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1.
A miniaturized supported liquid membrane device has been developed for sample preparation and connected on-line to a packed capillary liquid chromatograph. The device consists of hydrophobic polypropylene hollow fiber, inserted and fastened in a cylindrical channel in a Kel-F piece. The pores of the fiber are filled with an organic solvent, in this study 6-undecanone, thus forming a liquid membrane. The sample is pumped on the outside of the hollow fiber (donor), and the analytes are selectively enriched and trapped in the fiber lumen (acceptor). With this approach, the volume of the acceptor solution can be kept as low as 1-2 μL. This stagnant acceptor solution is then transferred through capillaries attached to the fiber ends to the LC system. The system was tested with a secondary amine (bambuterol), as a model substance in aqueous standard solutions as well as in plasma. The best extraction efficiency in aqueous solution, with an acceptor volume of 1.9 μL, was 32.5% at a donor flow rate of 2.5 μL/min. At flow rates above 20 μL/min, the concentration enrichment per time unit was approximately constant, at 0.9 times/min, i.e., 9 times enrichment in about 10 min. The overall repeatability (RSD) for spiked plasma samples was ~4% (n = 12). Linear calibration curves of peak area versus bambuterol concentration were obtained for both aqueous standard solutions and spiked plasma samples. The detection limit for bambuterol in plasma, after 10 min of extraction at a flow rate of 24 μL/min, was 80 nM.  相似文献   

2.
Jiang X  Oh SY  Lee HK 《Analytical chemistry》2005,77(6):1689-1695
A new dynamic liquid-liquid-liquid microextraction procedure, with the automated movement of acceptor phase (LLLME/AMAP) to facilitate mass transfer, was developed in this study. Four compounds, 3-nitrophenol, 4-nitrophenol, 3,4-dinitrophenol, and 2,4-dichlorophenol, were used as model compounds to be preconcentrated from water samples. The extraction involved filling a 2-cm length of hollow fiber with 4 muL of acceptor solution using a conventional microsyringe, followed by impregnation of the pores of the fiber wall with 1-octanol. The fiber was then immersed in 4 mL of aqueous sample solution. The analytes in the sample solution were extracted into the organic solvent and then back-extracted into the acceptor solution. During extraction, the acceptor phase was repeatedly moved in and out of the hollow fiber channel and the syringe controlled by a syringe pump. Separation and quantitative analyses were then performed by using high-performance liquid chromatography. The results indicated that up to 400-fold enrichment of the analytes could be obtained under the optimized conditions. The enrichment factors were two times those of static liquid-liquid-liquid microextraction. Good repeatabilities (RSD values below 9.30%) were obtained. The calibration linear range was from 10 to 1000 ng/mL with the square of the correlation coefficient (r2) >0.9916. Detection limits were in the range of 0.45-0.98 ng/mL. In addition, as compared with the previously reported dynamic three-phase microextraction in which there was no relative movement between the acceptor and the organic phase (which is not conducive to effective mass transfer), this new method shows much higher extraction efficiency. All these results suggest that this new dynamic LLLME/AMAP technique could be a better alternative to the previous LLLME for the extraction of analytes from aqueous samples.  相似文献   

3.
The recovery of several semivolatile organic compounds (SVOCs) using a new thermospray liquid/liquid extractor (TSLLE) was investigated. The base system includes a 300 mL multiport extraction vessel, jacketed in a 500 mL cooling flask, a dual-stage condenser for progressive cooling, several thermospray probes, and solvent/sample delivery systems. Aqueous mixtures of SVOCs were used to evaluate the TSLLE. For most compounds, recovery values of 80-100% were obtained during a single cycle in <1 h. The design, evaluation, and extraction capability of the TSLLE are discussed.  相似文献   

