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1.
Two miniature and compact optoelectronic devices fabricated by means of integration of light emitting diodes have been developed for turbidimetric and nephelometric measurements. These devices are operating according to paired-emitter-detector-diode (PEDD) principle. The detectors have been characterized using bovine serum albumin and Exton protein assay as a model analyte and a model analytical method, respectively. The developed detectors have been adapted for measurements under conditions of flow injection analysis (FIA). Under optimized conditions the turbidimetric flow system offers the range of linear response up to 400 mg L−1 with the detection limit at 20 mg L−1. The linear range and detection limit found for optimized nephelometric FIA system are 15–500 mg L−1 and 8 mg L−1, respectively. The PEDD-based FIA systems with the detector operating according to both modes of measurements have been successfully applied for urinalysis offering total protein determination at physiological and pathological levels with high throughput (over 60 injections per hour).  相似文献   

2.
A highly sensitive flow analysis system has been developed for the trace determination of reactive phosphate in natural waters, which uses a polymer inclusion membrane (PIM) with Aliquat 336 as the carrier for on-line analyte separation and preconcentration. The system operates under flow injection (FI) and continuous flow (CF) conditions. Under optimal FI conditions the system is characterised by a linear concentration range between 0.5 and 1000 μg L−1 P, a sampling rate of 10 h−1, a limit of detection of 0.5 μg L−1 P and RSDs of 3.2% (n = 10, 100 μg L−1) and 7.7% (n = 10, 10 μg L−1). Under CF conditions with 10 min stop-flow time and sample solution flow rate of 1.32 mL min−1 the flow system offers a limit of detection of 0.04 μg L−1 P, a sampling rate of 5 h−1 and an RSD of 3.4% (n = 5, 2.0 μg L−1). Interference studies revealed that anions commonly found in natural waters did not interfere when in excess of at least one order of magnitude. The flow system, operating under CF conditions, was successfully applied to the analysis of natural water samples containing concentrations of phosphate in the low μg L−1 P range, using the multipoint standard addition method.  相似文献   

3.
A HPLC method using a coulometric electrode array detector (CEAD) to analyse 4-ethylcatechol in wine was established. The procedure does not require any sample preparation or analyte derivatisation and performs chromatographic separation in a short time. The assay method is linear up to 1520 μg L−1 and precise (R.S.D. < 3%), with limits of detection and quantitation of 1.34 μg L−1 and 2.2 μg L−1, respectively. Recoveries in spiked wine samples ranged from 95% to 104% with a median value of 102% and matrix effects were not observed. The method was applied to the evaluation of the concentration of 4-EC in 250 commercial Italian wines. The red wines analysed had median, 75° percentile and maximum values of 37 μg L−1, 89 μg L−1 and 1610 μg L−1, respectively. For Sangiovese-based wines the mean ratios of 4-EP and 4-EG to 4-EC were 3.7:1 and 0.7:1, respectively. The feasibility of a cheaper fluorimetric approach to 4-EC quantification was investigated.  相似文献   

4.
Present study developed a new method for the sensitive determination of pyrethroid insecticides with solid phase extraction in combination with high performance liquid chromatography and UV detector. SiO2 microspheres, a new SiO2 based material, was investigated for the enrichment ability and applicability as the solid phase extraction sorbent. Four pyrethroid pesticides such as fenpropathrin, cyhalothrin, fenvalevate and biphenthrin were used as the target analytes. Parameters that maybe influence the extraction efficiency such as the eluent type and its volume, sample flow rate, sample pH, and the sample volume were optimized in detail, and the optimal conditions were as followed: sample volume, 100 mL; concentration of methanol, 30%; acetone volume, 5 mL; sample flow rate, 4.2 mL min−1; sample pH, 7. The experimental results indicated that there was good linearity in the concentration range of 0.1–50 μg L−1 except biphenthrin in the range of 0.05–25 μg L−1. The detection limits for fenpropathrin, cyhalothrin, fenvalevate and biphenthrin were in the range of 0.02–0.08 μg L−1. The intra-day and day to day precisions (RSDs, n = 6) were in the ranges of 2.6–4.4% and 5.3–7.2%, respectively. The method was validated with five real environmental water samples, and all these results proved that proposed method could be used as a good alternative for the routine analysis for such pollutants in environmental samples.  相似文献   

