Determination of N-nitrosamines in latex by sequential supercritical fluid extraction and derivatization

A new method to determine N-nitrosamines in latex products has been developed by combination of supercritical fluids and chemical derivatization. A new design for a liquid trap has been introduced. A factorial fractional design was used in order to evaluate the influence of the different factors affecting the process. Factors such as pressure, temperature, static and dynamic time, restrictor temperature and volume of an hydrobromic acid-acetic anhydride mixture (1:10, v/v) were included in the design. CO2 was used as the extraction fluid. Gas chromatography with nitrogen and phosphorus sensitive detection was employed to achieve good sensitivity attending to the molecular structure of these compounds (N-nitrosamines and their corresponding secondary amines). The obtained results have shown to be useful to increase selectivity and reduce sample handling.     

基于Hansen溶度参数的煤直接液化残渣超临界萃取

以丙酮、 异丙醇和苯为溶剂在超临界状态下对煤直接液化残渣进行萃取, 应用溶度参数分析了超临界萃取环境中溶剂和萃取原料的变化; 基于Hansen拓展方法建立了关联Hansen溶度参数和萃取收率的理论方程. 结果表明, 临界温度较高. 以色散力溶度参数为主的苯的萃取收率明显高于其它2种溶剂; 液化残渣中可萃出组分的理想溶解度随温度的升高而增大, 该效应也是超临界溶剂萃取重质组分时萃取收率提高的重要原因; 萃取收率与Hansen溶度参数之间的回归模型与实验结果具有较好的一致性, 证明Hansen溶度参数理论和Hansen拓展方法适用于描述煤直接液化残渣的超临界萃取过程.     

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.     

Selective extraction of astaxanthin from crustaceans by use of supercritical carbon dioxide

An on-line supercritical fluid extraction (SFE) system coupled to a continuous flow manifold including a UV detector was used as a screening system to extract astaxanthin from crayfish, which was found to be the major carotenoid present in the samples. This compound constitutes the principal additive used to dye salmon flesh. The flow manifold was used to confirm the presence of astaxanthin in the crustacean samples. Also, an HPLC/UV-vis method was used to ascertain that this compound was the major carotenoid extracted under the optimum SFE conditions employed. The influence of SFE operating variables such as pressure, temperature, equilibration time, extraction time, trap temperature, and volume of CO₂ modifier was examined in order to maximize the efficiency of analyte extraction. The use of supercritical CO₂ enables the expeditious, selective, quantitative extraction of astaxanthin from crustaceans.     

超临界流体萃取在天然药物分析中的应用

按物质的不同性质综述了１９９５年以来超临界流体萃取技术在天然药物分析中的一些进展情况,常见的分析主要包括萜类、生物碱、黄酮类、挥发油及苯丙素类。超临界流体萃取作为一门新型的样品前处理技术,在天然药物的分离分析中展示了其特有的优点。该技术操作温度低,不会引起热敏性的分解变质;使用的有毒溶剂少,从而减少化学药品对药物的污染。     

Optimisation of supercritical fluid extraction of essential oil components of Diplotaenia cachrydifolia: Box-Behnken design

Essential oil of Diplotaenia cachrydifolia cultivated in Iran was obtained by supercritical fluid extraction (SFE) method. The oils were analysed by capillary gas chromatography using flame ionisation and mass spectrometric detections. The compounds were identified according to their retention indices and mass spectra (EI, 70?eV). The effects of different parameters, such as pressure, temperature, modifier volume and extraction times (dynamic and static), on the SFE were inspected by a fractional factorial design (2(5-2)) to identify the significant parameters and their interaction. It showed that static and dynamic times had no effect on the extraction. Finally, a Box-Behnken design was applied to obtain the optimum condition of the significant parameters. The optimal condition was obtained as 30.2?MPa for pressure, 65.6°C for temperature and 258.4?μL for modifier volume. The main components that were extracted with SFE were dillapiole (35.1%), limonene (33.5%) and α-calacorene (25.5%).     

