Simultaneous supercritical fluid derivatization and extraction of formaldehyde by the Hantzsch reaction

A study where the Hantzsch reaction is used to produce the chemical derivatization of formaldehyde in a supercritical medium is presented in this paper. Pressure, temperature and other parameters such as static and dynamic extraction time must be optimized to increase the yield of this kinetically controlled reaction. A 2(5-1) (resolution V) factorial design was used to study the significant parameters affecting the supercritical process in terms of resolution and sensitivity. A subsequent central composite design was employed to find the conditions of maximum response. Ultraviolet-visible spectrophotometry was used as the detection technique. The optimum conditions were used for the determination of formaldehyde in real finger-paints by means of the previous addition of known quantities of this analyte to the paint. Results were compared with those obtained with supercritical fluid extraction and subsequent chemical derivatization and an improvement of sensitivity as well as a reduction of time of analysis, solvent waste and reagents consumption were observed.     

Optimization of parameters for the supercritical fluid extraction in the determination of N-nitrosamines in rubbers

The study of the possibilities of supercritical fluid extraction (SFE) with N-nitrosamines in rubbers has been carried out. Home-made materials fortified with several N-nitrosamines were prepared in order to optimize the SFE parameters. A Plackett-Burman design was employed to evaluate the influence of those parameters to be controlled in SFE, such as pressure, temperature, static and dynamic time, restrictor temperature and volume of modifier while CO2 was used as the extraction fluid. An extra central composite design for the main factors (according to the previously obtained results) was also developed in order to refine the best supercritical conditions for the extraction of N-nitrosamines from rubbers. Gas chromatography with a nitrogen and phosphorus sensitive detector was used to achieve sensitivity and limits of detection for the concentrations expected in plastic materials. The proposed analytical method has shown to be useful in the determination of N-nitrosamines even for complex matrices.     

超临界CO2萃取香草兰化学成分分析

香草兰 ,学名 :ＶａｎｉｌｌａｐｌａｎｉｆｏｌｉａＡｎｄｒ.,又名香荚兰 ,香子兰 ,属兰科香子兰属 ,是一种名贵的多年生热带藤本植物 ,有独特的香味 ,被称誉为“食品香料之王”。香草兰经加工后 ,是食品工业的重要天然香料 ,也用于烟草业、化妆品业和药物[1,2 ] 。香草兰原产于墨西哥 ,主产国还有马达加斯加、印尼、牙买加等[3 ] 。近年来 ,我国海南、云南等地也大力种植和推广。超临界流体萃取 (ＳｕｐｅｒｃｒｉｔｉｃａｌＦｌｕｉｄＥｘｔｒａｃｔｉｏｎ ,简称ＳＣＦＥ)是近 2 0年发展起来的现代提取分离技术 ,具有工艺简单、成本低、…     

Determination of benzophenones in a cosmetic matrix by supercritical fluid extraction and capillary electrophoresis

Benzophenones are common additives in commercial sunscreen products. These UV absorbers were extracted by supercritical fluid extraction (SFE), and then analyzed by capillary zone electrophoresis (CZE) and high-performance liquid chromatography. This study was applied to identify the contents of benzophenones in cosmetic matrix, and simultaneously, to investigate the behavior of migration in CZE. Adding non-ionic surfactant (Tween 20) to optimize the separation in the CZE operation improves resolution. In SFE, we chose carbon dioxide with 2.5% modifier of 10% aqueous phosphoric acid-MeOH (1:1) as the supercritical fluid. Real recoveries of up to 92% with relative standard deviations of less than 4.0% were achieved. These analytical techniques were also applied to assay benzophenones for ten commercial sunscreen cosmetics. We found benzophenone 3 was the most commonly used sunscreen additive in Taiwan.     

Determination of atractylon in Atractylodes rhizome using supercritical fluid chromatography on-line coupled with supercritical fluid extraction by the direct induction method

Atractylon was extracted from Atractylodes rhizome within 15 s with supercritical carbon dioxide. The extraction was so rapid that SFE extracts could be transported directly into an SFC column and analyzed. Atractylon was eluted and separated in ca. 5 min. Analyte recovery was 30% higher than when using solvent extraction. Determination of atractylon in Atractylodes rhizome was achieved with only a few mg of crude drug sample. Atractylon is unstable due to oxidation and is easily transformed to atractylenolides. Loss of analytes during the procedures was also minimal with this on-line SFE–SFC system.     