4.
To obtain a high degree of selectivity in sample preparation, supported liquid membrane (SLM) extraction was combined with immunologic recognition. The SLM employs a hydrophobic polymer for supporting the immobilization of an organic solvent, thus forming a nonporous membrane. Said membrane separates the aqueous sample on one side (donor) from a receiving aqueous phase on the other (acceptor). The extraction involves the partitioning of neutral compounds between the sample solution, continuously pumped alongside the membrane, and the membrane. From the membrane, reextraction takes place into a second aqueous phase containing antibodies specific for the target compound(s). Hence, there is a formation of an antibody-antigen complex at the heart of the sample preparation (ImmunoSLM). When the immunocomplex forms, the antigen can no longer redissolve in the organic membrane, thus being trapped in the acceptor. Consequently, the concentration gradient of free antigen over the membrane is ideally unaffected, this being the driving force for the process. With a surplus of antibody, the concentration of analyte in the receiving phase will easily exceed the initial sample concentration. In this work, the so formed immunocomplex was quantified on-line, using a fluorescein flow immunoassay in a sequential injection analysis (SIA) setup. The outlined ImmunoSLM-SIA scheme was successfully applied for the extraction of 4-nitrophenol from spiked water solutions as well as from a spiked wastewater sample, indicating that the immunoextraction can be suitable when dealing with difficult matrixes.  相似文献   

5.
Methamphetamine as a model compound was extracted from 2.5-mL aqueous samples adjusted to pH 13 (donor solution) through a thin phase of 1-octanol inside the pores of a polypropylene hollow fiber and finally into a 25-microL acidic acceptor solution inside the hollow fiber. Following this liquid-liquid-liquid microextraction (LLLME), the acceptor solutions were analyzed by capillary zone electrophoresis (CE). Extractions were performed in simple disposable devices each consisting of a conventional 4-mL sample vial, two needles for introduction and collection of the acceptor solution, and a 8-cm piece of a porous polypropylene hollow fiber. From 5 to 20 different samples were extracted in parallel for 45 min, providing a high sample capacity. Methamphetamine was preconcentrated by a factor of 75 from aqueous standard solutions, human urine, and human plasma utilizing 10(-1) M HCl as the acceptor phase and 10(-1) M NaOH in the donor solution. In addition to preconcentration, LLLME also served as a technique for sample cleanup since large molecules, acidic compounds, and neutral components were not extracted into the acceptor phase. Utilizing diphenhydramine hydrochloride as internal standard, repetitive extractions varied less than 5.2% RSD (n = 6), while the calibration curve for methamphetamine was linear within the range 20 ng/microL to 10 micrograms/mL (r = 0.9983). The detection limit of methamphetamine utilizing LLLME/CE was 5 ng/mL (S/N = 3) in both human urine and plasma.  相似文献   

6.
The freely dissolved concentration (C(free)) of pollutants is generally believed to be bioavailable and thus responsible for toxic effects. The C(free) of organic weak acids and bases consists of a dissociated and a nondissociated fraction. By using chlorophenols as model compounds, a negligible-depletion extraction technique, equilibrium sampling through membranes (ESTM), was developed for the measurement of the nondissociated part of the C(free). Polypropylene hollow fiber membranes (280-microm i.d., 50-microm wall thickness, 0.1-microm pore size, 15-cm length) were impregnated with undecane in the pores in the fiber wall as liquid membrane and filled with buffer solution in the lumen as acceptor. Then, the hollow fiber membranes were placed into the sample (donor) for an equilibrium extraction after sealing the two ends. The chlorophenol concentrations in the acceptor were then determined by direct injection into a HPLC system. Finally, the C(free) of the nondissociated and the dissociated species of a chlorophenol were calculated based on its measured concentration in the acceptor, its pK(a) value, and the measured pH in sample and acceptor. Theoretically calculated distribution coefficients (D = 8-970) agree well with the experimental enrichment factors (E(e(max)) = 6-1124), and the equilibration time was observed to increase with increasing distribution coefficients (hours to days). The freely dissolved concentration of five chlorophenols, with a wide range of pK(a) (4.9-9.2) and log K(ow) (2.35-5.24), were successfully determined in model solutions of humic acids and at low-ppb levels in river and leachate water.  相似文献   

