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1.
A method for the enantioselective determination of the amphetamine-derived designer drugs 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyamphetamine (MDA) and 3,4-methylenedioxyethylamphetamine (MDE) based on their derivatization with (-)-1-(9-fluorenyl)ethyl chloroformate (FLEC) is described. The proposed procedure entails preconcentration and derivatization of the analytes into C18-packed solid-phase extraction cartridges, chromatographic separation of the diastereomers originated in a C18 column under gradient elution, and UV detection at 265 nm. Compared with the solution derivatization approach the described procedure increased analyte responses by factors of 28–58. The reliability of the method has been tested by analysing plasma and urine samples spiked with the analytes in the 0.015–1.0 μg mL?1 concentration interval. The proposed conditions provided adequate linearity, and coefficients of variation ranging from 5% to 14% in plasma, and from 3% to 12% in urine. The recoveries of the analytes were of 78%–126% and 78%–128% in plasma and urine, respectively. The limits of detection (LODs) obtained for all the analytes were 5 ng mL?1 in both biological matrices.  相似文献   

2.
A new method for the simultaneous determination of 1,4-dichlorobenzene (p-DCB), naphthalene and 1,2-dibromoethane (1,2-DBE) residues in honey has been developed. Analysis is carried out using gas chromatography-mass spectrometry (GC/MS) in selected ion monitoring mode (SIM), after extraction and preconcentration of target analytes by headspace solid-phase microextraction (HS-SPME), with a 100 microm film thickness polydimethylsiloxane (PDMS) fiber. Several parameters affecting the extension of the adsorption process (i.e., addition of salt, extraction time, extraction temperature) were studied. The optimal conditions for the determination of these analytes were established. The proposed HS-SPME method showed good sensitivity, without carryover between the samples. Linearity was studied from 5 to 2500 microg kg(-1) for p-DCB, 0.5 to 500 microg kg(-1) for naphthalene and 5 to 500 microg kg(-1) honey for 1,2-DBE with correlation coefficients (r(2)) ranging from 0.9901 to 0.9999. Precision was assessed and both intra and inter-day R.S.D.s (%) were below 6.3%. The detection limits were found to be 1, 0.1 and 2 microg kg(-1) honey for p-DCB, naphthalene and 1,2-DBE, respectively. The percentage recoveries that were evaluated with the proposed HS-SPME method and the standard addition calibration technique gave values among 72.8 and 104.3% for measurements in samples spiked with one target analyte or mixtures of the three. This method has been applied for the analysis of unknown honey samples. The results showed an excellent applicability of the proposed method for the determination of the target compounds in honey samples.  相似文献   

3.
A simple and efficient automated method for extraction and preconcentration of some organophosphorus and organochlorine pesticides from drinking and agriculture waters has been developed. In this work, a pyrrole-based polymer was synthesized and applied as an efficient sorbent for micro-solid-phase extraction (mu-SPE). Polypyrrole (PPY) was synthesized by chemical oxidation of the monomer in nonaqueous solution. The mu-SPE of selected pesticides, from aqueous samples was performed using 20mg of PPY. After extraction, analytes were desorbed in ethyl acetate and analyzed using gas chromatography-flame ionization detection. The acid-base and other physico-chemical interactions with the analytes facilitated the adsorption of analytes, with good selectivity and reproducibility. Under the optimized extraction conditions, the method showed good linearity in the range of 0.001-0.3 microg ml(-1) of water sample (phosphate buffer 1.0 x 10(-3) M, pH 8.5), RSD=1.5-4.2% (n=4), and limits of detection 200-600 pg ml(-1). Each mu-SPE cartridge could be used for up to 20 extractions.  相似文献   