环境模拟样品中多环芳烃的超临界流体萃取I．利用正交设计选择最佳萃取条件

采用正交设计实验方法，研究了从环境模拟样品中超临界流体萃取（ＳＦＥ）多环芳烃（ＰＡＨ）的最佳萃取条件。着重考察了超临界流体的压力、温度和用量等对萃取效率的影响。结果表明，压力的影响居第一位，温度影响次之，超临界ＣＯ２的用量的影响居第三位。建立了选择超临界流体萃取条件的简单方法     

Optimization of the extraction of azo colorants used in toy products

Azo dyes are widely used in formulations intended for children use. But their potential toxicity raised the need of an efficient and fast method of analysis. A study for the optimization of the extraction of some azo colorants used in toys was conducted. Several extraction methods for the selected analytes were evaluated and compared, i.e., supercritical fluid extraction (SFE), microwave-assisted extraction (MAE) and Soxhlet extraction. Poly(vinyl chloride) samples spiked with known quantities of the studied dyes were prepared. The influence of critical variables on analyte recoveries in SFE and MAE was investigated by using a full-level factorial design, where most significant parameters as well as order interactions were studied in each case. The analytes were subsequently detected by high-performance liquid chromatography with UV detection. The three extraction techniques were compared in terms of reproducibility, selectivity and analyte recoveries. MAE showed higher recoveries (above 98%), except for the diazo dye (nearly 60%). Reproducibilities were generally good for the three methods (relative standard deviation lower than 2.0%).     

Supercritical fluid extraction with in situ chiral derivatization for the enantiospecific determination of ibuprofen in urine samples

In situ chiral derivatization was used to obtain diastereomeric amides of ibuprofen for their subsequent extraction with supercritical carbon dioxide. For this purpose, ibuprofen [racemic 2-(4-isobutylphenyl)propionic acids] was previously extracted on a C-18 SPE device and quantitatively transferred into the supercritical fluid extraction (SFE) vessel for derivatization and extraction with (R)-1-(naphthen-1-yl)ethylamine as chiral derivatizing base, and a mixture of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 1-hydroxybenzotriazole as reagents, in order to obtain and extract the corresponding diastereoisomeric amides, which were subsequently determined by liquid chromatography. The influence of different extraction and derivatization variables (pressure, temperature, extraction time in the static and dynamic extraction modes, and amount of chiral base) on the extraction efficiency was studied. Spiked and native urine samples containing ibuprofen were used to demonstrate the application of this method. The absolute recovery, selectivity, precision and accuracy of the combined solid-phase extraction (SPE)/SFE approach were compared to those provided by conventional liquid–liquid extraction. The results indicated that SFE seems to be an effective choice for in situ derivatization since analysis times and solvent consumption were dramatically reduced.     

Determination of fat in leather by the use of supercritical fluid extraction combined with on-line piezoelectric detection.

Leather samples were prepared and characterized as 'in house' matrix standards for the determination of fat. The Soxhlet standard method was used to establish the reference fat content in every standard sample. Sample homogeneity and stability were examined under specific storing conditions. The materials were subsequently used as matrix standards for the determination of fat in leather samples, using supercritical fluid extraction (SFE) with on-line piezoelectric detection. Real samples were weighed in the extraction SFE thimble, previously loaded with 1 g of diatomaceous earth. A temperature of 45 degrees C and a CO2 fluid density of 0.85 g ml-1 were used for extraction. The linear calibration range thus achieved was 0.001-0.040% m/m total fat (related to the weight of the leather) and the relative standard deviation +/- 3% (n = 11; P = 0.05). The results were compared with those obtained with the Soxhlet method and no significant differences were found.     

A Unified Sample Preparation System for Extraction of Various Analyte/Matrix Combinations

A supercritical fluid extraction/enhanced solvent extraction system (SFE/ESE) was used to remove polar and non-polar analytes from various matrices. Extraction of environmental pollutants from soil, additives from low density polyethylene, sulfa drugs from animal tissue, and drug from tablet was performed using both SFE and ESE. Results showed that a single instrumental system can be used to perform both ESE with organic solvents and SFE with carbon dioxide-based fluids. Each method has its own unique advantages and applications. The ability to carry out both solvent extraction and supercritical fluid extraction with one system has obvious economical advantages.     