7.
Wu HF  Yen JH  Chin CC 《Analytical chemistry》2006,78(5):1707-1712
A novel analytical technique termed drop-to-drop solvent microextraction (DDSME) was developed to determine three methoxyacetophenone isomers in one drop of water, which were then detected by gas chromatography/mass spectrometry using electronic ionization mass spectrometry for quantification analysis and self-ion/molecule reaction/tandem mass spectrometry for isomer differentiation. The best optimum parameters for the DDSME technique were as follows: extraction time, 5 min; using toluene as the extraction solvent; volume of extraction solvent, 0.5 microL and no salt addition. The advantages of this method are rapidity, convenience, ease of operation, simplicity of the device, and extremely little solvent and sample consumption. The limit of detection (LOD) for this technique was 1 ng/mL. The relative standard deviation was less than 2.6% (n = 5). The linear range of the calibration curve of DDSME is from 0.01 to 5 microg/mL with correlation coefficient (r2) of >0.954. In the comparison of the LOD of DDSME with other sample pretreatment methods including liquid/liquid extraction (LLE), single-drop microextraction (SDME), solid-phase microextraction (SPME), and liquid-phase microextraction (LPME) using a dual gauge microsyringe with hollow fiber methods, this method shows much better in sensitivity than the LLE (25 ng/mL) and it is compatible with SDME (0.5 ng/mL), SPME (0.5 ng/mL), and LPME using a dual gauge microsyringe with a hollow fiber (1 ng/mL). However, DDSME was more convenient than the LPME using a dual gauge microsyringe with a hollow fiber method and much lower cost than the SPME technique.  相似文献   

8.
Hou L  Lee HK 《Analytical chemistry》2003,75(11):2784-2789
Dynamic three-phase (liquid-liquid-liquid) microextraction was developed for capillary electrophoresis. Four aromatic amines as model compounds were extracted from 4-mL aqueous samples adjusted to basic condition (donor solution) through a small volume of organic solvent impregnated in a hollow fiber, which was held by the needle of a conventional syringe, and retracted into a 5-microL acidic acceptor solution inside the syringe. A renewable organic film and aqueous sample plug were formed inside the hollow fiber with the repeated movement of the syringe plunger enabled by a programmable syringe pump. This is believed to be the first reported instance of a semiautomated dynamic liquid-liquid-liquid microextraction (LLLME) procedure. Following this microextraction, the 5-microL acceptor solution was analyzed by capillary zone electrophoresis (CE). This new technique provided approximately 140-fold enrichment in 20 min. Utilizing 4-chloroaniline as internal standard, dynamic LLLME could provide good reproducibility (<4.0%). In addition, this method allowed the direct transfer of extracted analytes to a CE system for analysis.  相似文献   

9.
Zeng Z  Qiu W  Huang Z 《Analytical chemistry》2001,73(11):2429-2436
A novel solid-phase microextraction (SPME) fiber containing hydroxydibenzo-14-crown-4 (OH-DB14C4)/hydroxy-terminated silicone oil (OH-TSO) was first prepared by a sol-gel method and investigated for the determination of phenols. The possible mechanism is discussed and confirmed by IR spectra. The coating has stable performance in high temperature (to 350 degrees C) and solvents (organic and inorganic) due to the chemical binding between the coating and the fiber surface. The addition of crown ether enhances the polarity of the coating compared with that of the sol-gel OH-terminated silicone oil fiber and, accordingly, provides higher extraction efficiency for polar phenolic compounds. On the other hand, OH-terminated silicone oil in the coating can not only increase the length of network but also help to spread the stationary phase on the silica surface uniformly. The fluorescence microscopy experiment suggests the benefit the more uniform surface of the sol-gel-derived OHDB14C4/OH-TSO fiber in comparison with sol-gelderived OH-DB14C4 fiber. Some parameters of the SPME fiber for the determination of phenols were investigated. Limits of detection of the phenols are below 1.0 ng/mL, and the precisions are from 2.9 to 4.6% (n = 6). Linear ranges were found to be 0.1-10 microg/mL The sensitivity of the method is enhanced at a low-pH level (pH approximately 1) and with the addition of salt. The method was applied to the analysis of wastewater sample from a paper mill.  相似文献   