Determination of sunscreen agents in cosmetic products by supercritical fluid extraction and high-performance liquid chromatography

A rapid supercritical fluid extraction (SFE) procedure for the isolation of five of the most common sunscreen agents (2-ethylhexyl-p-dimethylaminobenzoate, 2-hydroxy-4-methoxybenzophenone, 2-ethylhexyl-p-methoxycinnamate, 4-methylbenzylidene camphor and 4-tert.-butyl-4′-methoxydibenzoylmethane) from cosmetic products is described. Investigation of the factors affecting the extraction efficiency in SFE indicated that sunscreen recoveries were affected mainly by the supercritical CO₂ pressure and by the trapping method. The sunscreens were analyzed by reversed-phase high-performance liquid chromatography after a 10-min extraction of the cosmetic product with CO₂ at 250 bar and 40°C, using sequential glass surface and C₁₈ sorbent as collection system. A quantitative comparison of SFE with a liquid extraction procedure was performed on commercial cosmetics. The SFE method yielded recoveries higher than 94.8% compared with conventional liquid extraction and exhibited a precision better than 5.3% relative standard deviation. Moreover, SFE minimized sample handling, reduced the consumption of harmful solvents and afforded a more effective purification of the cosmetic matrices.     

Determination of total fat in milk- and soy-based infant formula powder by supercritical fluid extraction

Commercially available simple benchtop systems using CO2 supercritical fluid extraction (SFE) eliminate expensive organic solvent disposal problems and offer potential to meet a demand for rapid, accurate high-volume gravimetric determinations of total fat content of infant formula powders. A Data Quality Objectives (DQOs) approach was used to evaluate the performance characteristics of instrumental SFE extraction for determination of total gravimetric fat in infant formula. The established DQOs included the following: ACCURACY: Correct values were obtained for a suitable reference material, SRM 1846 Infant Formula [National Institute of Standards and Technology (NIST), Gaithersburg, MD]. RUGGEDNESS: Variables were defined as (1) extraction time (35 min optimum); (2) ratio of sample size to diatomaceous earth support material (1 g sample/2 g support); (3) ratio of distilled water to alcohol (50% isopropanol optimum for both milk- and soy-based infant formula samples); (4) extraction flow rate was 3-3.5 mL/min optimum. PRECISION: Relative standard deviations of multiple determinations fell within the Horwitz limits of acceptability of < or = 2.8% at the level of analyte determined (0.34-2.5% obtained). SCOPE OF APPLICABILITY: Includes milk- and soy-based infant formula powders. Research data were obtained by use of a commercially available fat analyzer. Samples of the SRM, 2 commercial milk-based and 3 commercial soy-based infant formula products were distributed to 2 additional collaborating laboratories. Very good agreement was obtained among the submitting and collaborating laboratories for these samples. The use of clearly defined DQOs to establish method performance characteristics, along with the commercially available reference material, provided the mechanism for verification and validation of analytical methodology.     

Determination of anabolic steroids in creatine nutritional supplements after supercritical fluid extraction

The effects of various parameters, i.e. extraction pressure, temperature, time, and modifier on the efficiency of extraction were investigated using an analytical-scale supercritical fluid extraction system. An optimal set of conditions for the extraction and determination by gas chromatography-mass spectrometry of trimethylsilyl derivatives of 4-androstene-3,17-dione, 1,4-androstadiene-3,17-dione, nandrolone, and testosterone in nutritional supplements was developed. The optimum amount of creatine supplement was 1 g, while the optimum pressure and temperature were determined to be 35 MPa and 80 °C, respectively. The optimum dynamic extraction time was 45 min. The limit of detection (LOD) of the investigated compounds ranged from 5 to 25 ng · g⁻¹ of supplement, while recoveries ranged from 76.1 to 86.6%. Correspondence: Petra Mikulcikova, Department of Analytical Chemistry, Faculty of Chemical Technology, University of Pardubice, nám. Cs. Legií 565, CZ 532 10 Pardubice, Czech Republic     

Collection in analytical-scale supercritical fluid extraction

This review is a comprehensive summary of available collection techniques in supercritical fluid extraction (SFE), with emphasis on which parameters are especially important for a successful analyte collection. Environmental, biological and agricultural applications, including several types of sample matrices and analyte groups, are discussed with respect to choice of collection mode and optimization of collection conditions. This review also includes discussions about collection when a modifier is used or when the sample contains large amounts of fat or water, as well as possibilities to achieve enhanced selectivity.     