4.
A combined approach based on solid-phase optosensing and multicommutation principles has been applied to develop a method for the simultaneous analysis of two pharmaceuticals (naproxen and salicylic acid) in biological fluids. The multicommuted flow-through optosensor was based on direct native fluorescence measurements of both analgesics using a non-polar sorbent (C18 silica gel) as a solid sensing zone. The flow system was controlled by Java-written home-made software and designed using three-way solenoid valves for an independent automated manipulation of sample and carrier solutions. Using an optimized sampling time, the method was calibrated in the range of 1 - 25 and 5 - 200 ng mL(-1). The obtained detection limits were 0.3 and 1.3 ng mL(-1) for naproxen and salicylic acid, respectively, with RSD (%) values of better than 2% for both analytes. The proposed methodology was successfully applied to urine, serum and pharmaceutical preparations. Recovery percentages ranging from 96.1 to 104% were obtained for both analytes.  相似文献   

5.
A method for direct determination of cadmium, chromium, copper and lead in sediments and soil samples by electrothermal atomic absorption spectrometry using Zr, Ir, etylenediamine acetic acid (EDTA), Zr + EDTA, Ir + EDTA, Zr + Ir and Zr + Ir + EDTA as chemical modifiers in 0.5% (v/v) Triton X-100 plus 0.2% (v/v) nitric acid mixture used as diluent was developed. The effects of mass and mass ratio of modifiers on analytes in sample solutions were studied. The optimum masses and mass ratios of modifiers: 20 microg of Zr, 4 microg of Ir, 100 microg of EDTA and 20 microg of Zr + 4 microg of Ir + 100 microg of EDTA, were used to enhance the analyte signals. Pyrolysis and atomization temperatures, atomization and background absorption profiles, characteristic masses, and detection limits of analytes in samples were compared in the presence or absence of a modifier. The detection limits and characteristic masses of analytes in a 0.5% (m/v) dissolved sample (dilution factor of 200 ml g(-1)) obtained with Zr + Ir + EDTA are 8.0 ng g(-1) and 1.2 pg for Cd, 61 ng g(-1) and 4.3 pg for Cr, 32 ng g(-1) and 23 pg for Cu, and 3.4 ng g(-1) and 19 pg for Pb, respectively. The Zr + Ir + EDTA modifier mixture was found to be preferable for the determination of analytes in sediment and soil-certified and standard reference materials. Depending on the sample type, the percent recoveries of analytes were increased from 81 to 103% by using the proposed modifier mixture; the results obtained are in good agreement with the certified values.  相似文献   

6.
A novel ion chromatographic method was proposed for the simultaneous determination of artificial sweeteners (sodium saccharin, aspartame, acesulfame-K), preservatives (benzoic acid, sorbic acid), caffeine, theobromine and theophylline. The separation was performed on an anion-exchange analytical column operated at 40 degrees C within 45 min by an isocratic elution with 5 mM aqueous NaH2PO4 (pH 8.20) solution containing 4% (v/v) acetonitrile as eluent, and the determination by wavelength-switching ultraviolet absorbance detection. The detection limits (signal-to-noise ratio 3:1) for all analytes were below the sub-microg/ml level. Under the experimental conditions, several organic acids, including citric acid, malic acid, tartaric acid and ascorbic acid, did not interfere with the determination. The method has been successfully applied to the analysis of various food and pharmaceutical preparations, and the average recoveries for real samples ranged from 85 to 104%. The levels of all analytes determined by this method were in good agreement with those obtained by the high-performance liquid chromatographic procedure. The results also indicated that ion chromatography would be possibly a beneficial alternative to conventional high-performance liquid chromatography for the separation and determination of these compounds.  相似文献   

