反相高效液相色谱法测定吴茱萸及制剂中吴茱萸碱和吴茱萸次碱

用反相高效液相色谱法测定了吴茱萸及制剂中吴茱萸碱和吴茱萸次碱，建立了中药及制剂中吴茱萸碱、吴茱萸次碱分离、测定的色谱方法。色谱条件：ＯＤＳ柱，乙腈＋水＋四氢呋喃＋乙酸（５２＋４８＋１＋０．１）为流动相，紫外检测波长２８０ｎｍ。方法简便、灵敏、准确、快速。     

Glyoxylic acid in the reaction of isatoic anhydride with amines: a rapid synthesis of 3-(un)substituted quinazolin-4(3H)-ones leading to rutaecarpine and evodiamine

A dual reactant/catalyst role of glyoxylic acid in the reaction of isatoic anhydride with various amines afforded a novel, robust and rapid synthesis of 3-(un)substituted quinazolin-4(3H)-ones. This metal catalyst-free reaction proceeds via an unusual and unexpected cleavage of C–C bond. A shorter and common route to two alkaloids, that is, rutaecarpine and evodiamine is also accomplished.     

Extraction of cationic surfactant templates from mesoporous materials by CH(3)OH-modified CO(2) supercritical fluid

Extraction of cationic surfactant templates from MCM-41, MCM-48, SBA-1 and SBA-3 has been conducted using CH₃OH-modified CO₂ supercritical fluid. The supercritical fluid extraction (SFE) has been integrated with thermogravimetry (TG), X-ray diffraction (XRD) and N₂ adsorption-desorption to evaluate extraction efficiency and structural stability of mesoporous materials. Experiments of optimization indicate that the conditions of 90 bar, 85 °C, CH₃OH/CO₂ = 0.1/1.0 ml/min and 3 h are most suitable for the SFE of cationic templates. 76-95% of the cationic templates can be extracted from the mesoporous materials. XRD and N₂ adsorption-desorption studies illustrate that SFE possesses some advantages over calcination in maintaining mesoporous uniformity and structural stability when used to remove templates. The impact of curing on mesoporous structure is also dealt with.     

Direct coupling of capillary supercritical fluid chromatography with supercritical fluid extraction using modified carbon dioxide

Capillary supercritical fluid chromatography has been directly coupled with supercritical fluid extraction using modified carbon dioxide. The mixed fluids were prepared with a single pump on-line mixing system. The most important step in the SFE-SFC interface was the elimination of the modifier solvent. This was achieved by use of a coupled trap, 0.1 mm i.d. and 0.53 mm i.d. capillary tubing connected in series, with the collected solutes refocused on the second (0.53 mm i.d.) trap before transfer into the separation column. This enabled complete elimination of various modifier solvents and high efficiency collection of the solutes. The effect of the modifier on trapping efficiency was investigated using methanol, ethanol, dichloromethane, hexane, and toluene at a variety of concentrations. n-Eicosane was, for example, trapped quantitatively by modified carbon dioxide containing up to 13 % (w/w) methanol. The use of the technique has been demonstrated by selective extraction of n-paraffins, fatty acid methyl esters, and alcohols from a silica matrix; the effect of different modifiers on the extraction of a mixture of pesticides from soil has also been investigated.     

Optimization of supercritical fluid extraction of saikosaponins from Bupleurum falcatum with orthogonal array design

Supercritical fluid extraction (SFE) was used to extract saikosaponins a, c and d from the root of Bupleurum falcatum. An orthogonal array design L₉(3)⁴ was employed as a chemometric method for the optimization of the SFE conditions. The effects of four factors including pressure (30–40 MPa), temperature (40–50°C), ethanol concentration (60–100%) and time (2.5–3.5 h) on the yields of saikosaponins were investigated by a preparative SFE system in the SFE mode. Under the optimized conditions, namely 35 MPa of pressure, 45°C of temperature, 80% of ethanol concentration and 3.0 h of time, the yields of saikosaponin c, saikosaponin a, saikosaponin d, total saikosaponins and SFE extract were 0.16, 0.12, 0.96, 1.24 and 16.48 mg/g, respectively. Determinations of the saikosaponins were performed by HPLC.     