Chemicals from forest products by supercritical fluid extraction

Supercritical acetone or methanol extraction of wood gave liquid products with a maximum yield of 74%. Approximately 5% of these complex products was identified as substituted guaiacols and levoglucosan. Acetone extract could substitute for 30% of the phenol in phenolic resins.

Resin and fatty acids were extracted from southern pine and waxes from Douglas-fir bark using supercritical carbon dioxide, nitrous oxide, propane or ethylene. Of these, propane and nitrous oxide gave the best yields.     

Determination of prostaglandins in human seminal fluid by solid-phase extraction, pyridinium dichromate derivatization and high-performance liquid chromatography

Prostaglandins of the E type (PGEs) in human seminal fluid have been determined by reversed-phase high-performance chromatography on a C18 column and ultraviolet detection at 230 nm after solid-phase extraction (C18) and oxidation to the corresponding 15-oxoprostaglandin derivatives by pyridinium dichromate in acetonitrile. Under optimized conditions, PGEs from 10-ml seminal samples were extracted into 4 ml of methyl formate with high recoveries (estimated at greater than 95%) and subsequently separated under mild chromatographic conditions (0.5 mM formic acid-acetonitrile, apparent pH 3.8). Comparable analytical sensitivities were obtained with detection at 230 nm with a conventional deuterium lamp spectrophotometer and a photometer equipped with a cadmium emission source, while with a diode-array spectrophotometer, signal-to-noise ratios were reduced with factors between 4.4 and 3.1, depending on the spectral bandwidth of the instrument. Theoretical aspects of signal-to-noise optimization of ultraviolet detectors are discussed. The stability of dilute standard solutions of PGE2 and PGD2 was measured, showing solutions in dichloromethane at 20 degrees C to be as stable as acetonitrile solutions at 5 degrees C over a period of thirty days. Absolute ethanol and acetonitrile were equally suited as solvents.     

Enrichment of tocopherols in wheat germ by directly coupled supercritical fluid extraction with semipreparative supercritical fluid chromatography

Enrichment of tocopherol by coupled supercritical fluid extraction/preparative supercritical fluid chromatography is described. Wheat germ powder is used as the starting material and is subjected to supercritical fluid extraction with carbon dioxide. The extracted oil containing tocopherols is concentrated and trapped on a silica gel column by reducing the pressure of carbon dioxide. The trapped oil is then eluted and separated on a silica gel column of 20 mm i.d. x 20 mm length. The column effluent is fractionated by monitoring UV absorption at 290 nm. With this method, tocopherol content of the wheat germ is enriched 100-fold.     

Analysis of organic pollutants in sewage by supercritical fluid extraction

Summary Analytical methods have been developed for the determination of organic pollutants of intermediate polarity in sewage. Water samples are first passed through a solid phase adsorption cartridge. The analytes are then extracted from the absorbent with supercritical CO₂ into a small volume of trapping solvent. Finally, the extracts are analyzed directly by capillary gas chromatography and gas chromatography-mass spectrometer. The various parameters (pressure, temperature, type and concentration of modifiers, trapping solvent, flow rate and volume of supercritical fluid and equilibrium time) influencing the efficiency of extraction were studied. Extraction efficiencies for the test compounds are >70%, and relative standard deviations are <4.6% (n=3). The methods established were applied to the analysis of sewage at the Lanzhou Wastewater Treatment Plant, China. 66 organic pollutants were detected, of which 15 compounds appeared in the list of priority pollutants suggested by the US EPA.     