7.
A simple, rapid and efficient method, the dispersive liquid-liquid microextraction (DLLME) in conjunction with gas chromatography-mass spectrometry (GC-MS), has been developed for the extraction and determination of phthalate esters (dimethyl phthalate, diallyl phthalate, di-n-butyl phthalate, benzyl butyl phthalate, dicyclohexyl phthalate and di-2-ethylhexyl phthalate) in water samples. Factors relevant to the microextraction efficiency, such as the kind of extraction, the disperser solvent and their volume, the salt effect and the extraction time were investigated and optimized. Under the optimized extraction conditions (extraction solvent: chlorobenzene, volume, 9.5microL; disperser solvent: acetone, volume, 0.50mL, without salt addition and extraction time below 5s), the figures of merit of the proposed method were evaluated. The values of the detection limit of the method were in the range of 0.002-0.008microgL(-1), while the RSD% value for the analysis of 1microgL(-1) of the analytes was below 6.8% (n=4). A good linearity (0.9962>/=r(2)>/=0.9901) and a broad linear range (0.02-100microgL(-1)) were obtained. The method exhibited enrichment factors and recoveries, ranging from 681 to 889 and 68.1 to 88.9%, respectively, at room temperature (25+/-1 degrees C). Finally, the proposed method was successfully utilized for the preconcentration and determination of the phthalate esters in different real water samples and satisfactory results were obtained.  相似文献   

8.
A novel method, dispersive liquid-liquid microextraction combined with liquid chromatography-fluorescence detection is proposed for the determination of three beta-blockers (metoprolol, bisoprolol, and betaxolol) in ground water, river water, and bottled mineral water. Some important parameters, such as the kind and volume of extraction and dispersive solvents, extraction time, pH, and salt effect were investigated and optimized. In the method, a suitable mixture of extraction solvent (60 μL carbon tetrachloride) and dispersive solvent (1 mL acetonitrile) were injected into the aqueous samples (5.00 mL) and the cloudy solution was observed. After centrifugation, the enriched analytes in the bottom CCl(4) phase were determined by liquid chromatography with fluorescence detection. Under the optimum conditions, the enrichment factors (EFs) for metoprolol, bisoprolol, and betaxolol were 180, 190, and 182, and the limits of detection (LODs) were 1.8, 1.4, and 1.0 ng L(-1) , respectively. A good linear relationship between the peak area and the concentration of analytes was obtained in the range of 3-150 ng L(-1) . The relative standard deviations (RSDs) for the extraction of 10 ng L(-1) of beta-blockers were in the range of 4.6-5.7% (n = 5). Compared with other methods, dispersive liquid-liquid microextraction is a very simple, rapid, sensitive (low limit of detection), and economical (only 1.06 mL volume of organic solvent) method, which is in compliance with the requirements of green analytical methodologies.  相似文献   

9.
A high-performance capillary electrophoretic (CE) method with electrochemical detection (ED) has been developed for determination of the pharmacologically active flavonoids in Ginkgo biloba L. and phytopharmaceuticals containing its extract. Epicatechin, catechin, rutin, apigenin, luteolin, and quercetin are important flavonoids in this plant. Operated in a wall-jet configuration, a 300 micro m diameter carbon-disk electrode was used as working electrode with good response to the six analytes at +1000 mV (relative to the SCE). Under the optimum conditions, the analytes were separated within 22 min in a borax buffer (pH 9.0). Excellent linearity was obtained over two orders of magnitude and detection limits (S/N=3) ranged from 1.4 x 10(-7) to 5.0 x 10(-7) g mL(-1) for all six analytes. The method was successfully used for assay of Ginkgo biloba L. and its phytopharmaceuticals after a relatively simple extraction procedure; the results obtained were satisfactory.  相似文献   

10.
In this paper, a sensitive, simple and direct method for simultaneous determination of glucose, ribose, isomaltose and maltose in serum sample by high-performance anion-exchange chromatography coupled with integrated pulsed amperometric detection was developed. The four target analytes were easily and completely separated on an anion-exchange column at a flow-rate of 0.25 mL/min by binary step gradient elution in about 16 min and the two eluents were deionized water and 500 mM sodium hydroxide, respectively. The separated four analytes were detected directly by using a gold electrode and quadruple-potential waveform integrated pulsed amperometry without derivatization. Under the optimized conditions, when the injection volume was 25 microL, the detection limits (signal-to-noise ratio equal to 3) for glucose, ribose, isomaltose and maltose were 0.92, 7.50, 12.9 and 10.3 ng/mL, respectively. The calibration graphs of peak area for the four analytes were linear over two to three orders of magnitude with correlation coefficients greater than 0.998. R.S.D. of peak areas of the four analytes for five determinations were no more than 5.6%. The analytical method had been applied to the determination of glucose, ribose, isomaltose and maltose in real serum samples and good results with low relative standard deviation not more than 5.3% were obtained. The accuracy of the proposed method was tested by recovery measurements on spiked samples and good recovery results (98.1-107.9%) were obtained.  相似文献   