Comparison of supercritical fluid and ultrasound-assisted extraction of carotenoids and chlorophyll a from Dunaliella salina

In the work described here the extraction processes of carotenoids and chlorophylls were analysed using two extraction techniques, namely ultrasound-assisted extraction and supercritical fluid extraction, and the results are compared. The solvents used for the ultrasound-assisted extraction were N,N′-dimethylformamide and methanol and for the supercritical fluid extraction, carbon dioxide. The raw material studied was Dunaliella salina, a microalgae characterized by the high levels of carotenoids present in its cellular structure. The results indicate that the supercritical fluid extraction process is comparable to the ultrasound-assisted extraction when methanol is used as solvent. In addition, the supercritical extraction process is more selective for the recovery of carotenoids than the conventional technique since it leads to higher values for the ratio carotenoids/chlorophylls. Finally, the effects of pressure and temperature on the extraction yields of the supercritical fluid extraction process were studied.     

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.     

Optimization of Algerian rosemary essential oil extraction yield by supercritical CO2 using response surface methodology

The present study deals with the determination of optimal values of operating parameters such as temperature and pressure leading to the best yield of a supercritical CO₂ extraction of essential oil from local rosemary plants, using the response surface methodology (RSM). The maximum of essential oil recovery percentage relative to the initial mass of leaf powder was 3.52 wt%, and was obtained at 313 K and 22 MPa.A second-order polynomial was used to express the oil recovery and the calculated mass of recovered oil using the RSM was very close to the experimental value, confirming the reliability of this technique.The chemical composition of the Algerian rosemary oil under the obtained optimal conditions (313 K and 22 MPa), determined by GC–MS analysis, revealed the presence of camphor (major compound) (52.12%), 1,8-cineole (9.65%), camphene (7.55%), α-pinene (6.05%), borneol (3.52%), aroma dendrene (2.11%), verbenone (1.97%), α-caryophyllene (1.71%), and others.     

Supercritical fluid extraction of Kava lactones from Kava root and their separation via supercritical fluid chromatography

Summary Seven Kava lactones were extracted from Kava root using both pure and 15% ethanol modified CO₂. Most of the Kava lactones were extracted employing 100% CO₂ with an efficiency greater than 90% relative to conventional solvent extraction using organic solvents. Extraction efficiency did not increase significantly when using 15% ethanol-modified CO₂ as an extraction fluid. Separation of extracted Kava lactones was obtained using various packed columns and methanol-modified CO₂. An optimized separation was achieved using either an amino or protein C₄ column at 125 atm and 80°C. Semi-preparative separation of Kava lactones was also obtained using two columns connected in series.     

墓头回CO2超临界萃取物的气相色谱-质谱分析

莫头回别名箭头风、臭罐子等,系败酱科败酱属植物异叶败酱patrinia heterophylla Bge或糙叶败酱patrinia scabra Bge。根及全草入药用,能治伤寒、温疟、妇女崩中,赤白带下,跌打损伤等疾病[1],对艾氏癌细胞有抑制及伤害作用[2]。目前对其化学成分的研究已有报道[3,4],对其挥发油     

Enrichment of the thymoquinone content in volatile oil from Satureja montana using supercritical fluid extraction