5.
Fernando Maya 《Talanta》2010,80(3):1333-18
A new, multisyringe flow injection set-up has been developed for the completely automated determination of trace thiazide compounds with diuretic action in different types of samples. The proposed instrumental set-up exploits for the first time, a low pressure on-line solid phase extraction-liquid chromatography-chemiluminescence detection method. This novel combination of sample treatments in flow systems expands the current applicability of low pressure liquid chromatography due to the isolation/preconcentration of the target compounds, besides high selectivity and sensitivity.For the determination of three thiazide compounds named hydroflumethiazide, furosemide and bendroflumethiazide, the proposed set-up provided with the preconcentration of only 1 mL of sample, limits of detection of 3, 60 and 40 μg L−1, respectively. Furthermore wide linear dynamic ranges of 6-4000, 140-20,000 and 90-40,000 μg L−1, respectively, were obtained. Besides of this, a high injection throughput of 12 h−1 was also achieved. As in sports, thiazide diuretics are prohibited substances, the proposed method has been applied to their determination in urine samples. Furthermore the potential of the proposed method as a fast-screening approach for emerging contaminants in waters has been also tested by applying it to well water and leachates from a solid waste landfill.  相似文献   

6.
An on-line solid phase extraction (SPE) preconcentration system coupled to flame atomic absorption spectrometer (FAAS) was developed for determination of copper and cadmium at μg L−1 level. The method is based on the on-line retention of copper and cadmium on a microcolumn of alumina modified with sodium dodecyl sulfate (SDS) and 1,10-phenanthroline and subsequent elution with ethanol and determination by FAAS. The effect of chemical and flow variables that could affect the performance of the system was investigated. The relative standard deviation (n = 6) at 20 μg L−1 level for copper and cadmium were 1.4 and 2.2% and the corresponding limits of detection (based on 3σ) were 0.04 and 0.14 μg L−1, respectively. The method was successfully applied to determination of copper and cadmium in human hair and water samples.  相似文献   

7.
In this paper, the conversion of azoxystrobin in a strongly fluorescent degradation product by UV irradiation with quantitative purposes and its fluorimetric determination are reported for the first time. A multicommuted flow injection-solid phase spectroscopy (FI-SPS) system combined with photochemically-induced fluorescence (PIF) is developed for the determination of azoxystrobin in grapes, must and wine. Grape samples were homogenized and extracted with methanol and further cleaned-up by solid-phase extraction on C18 silica gel. Wine samples were solid-phase extracted on C18 sorbent using dichloromethane as eluent. Recoveries of azoxystrobin from spiked grapes (0.5-2.0 mg Kg−1), must (0.5-2.0 μg mL−1) and wine (0.5-2.0 μg mL−1) were 84.0-87.6%, 95.5-105.9% and 88.5-111.2%, respectively. The quantification limit for grapes was 0.021 mg Kg−1, being within European Union regulations, and 18 μg L−1 and 8 μg L−1 for must and wine, respectively.  相似文献   