11.
As a result of thermal stability studies of carbamate pesticides, a method has been proposed for their direct determination by gas chromatography in the ranges 1-20 and 0.1-1 mg l(-1), using flame ionization and nitrogen-phosphorus detection, respectively. The method allows the determination of propham, propoxur, carbofuran, carbaryl, methiocarb, isopropoxyphenol and naphthol in powdered potato samples. The analytes were previously extracted with a light petroleum-dichloromethane (1:1, v/v) mixture and preconcentred by solid-phase extraction through a C8 cartridge. The recoveries obtained from spiked potato samples (n=4 replicates) at two concentration levels, 10 and 0.5 mg of pesticide per kg of sample, were in the ranges 72-115 and 50-73%, with relative standard deviations of 2-7 and 5-8%, respectively. The detection limits were 50-210 and 41-53 microg kg(-1) with flame ionization and nitrogen-phosphorus detection, respectively, and reaching the maximum residue levels, 0.05 mg kg(-1) for methiocarb and propoxur, set by the Real Decreto 280/1994 (based on the European directive).  相似文献   

12.
In this work, an ordered mesoporous titania film was introduced to coat a capillary by means of sol-gel technique. Sol-gel titania coating was developed for the preconcentration/separation of trace V, Cr and Cu by capillary microextraction (CME), and the adsorbed analytes were eluted for electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) detection. By immobilizing sol-gel titania on the inner surface of a fused-silica microextraction capillary, the sol-gel titania coating was prepared easily. Its adsorption properties, stability and the factors affecting the adsorption behaviors of V, Cr and Cu were investigated in detail. At pH range of 7 to 9, the titania-coated capillary (50 cm x 0.25 mm) is selective towards V, Cr and Cu, and the target analytes could be desorbed quantitatively with 50 microl of 1.0 mol l(-1) HNO3 at the rate of 0.05 ml min(-1). With a consumption of 2 ml sample solution, an enrichment factor of 33.3, and a detection limit (3 s) of 1.1 pg ml(-1) (10.5 fg) for V; 3.3 pg ml(-1) (33.0 fg) for Cr and 6.3 pg ml(-1) (63.1 fg) for Cu respectively were obtained. The precisions Relative Standard Deviations (RSDs) for nine replicate measurements of 1 ng ml(-1) V, Cr and Cu were 3.4, 5.1 and 6.4%, respectively. The proposed method has been applied to the determination of V, Cr and Cu in human urine and lake water, and the recoveries for these elements were 89.2 approximately 105%. The developed method was also applied to the determination of the target elements in NIES No. 10-a (rice flour-unpolished) and NIES No. 9 (sargasso) certified reference materials, and the results found are in good agreement with the certified values.  相似文献   

13.
A sensitive and rapid derivatization method for the simultaneous determination of 1,3-dichloro-2-propanol (1,3-DCP) and 3-chloropropane-1,2-diol (3-MCPD) in water samples has been developed. The aim was to research the optimal conditions of the derivatization process for two selected reagents. A central composite design was used to determine the influence of derivatization time, derivatization temperature and reagent volume. A global desirability function was applied for multi-response optimization. The analysis was performed by gas chromatography-mass spectrometry. During the optimization of the extraction procedure, four different types of solid-phase extraction (SPE) columns were tested. It was demonstrated that the Oasis HLB cartridge produced the best recoveries of the target analytes. The pH value and the salinity were investigated using a Doehlert design. The best results for the SPE of both analytes were obtained with 1.5 g of NaCl and pH 6. The proposed method provides high sensitivity, good linearity (R(2)≥0.999) and repeatability (relative standard deviations % between 2.9 and 3.4%). Limits of detection and quantification were in the range of 1.4-11.2 ng/mL and 4.8-34.5 ng/mL, respectively. Recoveries obtained for water samples were ca. 100% for 1,3-DCP and 3-MCPD. The method has been successfully applied to the analysis of different samples including commercially bottled water, an influent and effluent sewage.  相似文献   