Supercritical fluid extraction (SFE) of the volatile oil from Satureja montana L. was performed under different conditions of pressure (90 and 100 bar), temperature (40 and 50°C), mean particle sizes (0.4, 0.6 and 0.8 mm) and CO₂ flow rate (0.8, 1.1 and 1.3 kg/h) to understand the influence of these parameters on the composition and yield of this oil. The results were compared with those obtained for the essential oil isolated by hydrodistillation (HD). The volatile and the essential oil were analysed by GC and GC‐MS. The main compounds are carvacrol (52.2–62.0% for HD vs. 41.7–64.5% for SFE), thymol (8.6–11.0% for HD vs. 6.0–11.3% for SFE), p‐cymene (6.9–12.8% for HD vs. 6.0–17.8% for SFE), γ‐terpinene (6.4–9.4% for HD vs. 2.3–6.0% for SFE) and β‐bisabolene (2.0–2.7% for HD vs. 2.2–3.5% for SFE). The major difference between SFE and HD was the relative amount of thymoquinone, an oxygenated monoterpene with important biological activities, which can be ten‐fold higher in volatile oil (1.6–3.0 for SFE vs. 0.2% for HD). The morphology of the glandular trichomes of S. montana and the effect of the grinding process on them was also evaluated by SEM.     

Supercritical fluid extraction of polybrominated diphenyl ethers (PBDEs) from house dust with supercritical 1,1,1,2-tetrafluoroethane (R134a)

The extraction of polybrominated diphenyl ethers (PBDEs) from SRM 2585 (Organic Contaminants in House Dust) was investigated using supercritical fluid R134a as an extraction solvent. Three methods of dust extraction were studied: (1) extraction of dry dust, (2) extraction of dry dust dispersed on Ottawa sand and (3) extraction of dust wet with dichloromethane. For each of the three sample preparation methods, extracts at three temperatures (110, 150, and 200 °C) above the critical temperature of R134a were performed. Eight PBDE congeners (BDE-28, -47, -99, 100, -153, -154, -183, and -209) in the SFE extracts were analyzed by liquid chromatography negative-ion atmospheric pressure photoionization tandem mass spectrometry (LC/NI-APPI/MS/MS). The optimum extraction of PBDEs from house dust using supercritical R134a is obtained when the dust is pre-wet with dichloromethane prior to extraction to swell the dust. For all sample preparation methods, higher temperatures afforded higher percent recoveries of the eight PBDE congeners. Only a combination of high-temperature (200 °C) and pre-wetting the dust with dichloromethane produced high recovery of the environmentally important, fully brominated PBDE congener, BDE-209.     

Optimization of supercritical fluid extraction of geniposidic acid from plantain seeds using response surface methodology

The process parameters of supercritical CO₂ (SCCO₂) plus modifer for the extraction of geniposidic acid from plantain seeds were studied using a Box–Behnken design. The effects of independent variables, that is, ethanol concentration (0–70%, ethanol:water, v/v), extraction pressure (10–30 MPa), and temperature (50–80°C) on the yield of geniposidic acid were evaluated. Results indicated that the data could be well fitted to a second-order polynomial model. The effects of ethanol concentration and temperature, as well as the interaction between ethanol concentration and temperature were significant (p < 0.05). The yield (8.9 mg/g) of modified SCCO₂ extraction at optimal conditions was compared with that obtained by Soxhlet extraction or ultrasound assisted extraction.     

Direct determination of tagitinin C in Tithonia diversifolia leaves by on-line coupling of supercritical carbon dioxide extraction to FT-IR spectroscopy by means of optical fibres

Supercritical fluid extraction (SFE) with carbon dioxide as extraction medium was on-line coupled to a FT-IR spectrometer equipped with a Mercury Cadmium Telluride (MCT) detector using a tailor-made high-pressure fibre optic flow cell. This method was optimised and developed for the monitoring in real time and the quantification of dynamic extractions of tagitinin C from Tithonia diversifolia leaves.In order to demonstrate the method ability to allow the direct quantification of tagitinin C in the extract medium the standard addition method was used. The area integration of curves obtained by plotting the absorbance of the highly specific CO stretching vibration at 1668 cm⁻¹ versus time (i.e. extractograms) was used as instrumental response.The SFE/FT-IR process was successfully validated using the accuracy profile as decision tool. On this basis, a linear regression model was chosen for the calibration curve. The relative standard deviation for repeatability and intermediate precision were between 0.8 and 3.1 %, respectively. Moreover, the method was found to be accurate as the two-sided 95% beta-expectation tolerance interval did not exceed the acceptance limits of 85 and 115% on the analytical range investigated (500-2500 μg of added amount of tagitinin C).The proposed method allowed the non-destructive extraction of tagitinin C and its on-line quantitative determination in less than 25 min thus facilitating the subsequent experiments or the pharmacological studies performed on this compound.     