8.
Springer VH  Lista AG 《Talanta》2010,83(1):126-129
A new method to determine metsulfuron methyl (MSM) and chlorsulfuron (CS) in different water samples was developed. It consists in a solid phase extraction (SPE) procedure using multiwalled carbon nanotubes (MWCNTs) as sorbent material in combination with capillary zone electrophoretic determination. To carry out the pre-concentration step, a simple flow injection system was developed and optimized. Thus, 250 μL of aqueous solution containing methanol 50% (v/v) and acetonitrile 2% (v/v) as eluent, 10 mL of sample and a flow rate of 1.15 mL min−1 were selected. The CE variables also were optimized. A rapid determination and good resolution of two herbicides were obtained within 9 min using a simple electrophoretic buffer (50 mmol L−1 sodium tetraborate with 3% of methanol, pH = 9.0). Under the optimum conditions, the calibration curves were linear between 0.5 and 6 μg L−1 for MSM and CS with R2 = 0.995 and 0.997, respectively. The repeatability of the proposed method, expressed as relative standard deviation (RSD), varied between 4.1% and 5.4% (n = 10) and the detection limits for MSM and CS were 0.40 and 0.36 μg L−1, respectively. Good results were achieved when the proposed method was applied to spiked real water samples. The recoveries percentages of the two analytes were over the range 86-108%.  相似文献   

9.
A modified SBA-15 mesoporous silica material NH2-SBA-15 was synthesized successfully by grafting γ-aminopropyl-triethoxysilane. The material was characterized using transmission electron microscopy (TEM) and Fourier transform infrared/Raman (FT-IR/Raman) spectroscopy, and used for the first time in a flow injection on-line solid phase extraction (SPE) coupled with flame atomic absorption spectrometry (FAAS) to detect trace Cr (VI). Effective sorption of Cr (VI) was achieved at pH 2.0 with no interference from Cr (III) and other ions and 0.5 mol L−1 NH3·H2O solution was found optimal for the complete elution of Cr (VI). An enrichment factor of 44 and was achieved under optimized experimental conditions at a sample loading of 2.0 mL min−1 sample loading (300 s) and an elution flow rate of 2.0 mL min−1 (24 s). The precision of the 11 replicate Cr (VI) measurements was 2.1% at the 100 μg L−1 level with a detection limit of 0.2 μg L−1 (3 s, n = 10) using the FAAS. The developed method was successfully applied to trace chromium determination in waste water. The accuracy was validated using a certified reference material of riverine water (GBW08607).  相似文献   

10.
A flow amperometric enzymatic biosensor for the determination of glucose was constructed. The biosensor consists of a flow reactor based on porous silver solid amalgam (AgSA) and a flow tubular detector based on compact AgSA. The preparation of the sensor and the determination of glucose occurred in three steps. First, a self-assembled monolayer of 11-mercaptoundecanoic acid (MUA) was formed at the porous surface of the reactor. Second, enzyme glucose oxidase (GOx) was covalently immobilized at MUA-layer using N-ethyl-N′-(3-dimethylaminopropyl) carboimide and N-hydroxysuccinimide chemistry. Finally, a decrease of oxygen concentration (directly proportional to the concentration of glucose) during enzymatic reaction was amperometrically measured on the tubular detector under flow injection conditions. The following parameters of glucose determination were optimized with respect to amperometric response: composition of the mobile phase, its concentration, the potential of detection and the flow rate. The calibration curve of glucose was linear in the concentration range of 0.02–0.80 mmol L−1 with detection limit of 0.01 mmol L−1. The content of glucose in the sample of honey was determined as 35.5 ± 1.0 mass % (number of the repeated measurements n = 7; standard deviation SD = 1.2%; relative standard deviation RSD = 3.2%) which corresponds well with the declared values. The tested biosensor proved good long-term stability (77% of the current response of glucose was retained after 35 days).  相似文献   

11.
The potential of carbon nanotubes for the solid phase extraction of parabens in cosmetic products and the detection using a corona-charged aerosol detector (C-CAD) is presented in this work. The analytical procedure is based on a conventional solid phase extraction step for which 20 mg of multi-walled carbon nanotubes were packed in a 3-mL commercial SPE cartridge. Methylparaben, ethylparaben, propylparaben and butylparaben were thus isolated and preconcentrated from the pre-treated samples and subsequently separated on a RP-C18 column using acetonitrile:water, 50:50 (v/v) as mobile phase. The analytical signals for the individual parabens were obtained using C-CAD. The experimental variables affecting the extraction procedure and the instrumental detection have been deeply studied. Limits of detection were in the range of 0.5–2.1 mg L−1, while the linear range was extended up to 400 mg L−1. The average precision of the method varied between 3.3–3.8% (repeatability) and 4.3–7.6% (reproducibility). Finally, the optimized procedure was applied to the determination of the target preservatives in a variety of cosmetic products with satisfactory results.  相似文献   