Modeling of supercritical fluid extraction of flavonoids from Calycopteris floribunda leaves

The aim of this study was to obtain flavonoids extracts from Calycopteris floribunda leaves using supercritical fluid extraction (SFE) with CO₂ and a co-solvent. Pachypodol, a potential anticancer drug lead compound separated from the extracts, was examined. Classical organic solvent extraction (CE) with ethanol was performed to evaluate the high pressure method. HPLC analysis was introduced to interpret the differences between SFE and CE extracts in terms of antioxidant activity and the concentration of pachypodol. SFE kinetics and mathematical modeling of the overall extraction curves (OEC) were investigated. Evaluation of the models against experimental data showed that the Sovová model performs the best. The supercritical fluid extraction process was optimized using a central composite design (CCD), where temperature and pressure were adjusted. The optimal conditions of SFE were: pressure of 30 MPa and temperature of 35°C.     

Analysis of citrates and benzoates used in poly(vinyl chloride) by supercritical fluid extraction and gas chromatography

Supercritical fluid extraction (SFE) has been demonstrated to be a useful tool in the determination of additives in polymeric materials. This paper describes the determination of some citrates and benzoates in poly(vinyl chloride) blended with 33–34% of plasticizer using off-line SFE followed by gas chromatography. Experimental factors affecting SFE have been studied by gravimetric analysis, followed by analysis of the extracts using a gas chromatograph equipped with a flame ionization detector. The extraction process is governed by the solubility of the plasticizers in the supercritical fluid or by their diffusion through the polymer matrix, which depend on the pressure and temperature used. Maximum extraction (>99%) is obtained at pressures and temperatures higher than 40 MPa and 80 °C, respectively. Due to purge losses, the collection efficiency of plasticizers into a liquid solvent ranges from 85 to 90%. The applicability of the SFE method is demonstrated using real samples and comparing the results with those obtained by conventional Soxhlet extraction.     

Qualitative supercritical fluid extraction coupled to capillary gas chromatography

The usefulness and ease of utilizing supercritical fluid extraction (SFE) directly coupled to capillary gas chromatography (GC) as quantitative or qualitative analytical problem-solving tools will be demonstrated. As an alternative to conventional liquid solvent extractions, SFE presents itself as a means to achieve high extraction efficiencies of different compounds in complex solid matrices in very rapid tims frames. Moreover, SFE has an additional advantage of being able to achieve distinct extraction selectivities as a function of the solubilizing power of the supercritical fluid extracting phase. For on-line SFE/GC, the extraction effluent is directly transferred to the analytical chromatograph. On-line SFE/GC involves the decompression of pressurized extraction effluent directly into a heated, unmodified capillary split injection port of the GC. In this respect, SFE introduction into GC can be used as an alternative means of GC injection, comparable to such modes of injection as pyrolysis and thermal desorption. This paper will show applications of SFE/GC where mass spectrometric detection together with flame ionization detection was used for component identification from environmental, tobacco, and petroleum matrices.     

The use of alternative fluids in on-line supercritical fluid extraction – capillary gas chromatography

A key feature differentiating analytical supercritical fluid extraction (SFE) from conventional liquid extraction is the possibility of varying the solvent strength of a supercritical fluid to achieve selective extractions of specific target compounds, or functional classes of compound, from complex matrices. This can be accomplished by using supercritical fluids other than carbon dioxide, for example, sulfur hexafluoride, nitrous oxide, or sulfur hexafluoride-modified carbon dioxide. The use of these fluids will be demonstrated by the characterization of complex environmental and petroleum matrices by directly coupled SFE – capillary GC. On-line SFE-GC involves the decompression of pressurized extraction fluid directly into the heated, unmodified capillary split injection port of the chromatograph. This paper will also show how, by adjustment of the extraction temperature and pressure, SFE selectivity may be further enhanced.     

Optimization of supercritical fluid extraction-gas chromatography of methylmercury in marine samples

Two-level factor designs were used to optimize the supercritical fluid extraction (SFE) of methylmercury (Me---Hg) in marine samples, which were subsequently analysed by gas chromatography-electron capture detection (GC-ECD). Several variables potentially affect to extraction efficiency and kinetics. The factors studied were: CO₂ flow-rate and density, extraction cell temperature, static extraction time, nozzle and trap temperature, amount of hydrochloric acid and contact time between the acid and the sample before to extraction. The extraction kinetics was studied in all experiments by splitting extracts at 2, 7, 17 and 37 min. The results suggest that only the extraction cell temperature is statistically significant. The optimized SFE procedure to extract Me---Hg was validated by means of three available reference materials having certified methylmercury content.     