Multiresidue analysis of four pesticide residues in water dropwort (Oenanthe javanica) via pressurized liquid extraction, supercritical fluid extraction, and liquid-liquid extraction and gas chromatographic determination

The primary objective of this study was to simultaneously analyze the residues of the most commonly used pesticides, chlorpyrifos-methyl, endosulfan, EPN, and iprodione in the water dropwort, via accelerated solvent extraction (ASE), supercritical fluid extraction (SFE), and conventional solvent extraction (LLE) techniques. Residue levels were determined using GC with electron-capture detection (GC-ECD). The confirmation of pesticide identity was performed by GC-MS in a selected ion-monitoring (SIM) mode. In none of the ASE and SFE techniques were the extraction conditions optimized. Rather, the experimental variables were predicated on the author's experience. The ECD response for all pesticides was linear in the studied range of concentrations of 0.005-5.0 ppm, with correlation coefficients in excess of 0.9991. At each of the two studied fortification levels, the pesticides yielded recoveries in excess of 72% with RSDs between 1 and 19%. The LODs were achieved at a range of levels from 0.001 to 0.063 ppm, depending on the pesticide utilized. The LOQs, which ranged from 0.003 to 0.188 ppm, were lower than the maximum residue limits (MRLs) authorized by the Korean Food and Drug Administration (KFDA). All of the methods were applied successfully to the determination of pesticide residues in the real samples. It could, therefore, be concluded that any of the techniques utilized in this investigation might prove successful, given that the applied extraction conditions are wisely chosen.     

Effects of process parameters on supercritical CO2 extraction of total phenols from strawberry (Arbutus unedo L.) fruits: An optimization study

The aim of this work was to optimize total phenolic yield of Arbutus unedo fruits using supercritical fluid extraction. A Box–Behnken statistical design was used to evaluate the effect of various values of pressure (50–300 bar), temperature (30–80°C) and concentration of ethanol as co‐solvent (0–20%) by CO₂ flow rate of 15 g/min for 60 min. The most effective variable was co‐solvent ratio (p<0.005). Evaluative criteria for both dependent variables (total phenols and radical scavenging activity) in the model were assigned maximum. Optimum extraction conditions were elicited as 60 bar, 48°C and 19.7% yielding 25.72 mg gallic acid equivalent (GAE) total phenols/g extract and 99.9% radical scavenging capacity, which were higher than the values obtained by conventional water (24.89 mg/g; 83.8%) and ethanol (15.12 mg/g; 95.8%) extractions demonstrating challenges as a green separation process with improved product properties for industrial applications.     

超临界二氧化碳流体萃取中药苦参的生物总碱

超临界ＣＯ2流体萃取(ＣＯ2 ＳｕｐｅｒｃｒｉｔｉｃａｌＦｌｕｉｄＥｘｔｒａｃｔｉｏｎ,ＳＦＥ ＣＯ2)技术是一种新型分离提取技术,其选择分离效果好,提取率高,产物没有有机溶剂残留,有利于热敏性物质和易氧化物质的萃取[1]。苦参为豆科植物,是传统的清热燥湿类中药,其有效成分主要为生物碱。苦参生物碱具有抗肿瘤、平喘、升白、抗菌、抗病毒、抗原虫等多种功能[2]。由于生物碱在植物中多数以盐的形式存在,若直接用极性较弱的溶剂提取往往提取不完全,故在提取前需碱化,使之成为游离碱[3]。本实验用氨水作碱化剂,选用无水甲醇为夹带剂,…