提取液、甲醇提取液和75％乙醇提取液在ILC色谱柱上分别有3、6、9个保留峰,黄芪水提取液、甲醇提取液和75％乙醇提取液在ILC色谱柱上各有7个保留峰;建立了当归补血汤及其组分中阿魏酸和蒿本内酯的定量分析方法,当归补血汤水提取液和75％乙醇提取液中阿魏酸的含量分别为0．0743％和0．0688％,蒿本内酯的含量分别为0．0472％和0．457％,当归水提取液和75％乙醇提取液中阿魏酸的含量分别为0．0694％和0．0691％,蒿本内酯的含量分别为0．0781％和0．455％。     

Comparative analysis of the oil and supercritical CO(2) extract of Cymbopogon citratus Stapf

Dried and ground leaves of lemon grass (Cymbopogon citratus Stapf.) were used as a matrix for supercritical extraction of essential oil with CO(2). The objective of this study was to analyze the influence of pressure on the supercritical extraction. A series of experiments were carried out, for 360 min, at 50 degrees C and at different pressures: 90, 100, 110 and 120 bar. Extraction conditions were chosen to maximize citral content in the extract oil. The collected extracts were analysed by GC-MS and their composition was compared with that of the essential oil isolated by hydrodistillation and by steam distillation. At higher solvent density the extract aspect changes passing from a characteristic yellow essential oil to yellowish semi-solid mass because of the extraction of high molecular mass compounds. The optimum conditions for citral extraction were 90 bar and 50 degrees C, at these conditions citral represent more than 68% of the essential oil and the extraction yield was 0.65% while the yield obtained from hydrodistillation was 0.43% with a content of citral of 73%.     

Supercritical fluid extraction of Beauvericin from maize

Beauvericin (BEA), a supercritical fluid extraction with supercritical carbon dioxide from maize was investigated. Extraction efficiencies under several different extraction conditions were examined. Pressure, temperature, extraction time, organic modifier and water matrix content (10%) were investigated. The best extraction conditions were at a temperature of 60 °C, 3200 psi, for 30 min static extraction time and methanol as modifier solvent. Extraction recovery of 36% without modifier by adding water to the matrix in the extraction vessel (reproducibility relative standard deviations (R.S.D.)=3-5%) were recorded. Extraction recovery of 76.9% with methanol as co-solvent (reproducibility R.S.D.=3-5%) was obtained. Data shows that SFE gives a lower BEA recovery compared to conventional extraction protocol with organic solvents while SFE with modifier and conventional extraction yields are comparable. BEA extract contents were determined by high pressure liquid chromatography (HPLC) with a diode array detector (DAD) at 205 nm and BEA peak confirmed by LC-MS. Acetonitrile-water as mobile phase and column C-18 were both tested. Instrumental and analytical parameters were optimized in the range linear interval from 1 to 500 mg kg⁻¹ and reached a detection limit of 2 ng.     

Comparisons of soxhlet extraction, pressurized liquid extraction, supercritical fluid extraction and subcritical water extraction for environmental solids: recovery, selectivity and effects on sample matrix