Determination of fenpyroximate in apples by supercritical fluid extraction and packed capillary liquid chromatography with UV detection

A method using off-line supercritical fluid extraction (SFE) and micro liquid chromatography (μLC) with UV detection at 260 nm, was developed for selective determination of fenpyroximate in apple samples. The packed capillary liquid chromatography method utilises 20 μl injection volumes with on-column focusing. A 350×0.32 mm capillary column packed with Kromasil 100-C₁₈ of 5 μm particle size was used with a mobile phase of acetonitrile–10 mM ammonium acetate (85:15, v/v) at a flow of 5 μl/min. A two-step SFE procedure was used to extract fenpyroximate selectively in 2 g apple samples, with Hydromatrix (HMX) added as a water absorbent at a 1:1 (w:w) ratio. Fenpyroximate was extracted at 200 bar and 90°C for 15 min using carbon dioxide at a flow of 2 ml/min, and solvent trapping collection in 10 ml acetonitrile. The volume of the acetonitrile extract was reduced by evaporation and water was added to a final composition of acetonitrile–water (40:60, v/v). The resulting 2.0 ml solution was filtered using a 0.45 μm poly(vinylidene difluoride) syringe filter before μLC analysis. Validation of the method was accomplished with apple samples spiked with fenpyroximate, covering the range of 0.1 to 1.0 μg/kg. The within-day and between-day repeatabilities were in the range 4–18% relative standard deviation. Accuracy, measured as recovery, was found to be approximately 60%. Apple samples from a field treated with fenpyroximate were analysed. None of the samples contained fenpyroximate above the quantification level.     

Improved supercritical fluid extraction of sulphonamides

Summary Different ways used for enhancing the yield of sulphonamides leached from solid supports are reported. Supercritical CO₂ and methanol-modified CO₂ were used as extractants of the target analytes and the impregnation of the solid sample with buffer, derivatization of the analytes and ion-pair formation were assessed. Only the sulphonamide/tetramethyl-ammonium ion-pairs are quantitatively extracted from the solid supports using pure supercritical CO₂, while the other modifications and the presence of a cosolvent lead to recoveries lower than 30% for most of the analytes. Individual separation/quantitation of the analytes was performed off-line using a liquid chromatograph.     

Some applications of supercritical fluid extraction

Supercritical fluid extraction (SFE) exploits the solvation power of fluids at temperatures and pressures close to their critical point. Use of SFE with supercritical CO₂ is reported for the extraction of caffeine and quinine from various plant materials and of morphine from serum. Results are compared with those obtained by extractions with subcritical methanol and tetrahydrofuran, normal organic Soxhlet extractions and solid-phase extraction.     

Determination of major aromatic constituents in vanilla using an on‐line supercritical fluid extraction coupled with supercritical fluid chromatography

An on‐line supercritical fluid extraction coupled with supercritical fluid chromatography method was developed for the determination of four major aromatic constituents in vanilla. The parameters of supercritical fluid extraction were systematically investigated using single factor optimization experiments and response surface methodology by a Box–Behnken design. The modifier ratio, split ratio, and the extraction temperature and pressure were the major parameters which have significant effects on the extraction. While the static extraction time, dynamic extraction time, and recycle time had little influence on the compounds with low polarity. Under the optimized conditions, the relative extraction efficiencies of all the constituents reached 89.0–95.1%. The limits of quantification were in the range of 1.123–4.747 μg. The limits of detection were in the range of 0.3368–1.424 μg. The recoveries of the four analytes were in the range of 76.1–88.9%. The relative standard deviations of intra‐ and interday precision ranged from 4.2 to 7.6%. Compared with other off‐line methods, the present method obtained higher extraction yields for all four aromatic constituents. Finally, this method has been applied to the analysis of vanilla from different sources. On the basis of the results, the on‐line supercritical fluid extraction‐supercritical fluid chromatography method shows great promise in the analysis of aromatic constituents in natural products.     

超临界流体萃取法对有机锡化合物的选择性萃取

 研究了用超临界流体萃取法直接从脂肪基质的固体样品（大豆粉）中选择性地萃取有机锡化合物的方法。模拟试样萃取结果表明：用较低压力和较高温度的超临界态ＣＯ２作流动相时，有机锡达到最大萃取率，而脂肪类物质仅被少量萃取，从而消除了脂肪类物质对超临界流体色谱法测定有机锡的干扰。