14.
This paper described a new approach for the determination of organophosphorus pesticides by temperature-controlled ionic liquid dispersive liquid-phase microextraction prior to high-performance liquid chromatography with ultraviolet detection. Methylparathion and phoxim, two of the typical organophosphorus pesticides, were used as the model analytes for the investigation of the development and application of the new microextraction method. 1-Hexyl-3-methylimidazolium hexafluorophosphate [C6MIM][PF6] was used as the extraction solvent and the factors affecting the extraction efficiency such as the volume of [C6MIM][PF6], pH of working solutions, extraction time, centrifuging time, dissoluble temperature and salt effect were optimized. Under the optimal extraction conditions, methylparathion and phoxim exhibited good linear relationship in the concentration range of 1-100 ng mL(-1). The detection limits were 0.17 ng mL(-1) and 0.29 ng mL(-1), respectively. Precisions of proposed method (RSDs, n=6) were 2.5% and 2.7%, respectively. This proposed method was successfully applied in the analysis of four real environmental water samples and good spiked recoveries over the range of 88.2-103.6% were obtained. These results indicated that temperature-controlled ionic liquid dispersive liquid-phase microextraction had excellent application prospect in environmental field.  相似文献   

15.
Toral MI  Richter P  Rodríguez C 《Talanta》1997,45(1):147-153
A highly sensitive and selective second derivative spectrophotometric method has been developed for the determination of copper and iron in mixtures. The method is based on the separation of the analytes by liquid-liquid extraction as picrate ion pairs. Iron-picrate, reacts in the organic phase of DCE with 5-phenyl-3-(4-phenyl-2-pyridinyl)-1,2,4-triazine (PPT). Similarly the copper-picrate reacts with 2,9-dimethyl-4,7-diphenyl-1,10-phenantroline (bathocuproine). The extracts were evaluated directly by derivative spectrophotometric measurement, using the zero-crossing approach for determination of copper and graphic method for iron. Iron and copper were thus determined in the ranges 8-120 ng ml(-1) and 8-125 ng ml(-1), respectively, in the presence of one another. The detection limits achieved (3sigma) were 2.9 ng ml(-1) of iron and 2.8 ng ml(-1) of copper. The relative standard deviations were in all instances less than 2.1%. The proposed method was applied to the determination of both analytes in river and tap water and the results were consistent with those provided by the AAS standard method.  相似文献   

16.
A new methodology for the simultaneous determination of salicylic acid and salicylamide in biological fluids is proposed. The strong overlapping of the fluorescence spectra of both analytes makes impossible the conventional fluorimetric determination. For that reason, the use of fluorescence decay curves to resolve mixtures of analytes is proposed; this is a novel technique that provides the benefits in selectivity and sensitivity of the fluorescence decay curves. In order to assess the goodness of the proposed method, a prediction set of synthetic samples were analyzed obtaining recuperation percentages between 98.2 and 104.6%. Finally, a study of the detection limits was done using a new criterion resulting in values for the detection limits of 8.2 and 11.6 μg L(-1) for salicylic acid and salicylamide respectively. The validity of the method was tested in human serum and human urine spiked with aliquots of the analytes. Recoveries obtained were 96.2 and 94.5% for salicylic acid and salicylamide respectively.  相似文献   