Extractions of a polycyclic aromatic hydrocarbon (PAH)-contaminated soil from a former manufactured gas plant site were performed with a Soxhlet apparatus (18 h), by pressurized liquid extraction (PLE) (50 min at 100 degrees C), supercritical fluid extraction (SFE) (1 h at 150 degrees C with pure CO2), and subcritical water (1 h at 250 degrees C, or 30 min at 300 degrees C). Although minor differences in recoveries for some PAHs resulted from the different methods, quantitative agreement between all of the methods was generally good. However, the extract quality differed greatly. The organic solvent extracts (Soxhlet and PLE) were much darker, while the extracts from subcritical water (collected in toluene) were orange, and the extracts from SFE (collected in CH2Cl2) were light yellow. The organic solvent extracts also yielded more artifact peaks in the gas chromatography (GC)-mass spectrometry and GC-flame ionization detection chromatograms, especially compared to supercritical CO2. Based on elemental analysis (carbon and nitrogen) of the soil residues after each extraction, subcritical water, PLE, and Soxhlet extraction had poor selectivity for PAHs versus bulk soil organic matter (approximately 1/4 to 1/3 of the bulk soil organic matter was extracted along with the PAHs), while SFE with pure CO2 removed only 8% of the bulk organic matrix. Selectivities for different compound classes also vary with extraction method. Extraction of urban air particulate matter with organic solvents yields very high concentrations of n- and branched alkanes (approximately C18 to C30) from diesel exhaust as well as lower levels of PAHs, and no selectivity between the bulk alkanes and PAHs is obtained during organic solvent extraction. Some moderate selectivity with supercritical CO2 can be achieved by first extracting the bulk alkanes at mild conditions, followed by stronger conditions to extract the remaining PAHs, i.e., the least polar organics are the easiest organics to extract with pure CO2. In direct contrast, subcritical water prefers the more polar analytes, i.e., PAHs were efficiently extracted from urban air particulates at 250 degrees C, with little or no extraction of the alkanes. Finally, recent work has demonstrated that many pollutant molecules become "sequestered" as they age for decades in the environment (i.e., more tightly bound to soil particles and less available to organisms or transport). Therefore, it may be more important for an extraction method to only recover pollutant molecules that are environmentally-relevant, rather than the conventional attempts to extract all pollutant molecules regardless of how tightly bound they are to the soil or sediment matrix. Initial work comparing SFE extraction behavior using mild to strong conditions with bioremediation behavior of PAHs shows great promise to develop extraction methodology to measure environmentally-relevant concentrations of pollutants in addition to their total concentrations.     

Supercritical carbon dioxide extraction of Usnea longissima (L.) Ach.: Optimization by Box-Behnken design (BBD)

Usnic acid (UA) was extracted from Usnea longissima (L.) Ach. in supercritical carbon dioxide (SC-CO₂) medium. The selected process parameters were extraction temperature (35–45 °C), amount of co-solvent (0%–5%) and extraction time (5–9 h). These parameters were applied to Box-Behnken design (BBD) belonging to response surface methodology (RSM) to determine optimum process parameters for the highest amount of UA in the extract. g UA/100g lichen, extraction yield % and UA content values were calculated in the range of 0.045–0.317, 2.77–5.4 and 71%–82% in different experimental conditions, respectively. The optimum conditions were predicted as 42 °C, 4.3% (ethanol) and 7.48 h. It was determined that the predicted and experimental values of g UA/100g lichen were compatible, and the suggested model was valid.     

Isolation of Ferulic Acid from Wheat Bran with a Deep Eutectic Solvent and Modified Silica Gel

Five deep eutectic solvents (DESs) were synthesized with choline chloride and glycerol at ratios from 1:1 to 1:5 and used to extract ferulic acid from wheat bran. The DES with choline chloride:glycerol at a 1:2 molar ratio (DES-2) provided the highest extraction yield. The optimal extraction conditions for DES-2 were obtained using response surface methodology with a yield of 5.86?mg?·?g^?1 ferulic acid. The DES-2 was used to modify silica gel and purify ferulic acid from wheat bran by solid-phase extraction (SPE). The yields were compared for silica gel and silica gel modified with ionic liquid. The recoveries for ferulic acid were 64.1, 89.7, and 80.3%, respectively. Silica gel modified with DES-2 provided the highest recovery. The materials were characterized by infrared spectroscopy and scanning electron microscopy. The DESs were used as extraction solvents and to modify silica gel for SPE, expanding their use in the isolation of ferulic acid from wheat bran.     

酸洗脱灰及离子交换对低阶煤热溶剂提质分离的影响

采用酸洗脱灰、酸洗和Na/Co离子交换对两种低阶煤(MM和LY)进行预处理,然后以1-甲基萘为溶剂对预处理煤进行热溶剂提质萃取,把煤分成提质煤(UC)、高分子量萃取物(deposit)和低分子量萃取物(soluble)3种主要固体组分,以及少量水和气体产物。结果表明,通过脱灰和离子交换均提高了两种萃取物的收率及碳含量,并明显促进了煤中含氧官能团的脱除。脱灰后MM煤的高分子量萃取物收率从3.5%增加到9.5%,Na离子交换LY的低分子量萃取物的碳含量高达85.3%、氧含量低于6.4%。离子交换对两种萃取物的物理化学性质有明显的影响,Na+的影响尤为显著。酸洗脱灰和离子交换对低阶煤热溶剂提质萃取有明显促进作用。     