The use of nitrous oxide for supercritical fluid extraction of pharmaceutical compounds from animal feed

Supercritical fluid extraction (SFE) coupled “off-line” with HPLC analysis has been applied to pharmaceutical analysis: two different matrixes (rodent and dog feed) were spiked with compounds under investigation in pharmacological studies in order to study the supercritical extraction of such matrixes prior to further analysis and quantification of the compounds of interest. The fluid flow-rate in the SFE system was governed by the geometric characteristics (internal diameter and length) of the linear fused silica capillaries. The changes in fluid flow-rate, between experiments, for each new restrictor, required the introduction of the term Total Gaseous Fluid Volume (TGFV), which enabled a series of extraction results to be compared. The comparative behavior of nitrous oxide and carbon dioxide as supercritical extraction fluids was investigated. Results obtained using pure supercritical fluids with high solvating power (density 0.79 g ml^?1) and fluids modified with a polar liquid solvent (methanol and acetonitrile) are discussed.     

Application of supercritical fluid extraction and supercritical fluid chromatography to the production of taxanes as anti-cancer drugs

The supercritical fluid extraction (SFE) of taxicin from the dried needles of the English yew tree, Taxus baccata is described. Analysis by supercritical fluid chromatography (SFC) and proton NMR spectroscopy was used to confirm identity and purity. The extraction efficiency of SFE is comparable with that obtained using liquid solvents. Such taxanes may be used semi-synthetically to prepare potential anti-cancer drugs.     

Determination of PAHs in dust from Shanghai by optimized SFE and GC/MS

EPA 16 priority polycyclic aromatic hydrocarbons (PAHs) were extracted from dust by supercritical fluid extraction (SFE). Parameters (pressure, temperature and time) affecting the collection efficiencies of PAHs were assessed according to the extraction efficiency, and 30 MPa, 80 degrees C and 30 min dynamic extraction time were confirmed to be the best and simplest conditions of SFE to extract 16 priority PAHs from dust. The characterization of the extracts was carried out by gas chromatography with mass detector in selective ion mode (GC/MS/SIM). Ultrasonic extraction (USE) was used as a comparison with SFE. The results showed that the SFE method has a better efficiency than USE for the extraction of PAHs in dust. With the optimized conditions of SFE, the distribution of PAHs in dust samples in urban areas of Shanghai from Mar 10, 2005 to May 28, 2005 was investigated. The results demonstrated that traffic emission, especially from gasoline engines, was the main source of PAHs in dust of Shanghai.     

A two-step supercritical fluid extraction of polycyclic aromatic hydrocarbons from roadside soil samples

A two-step procedure for the supercritical fluid extraction (SFE) of polycyclic aromatic hydrocarbons from soil samples was developed. The procedure consists of a static supercritical fluid treatment in a closed extraction cell at a high temperature (T=250 or 340degreesC for 20 min) and an SFE with a solvent trapping. During the static phase, the sample is exposed to a supercritical organic solvent (methanol, toluene, dichloromethane, ACN, acetone, and hexane). The solvent penetrates particles of the matrix to substitute strongly bonded molecules and dissolves the analytes in the supercritical phase. At ambient temperature, supercritical fluids became liquid and lost their solvation abilities. Most of the analytes condense on the surface of the particles or on the extraction cell walls without forming strong bonds or penetrating deep into the matrix. Thus, the pretreatment liberates the analytes and they behave similar to those in freshly spiked samples. The common SFE with toluene-modified CO2 as an extraction fluid follows the static phase. With the use of the most suitable extraction phases (toluene, ACN), the extraction efficiency of the combined procedure is much higher (approximately100%). The results of the combined procedure are compared to the SFE procedure of the same untreated sample (difference less than 5%) and to the Soxhlet extraction. The extracts were analyzed using a GC with the flame ionization detection.