10.
The technique of automated in-tube solid-phase microextraction (SPME) coupled with liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS) was evaluated for the determination of beta-blockers in urine and serum samples. In-tube SPME is an extraction technique for organic compounds in aqueous samples, in which analytes are extracted from the sample directly into an open tubular capillary by repeated draw/eject cycles of sample solution. LC/MS analyses of beta-blockers were initially performed by liquid injection onto a LC column. Nine beta-blockers tested in this study gave very simple ESI mass spectra, and strong signals corresponding to [M + H]+ were observed for all beta-blockers. The beta-blockers were separated with a Hypersil BDS C18 column using acetonitrile/methanol/water/acetic acid (15:15:70:1) as a mobile phase. To optimize the extraction of beta-blockers, several in-tube SPME parameters were examined. The optimum extraction conditions were 15 draw/eject cycles of 30 microL of sample in 100 mM Tris-HCl (pH 8.5) at a flow rate of 100 microL/min using an Omegawax 250 capillary (Supelco, Bellefonte, PA). The beta-blockers extracted by the capillary were easily desorbed by mobile-phase flow, and carryover of beta-blockers was not observed. Using in-tube SPME/LC/ESI-MS with selected ion monitoring, the calibration curves of beta-blockers were linear in the range from 2 to 100 ng/mL with correlation coefficients above 0.9982 (n = 18) and detection limits (S/N = 3) of 0.1-1.2 ng/mL. This method was successfully applied to the analysis of biological samples without interference peaks. The recoveries of beta-blockers spiked into human urine and serum samples were above 84 and 71%, respectively. A serum sample from a patient administrated propranolol was analyzed using this method and both propranolol and its metabolites were detected.  相似文献   

11.
Wen X  Tu C  Lee HK 《Analytical chemistry》2004,76(1):228-232
A simple and novel two-step liquid-liquid-liquid microextraction technique combined with reversed-phase HPLC has been developed for the determination of the nonsteroidal antiinflammatory drugs ibuprofen and 2-(4-chlorophenoxy)-2-methylpropionic acid in wastewater samples. In the first step, the analytes were extracted from an acidified sample (donor solution) into 1-octanol immobilized in the pores of 10 pieces of polypropylene hollow fiber and further into a basic acceptor phase inside the hollow fiber channels. This first extraction step, using 0.01 M NaOH as the acceptor phase and 0.1 M HCl within the donor phase, had a 100% relative recovery with an enrichment factor of 100-fold. The extract in the first step was then adjusted to acidic condition with HCl. It now represented the donor phase for the second step of the extraction, using a single piece of hollow fiber, with 2 microL of 0.01 M NaOH solution as the acceptor phase. This analyte-enriched acceptor phase was subsequently withdrawn into a microsyringe and directly injected into an HPLC system for analysis. With this two-step microextraction, sensitivity enhancement of >15,000-fold could be obtained. Detection limits of < or =100 ng/L could be achieved for both compounds. The method was applied to the analysis of wastewater.  相似文献   

12.
A sensitive spectrophotometric method for the determination of freely dissolved copper concentrations in aqueous samples after preconcentration with hollow fiber membrane extraction has been developed. The method is based on the equilibrium sampling through a selective membrane into an acceptor solution containing 4-(pyridyl-2-azo)resorcinol (PAR), which serves as stripping agent and metal indicator. Negligible extraction of interferences and equilibrium enrichment of copper allowed for selective spectrophotometric determination of the Cu-PAR complex. Some important extraction parameters such as acceptor composition, shaking, equilibrium time, and sample volume were studied. The optimized methodology showed good linearity in the range of 5-100 microg/L, an enrichment factor of 93, good repeatability and reproducibility (RSDs < 6%, n = 6), and a detection limit of 4 microg/L. The cationic metals Ni2+, C(2+, Cd2+, Fe3+, Pb2+, Zn2+, and Mn2+ were shown not to interfere with the measurement of Cu2+. Measurements on samples containing mixtures of various ligands and cations were in good agreement with theoretically calculated concentrations, and the method was also applied to environmental samples. The developed technique requires less labor and less sophisticated equipment than conventional methods typically based on atomic absorption spectrometry or ICP.  相似文献   