"四物汤"中当归有效部位及有效成分的研究

研究发现“四物汤”中的当归对家兔主动脉血管有舒张作用的有效部位及有效成分。采用超临界CO2流体萃取当归中的脂溶性部位,经柱层析法分离和高效液相色谱法纯化,并结合细胞膜色谱法筛选和气相-质谱联用色谱法鉴定,确定当归中的有效成分。结果表明：当归脂溶性部位经柱层析分离得到的正己烷-醋酸乙酯洗脱部位为有效部位,其中藁本内酯、邻苯二甲酸二甲酯和邻苯二甲酸二乙酯等是当归中对兔主动脉血管有生理活性的有效成分。     

Orthogonal array design for the optimization of supercritical fluid extraction of baicalin from roots of Scutellaria baicalensis Georgi

Supercritical fluid was used to extract baicalin from the roots of Scutellaria baicalensis Georgi. An orthogonal array design (OAD), OA(9)(3(4)), was employed as a chemometric method for the optimization of the supercritical fluid extraction of baicalin from the herbal medicine. Four parameters, namely, modifiers, temperature and pressure of supercritical fluid, and the dynamic extraction time, were studied and optimized by a three-level OAD in which the interactions between the parameters were neglected. Determinations of the extracts were performed by high-performance liquid chromatography. The effects of parameters were studied using analysis of variance. The results showed that selection of the modifier was the main factor in attaining higher yields of baicalin. While the other three factors had some effect on the extraction of the compound, the effect was much less than that of the modifiers. 1,2-Propanediol-modified supercritical fluid was more effective than 95% ethanol-modified supercritical carbon dioxide or methanol-modified supercritical carbon dioxide for the extraction of baicalin from the solid matrix. Finally, experimental conditions were proposed which can provide the highest extraction yield with respect to the considered factors.     

Supercritical fluid extraction and liquid chromatography-electrospray mass analysis of vinblastine from Catharanthus roseus

Supercritical fluid extraction using carbon dioxide modified with methanol, methanol-diethylamine, or methanol-triethylamine was used to extract vinblastine from the aerial portions of Catharanthus roseus. An HPLC-electrospray ionization (ESI)/MS analysis method was also developed to quantify the alkaloids in these extracts. Of the supercritical solvents evaluated, carbon dioxide-methanol-triethylamine (80 : 18 : 2) at 80 degrees C and 34.0 MPa greatly improved the supercritical fluid extraction (SFE) yield of vinblastine by as much as 76.4% over methanol extraction, while the other solvent conditions extracted the compound at yields less than 25% that of a methanol extraction. These results were confirmed by the robust HPLC-ESI/MS analytical method developed in this study.     

Valuable Natural Antioxidant Products Recovered from Tomatoes by Green Extraction

Lycopene, β-carotene and ω-fatty acids are major compounds in tomatoes with known antioxidant activity, capable of preventing health disorders. The identification of potential natural sources of antioxidants, extraction efficiencies and antioxidant activity assessments are essential to promote such products to be used in the food, pharmaceutical or cosmetic industries. This work presents four added-value products recovered from tomatoes: pigmented solid oleoresin, pigmented oil and two raw extracts from supercritical and Soxhlet extraction. Different parameters including the matrices of tomatoes, extraction methods, green solvents and operating parameters were varied to obtain extracts with different qualities. Extract analysis was performed using UV–VIS, FT–IR, GC–MS, Folin–Ciocalteu and DPPH methods. The highest-quality extract was the solid oleoresin obtained from pomace using supercritical CO₂ extraction at 450 bar, 70 °C and 11 kg/h: 1016.94 ± 23.95 mg lycopene/100 g extract, 154.87 ± 16.12 mg β-carotene/100 g extract, 35.25 ± 0.14 mg GAE/g extract and 67.02 ± 5.11% inhibition DPPH. The economic feasibility of the three extraction processes (1:10:100 kg dried pomace/batch as scalability criterion) was evaluated. The most profitable was the supercritical extraction process at the highest capacity, which produces pigmented solid oleoresin and oil with high content of lycopene valorized with a high market price, using natural food waste (pomace).     