17.
The use of microemulsion electrokinetic chromatography was proposed to separate psoralen and isopsoralen in Psoralea corylitolia L. and its preparations. After conducting a series of optimizations, baseline separation was obtained for the analytes under the optimum conditions [sodium dodecyl sulfate 1.05% (m/v), ethyl acetate 0.96% (v/v), butan-1-ol 0.24% (v/v), 25 mm borate, pH 8.5, applied voltage 17.5 kV and detection at 254 nm]. Regression equations revealed linear relationships (correlation coefficients 0.9997 for psoralen and 0.9999 for isopsoralen) between the peak area of each analyte and the concentration. The limits of detection (defined as a signal-to-noise ratio of about 3) were 0.42 microg/mL for psoralen and 0.32 microg/mL for isopsoralen, respectively. The analytes were successfully determined with recoveries ranging from 95.50 to 102.03%. The method has been successfully applied for the analysis of psoralen and isopsoralen in medical samples. Furthermore, a simple and effective extraction method, with methanol in an ultrasonic water bath for 20 min three times, was used for sample preparation.  相似文献   

18.
Chao YY  Wei YT  Lee CT  Kou HS  Huang YL 《Analytical sciences》2011,27(10):1025-1030
An on-line microdialysis/high-performance liquid chromatography method was developed for the simultaneous determination of melamine and cyanuric acid in non-dairy coffee creamer. To collect these analytes from aqueous samples, the microdialysis system featured a microdialysis probe incorporating a polyarylethersulfone membrane and employed 0.05 M HCl in 0.1% (v/v) MeOH as the perfusate, with optimal efficiency obtained at a flow rate of 1 μL min(-1). The chromatographic conditions were optimized when using a reverse-phase phenyl column and a mobile phase of phosphate buffer solution in 10% (v/v) MeOH, buffered at pH 3.0. Good linearity relationship (r(2) > 0.9987), intra- and inter-day precisions (RSDs < 6.6%), recoveries (96.9 - 105.0%), and limits of detection (melamine, 3 ppb; cyanuric acid, 150 ppb) were observed for the two analytes. This method has been successfully applied to simultaneous determination of melamine and cyanuric acid in commercial creamers with the recoveries in the range of 97.5 to 102.6%.  相似文献   

19.
A method for rapid separation and sensitive determination of three water-soluble vitamins, pyridoxine, ascorbic acid (VC), and p-aminobenzoic acid (PABA) has been developed by PDMS microchannel electrophoresis integrated with amperometric detection. After treatment of the microchip with oxygen plasma, the peak shapes of the three analytes were essentially improved. Pyridoxine, VC, and PABA were well separated within only 80 s in a running buffer of 20 mM borate solution (pH 8.5). Good linearity was obtained within the concentration range of 2-200 microM for the three water-soluble vitamins. The detection limits were 1.0 microM for pyridoxine and VC, and 1.5 microM for PABA. The proposed method has been successfully applied to real human urine sample, without solid phase extraction, with recoveries of 80-122% for the three water-soluble vitamins.  相似文献   

20.
A fast ion chromatographic method with suppressed conductivity detection has been developed for the simultaneous determination of methane-, ethane-, 1-propane-, 1-butane-, 1-pentane-, 1-hexane-, 1-heptane-, 1-octane-, 1-nonane-, 1-decane-, 1-dodecane-, dodecylbenzene-, p-toluene-, benzenesulfonic acids, octylsulfate and dodecylsulfate in water samples. Due to the high number of analytes and their heterogeneity, the effect of the mobile phase parameters (NaOH, CH(3)OH and CH(3)CN concentration) on the retention factors has been studied in detail, so achieving, for the first time, the separation among 15 of these analytes by a gradient elution. Detection limits included within 0.06-0.16 microM have been obtained. Interferences from Cl(-), NO(3)(-) and SO(4)(2-), possible anions present in water samples, have been considered and a SPE procedure has been developed for analytes enrichment and matrix removal in a seawater sample. This is the first application of an ion-exchange chromatographic method to a seawater sample for this kind of analytes.  相似文献   

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