13.
A novel threshold-voltage extractor architecture is presented. A differential-difference transconductor (DDT) loop automatically biases the device-under-test in continuous time around the inflection point of the /spl radic/I/sub D/ versus V/sub GS/ characteristics. Another DDT operates as an arithmetic processor to precisely implement multiplication by two and subtraction as needed for extrapolation. The extraction procedure thus complies entirely with all steps of the manual saturation method. With appropriate modifications, the architecture can also serve as an extractor implementing the linear method. The proposed architecture is applicable to both PMOS and NMOS on the same chip, and generates the value of V/sub T/ as a voltage with respect to the appropriate rail. It has been fabricated on silicon, and its accuracy has been experimentally verified by comparing automatically and manually extracted parameter values.  相似文献   

14.
A stable three-layer flow system, water/organic solvent/water, has been successfully applied for the first time in a microchannel to get rapid transport through an organic liquid membrane. In the continuous laminar flow region, the analyte (methyl red) was rapidly extracted across the microchannel from the donor to the acceptor phase through the organic solvent phase (cyclohexane). Thermal lens microscopy was used to monitor the process. The thickness of the organic phase, sandwiched by the two aqueous phases, was approximately 64 microm, and it was considered as a thin liquid organic membrane. Permeability studies showed the effects of molecular diffusion, layer thickness, and organic solvent-water partition coefficient on the molecular transport. In the microchip, complete equilibration was achieved in several seconds, in contrast to a conventionally used apparatus, where it takes tens of minutes. The thickness of the organic and aqueous boundary layers was defined as equal to the microchannel dimensions, and the organic solvent-water partition coefficient was determined on a microchip using the liquid/liquid extraction system. Experimental data on molecular transport across the organic membrane were in agreement with the calculated permeability based on the three-compartment water/organic solvent/water model. This kind of experiment can be performed only in a microspace, and the system can be considered as a potential biological membrane for future in vitro study of drug transport.  相似文献   

15.
A magnetic particle-based immuno-supported liquid membrane assay (m-ISLMA) based on chemiluminescence detection of a horseradish peroxidase-labeled hapten tracer that allows sample cleanup, analyte enrichment, and detection in a single analysis unit has been developed. Antibodies were immobilized on magnetic beads, and their position in the acceptor was controlled by two alternating opposing electromagnetic fields generated by a voltage applied to either of two electromagnets placed below and above the acceptor channel of the supported liquid membrane unit. The influence of antibody bead dilution in the acceptor was investigated and found to follow the ISLM theory, that is improved enrichment and sensitivity with increasing antibody concentration. Two different extraction procedures were investigated: procedure 1 (m-ISLMA-P1), which keeps the antibody beads trapped at the bottom of the acceptor during the entire analysis process; and procedure 2 (m-ISLMA-P2), which keeps the antibody beads dispersed and in motion in the acceptor phase during the extraction process. m-ISLMA-P2 resulted in 2000 times improved enrichment of simazine and a more than 3 orders of magnitude better limit of detection (LOD(10%)) (1.29 x 10(-5) microg L(-1)) than for m-ISLMA-P1 (2.00 x 10(-2) microg L(-1)) and corresponding microtiter plate magnetic particle-based ELISA (m-ELISA, LOD(10%) 1.30 x 10(-1) microg L(-1)). m-ISLMA-P2 and m-ELISA were further applied for the extraction and analysis of simazine-spiked surface water and fruit juice, finding no evidence for matrix influence for the former method; however, indications that trace amounts (nanograms per liter) of simazine or specific cross-reactants were present in both samples.  相似文献   

16.
高效液相色谱法检测食品接触材料中三聚氰胺的残留量   总被引:2,自引:0,他引:2  
建立了一种用液相色谱技术检测分析食品接触材料中三聚氰胺残留量的方法。样品采用0.1 mol/L盐酸作为提取溶液,70℃水浴超声提取。色谱分离采用NH2柱,流动相为V(乙腈):V(5mmol/L磷酸盐缓冲溶液,pH 6.5)=75:25,二极管阵列检测器检测。在优化条件下,三聚氰胺浓度在0.2-100 mg/L范围内与其峰面积线性关系良好,检出限(S/N=3)为0.02 mg/L。在100μg的添加水平下,三聚氰胺的回收率在80-99%之间,相对标准偏差(RSD)为2.80-4.32%。揭示了原料中三聚氰胺残留量与成型品的三聚氰胺迁移量的正相关关系。结果表明,该法简便、快速,可准确测定食品接触材料中三聚氰胺残留量。  相似文献   