Optimization of Ethanol Supercritical Fluid Extraction of Medicinal Compounds from St. John's Wort by Central Composite Design

Extraction of medicinal compounds from St John's Wort was performed using supercritical ethanol. The supercritical fluid extraction parameters were optimized via response surface methodology which included a central composite design. The independent variables were extraction temperature (ranging from 300°C to 340°C), extraction times (ranging from 60 to 120 min), and plant concentration (ranging from 8% to 12%). The response was the St John's Wort extract yield. The extraction temperature was the most significant factor which affects St John's Wort yields according to statistical results. The coefficient of determination was estimated to be 0.98 which indicates the effectiveness of the model and its adaptability to the experimental data. The extract of St John's Wort was comprised of a wide array of compounds including phenols, acids, acid esters, and alkanes. The most prominent components of the extract of St. John's Wort in terms of their relative concentrations were linoleic acid ethyl ester, oleic acid ethyl ester, hexadecanoic acid ethyl ester, and nonacosane.     

Optimized Green Extraction of Polyphenols from Cassia javanica L. Petals for Their Application in Sunflower Oil: Anticancer and Antioxidant Properties

The total phenolic content (TPC) from Cassia javanica L. petals were extracted using ethanolic solvent extraction at concentrations ranging from 0 to 90% and an SCF-CO₂ co-solvent at various pressures. Ultrasound-assisted extraction parameters were optimized using response surface methodology (RSM). Antioxidant and anticancer properties of total phenols were assessed. An SCF-CO₂ co-solvent extract was nano-encapsulated and applied to sunflower oil without the addition of an antioxidant. The results indicated that the best treatment for retaining TPC and total flavonoids content (TFC) was SCF-CO₂ co-solvent followed by the ultrasound and ethanolic extraction procedures. Additionally, the best antioxidant activity by β-carotene/linoleic acid and DPPH free radical-scavenging test systems was observed by SCF-CO₂ co-solvent then ultrasound and ethanolic extraction methods. SCF-CO₂ co-solvent recorded the highest inhibition % for PC3 (76.20%) and MCF7 (98.70%) and the lowest IC₅₀ value for PC3 (145 µ/mL) and MCF7 (96 µ/mL). It was discovered that fortifying sunflower oil with SCF-CO₂ co-solvent nanoparticles had a beneficial effect on free fatty acids and peroxide levels. The SCF-CO₂ method was finally found to be superior and could be used in large-scale processing.     

Separation of γ-linolenic and other polyunsaturated fatty acids from Boraginaceae via supercritical CO2

Essential fatty acids were extracted from Echium amoenum (Boraginaceae) seed oil via supercritical carbon dioxide and the results were compared with conventional Soxhlet method as the base case of 100% recovery. The response surface methodology was used to optimize the effective extraction parameters. The chemical composition of recovered oil was analyzed by polar and non-polar gas chromatograph-flame ionization detector columns. The experimental results indicated that echium seed contained 25 wt% oil and the maximum extraction oil recovery of 92% was obtained via supercritical CO(2) at optimal operating conditions (43°C, 280 bar, 1.5 mL/min, 25 min static time and 130 min dynamic time). At similar operating conditions, applying 2.5 and 5 mol% ethanol as a modifier enhanced the recovery to 96 and 112%, respectively. The results showed that supercritical fluid extraction is a viable technique for separation of constituents such as γ-linolenic acid (7-8%), palmitic acid (6-7%), stearic acid (3-4%), oleic acid (12-13%), linoleic acid (19-20%), α-linolenic acid (40-41%) and stearidonic acid (8-9%) from Boraginaceae.     

Supercritical fluid extraction of phenol compounds from olive leaves

A clean, highly selective supercritical fluid extraction (SFE) method for the isolation of phenols from olive leaf samples was examined. Total phenol extracts were determined using the Folin-Ciocalteu reagent. Dried, ground, sieved olive leaf samples (30 mg) are subjected to SFE, using carbon dioxide modified with 10% methanol at 334 bar, 100 degrees C (CO(2) density 0.70 g ml(-1)) at a liquid flow-rate of 2 ml min(-1) for 140 min. Diatomaceous earth is used to reduce the void volume of the extraction vessel. The influence of extraction variables such as modifier content, pressure, temperature, flow-rate, extraction time, and collection/elution variables, were studied. Supercritical fluid extracts were screened for acid compounds such as carboxylic acids and phenols using Electrospray-MS (in the negative ionization mode). SFE was found to produce higher phenol recoveries than sonication in liquid solvents such as n-hexane, diethyl ether and ethyl acetate. However, the extraction yield obtained was only 45%, using liquid methanol.