17.
L Zhu  C Tu  H K Lee 《Analytical chemistry》2001,73(23):5655-5660
This paper describes a novel method that applies field-amplified sample injection (FASI) in micellar electrokinetic chromatography (MEKC) with a low pH background electrolyte (BGE). Six phenolic compounds prepared in water or NaOH solution were used as the test analytes. Sample was injected electrokinetically after the introduction of a plug of water. During the injection, the water plug was pumped out of the capillary inlet by the electroosmotic flow, and the phenolic anions migrated very quickly in the direction of the outlet. When the anions reached the boundary between the water plug and BGE, they were neutralized and ceased moving. Thereafter, MEKC was initiated for the separation. This on-line preconcentration method could be conveniently coupled with a liquid-liquid-liquid microextraction procedure, in which a hollow fiber was used as an extraction solvent support to extract the analytes from the water sample. The acceptor phase consisted of 8 mM NaOH. After extraction, the extract was analyzed directly by MEKC, as described.  相似文献   

18.
Two molecularly imprinted polymers were synthesized using either dichloromethane or toluene as the porogen and terbuthylazine as the template and were used as solid-phase extraction cartridges for the enrichment of six chlorotriazines (deisopropylatrazine, deethylatrazine, simazine, atrazine, propazine, and terbuthylazine) in natural water and sediment samples. The extracted samples were analyzed by liquid chromatography/diode array detection (LC/DAD). Several washing solvents, as well as different volumes, were tested for their ability to remove the matrix components nonspecifically adsorbed on the sorbents. This cleanup step was shown to be of prime importance to the successful extraction of the pesticides from the aqueous samples. The optimal analytical conditions were obtained when the MIP imprinted using dichloromethane was the sorbent, 2 mL of dichloromethane was used in the washing step, and the preconcentrated analytes were eluted with 8 mL of methanol. The recoveries were higher than 80% for all the chlorotriazines except for propazine (53%) when 50- or 100-mL groundwater samples, spiked at 1 microg/L level, were analyzed. The limits of detection varied from 0.05 to 0.2 microg/L when preconcentrating a 100-mL groundwater sample. Natural sediment samples from the Ebre Delta area (Tarragona, Spain) containing atrazine and deethylatrazine were Soxhlet extracted and analyzed by the methodology developed in this work. No significant interferences from the sample matrix were noticed, thus indicating good selectivity of the MIP sorbents used.  相似文献   

19.
A new method using a mini-column packed with sulfur as a new solid phase extractor has been developed for simultaneous preconcentration of lead and cadmium in water samples prior to flame atomic absorption spectrometric determinations. The effects of various parameters such as pH, flow rate of sample and eluent, type and concentration of eluent, sample volume, amount of adsorbent and interfering ions have been studied. The calibration graph was linear in the range of 10-300 and 1-20 ng mL(-1) for lead and cadmium, respectively. The limit of detection based on three times the standard deviation of the blank (3S(b)) was 3.2 and 0.2 ng mL(-1) (n=10) for lead and cadmium, respectively. A preconcentration factor of 250 was achieved in this method. The proposed procedure was applied to the determination of metal ions in tap, river and wastewater samples.  相似文献   

20.
左丹英  朱宝库  王绍洪  徐又一 《功能材料》2006,37(1):150-154,159
研究了聚丙烯中空纤维膜接触萃取器中二(2-乙基已基)磷酸萃取金属铜离子的工艺条件以及溶剂夹带,分析了原料的pH值、两相流速、有机相初始铜离子浓度以及萃取膜面积对萃取效率的影响,结果表明,两相流速、萃取膜面积对萃取率基本无影响,而水溶液的pH值和有机相初始铜离子浓度的改变使萃取率在40%~99%之间变化.这主要是由于整个萃取过程的传质阻力主要来源于D2EHPA和Cu2 的界面配位络合反应阻力,当铜浓度比较高时,传质阻力或传质系数与铜浓度无关,其值基本不变;而当铜浓度降低时,传质阻力随着铜浓度的降低而增大,传质系数则随着铜浓度的降低而减小.  相似文献   

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