12.
A flow solid phase extraction procedure based on biosorption of Pt(IV) and Pd(II) on Aspergillus sp. immobilized on cellulose resin Cellex-T was proposed for the separation and preconcentration of Pt and Pd before their determination by electrothermal atomic absorption spectrometry (ETAAS). The analytical conditions including sample pH, eluent type, flow rates of sample and eluent solutions were examined. The analytes were selectively retained on the biosorbent in acidic medium (pH 1) and subsequently eluted from the column with 1 mL of thiourea solution (0.25 mol L− 1 thiourea in 0.3 mol L− 1 HCl). The reproducibility of the procedure was below 5%. The limit of detection of the method was 0.020 ng mL− 1 for Pt and 0.012 ng mL− 1 for Pd. The method validation was performed by analysis of certified reference materials BCR-723 (tunnel dust) and SARM-76 (platinum ore). The developed separation procedure was applied to the determination of Pt and Pd in road dust samples by ETAAS.The applied biosorbent is characterized by high sorption capacity: 0.47 mg g− 1 for Pt and 1.24 mg g− 1 for Pd.  相似文献   

13.
Although the use of once widely applied selective herbicide, 4,6-dinitro-o-cresol (DNOC), was cancelled by US-EPA in 1987, it is still found in soil and water due to its slow degradation in the environment. Since solid phase extraction-spectrophotometry combinations are much simpler and cheaper than chromatography/MS based methods and most routine laboratories lack such sophisticated instrumentation, it is desirable to establish novel sensitive, well-established, and field-applicable spectrophotometric methods for the rapid assay of DNOC in water and soil. For this purpose, two distinct spectrophotometric methods utilizing the periodate and copper(II)-neocuproine (Nc) reagents have been developed following Zn/HCl reduction of the pesticide in a microwave oven for 15 s, and validated for DNOC determination at mg L−1 level. The LOD values were 1.6 and 0.2 mg L−1 for periodate and Cu(II)-Nc methods, respectively. Statistical comparison of the developed methods was made with the aid of high performance liquid chromatography (HPLC) equipped with a C18 (5 μm), 250 mm× 4.6 mm ID reversed phase column in conjunction with a UV (264 nm) detector, and a methanol (HPLC grade) +0.1% glacial acetic acid mixture mobile phase. Both spectrophotometric methods were directly applicable to soil since they were not interfered with common soil cations and anions, together with some pesticides. These methods were applied to real samples such as synthetically contaminated montmorillonite and lemon juice, and overall recovery efficiencies at the order of 95% or greater were achieved in the devised adsorption/elution procedures. An 8-hydroxyquinoline (oxine)-impregnated XAD copolymer resin stabilized with Fe(III) salt was used to preconcentrate DNOC at a concentration factor of 20 from lemon juice contaminated with 1 mg L−1 DNOC, and the analyte retained at pH 2.5 was eluted with 0.025 M methanolic NaOH. Both the devised spectrophotometric methods and the proposed preconcentration column with optimized sorption and desorption conditions are novel for DNOC assay in the natural environment.  相似文献   

14.
In this study a method for the determination of cadmium in fuel alcohol using solid-phase extraction with a flow injection analysis system and detection by flame atomic absorption spectrometry was developed. The sorbent material used was a vermicompost commonly used as a garden fertilizer. The chemical and flow variables of the on-line preconcentration system were optimized by means of a full factorial design. The selected factors were: sorbent mass, sample pH, buffer concentration and sample flow rate. The optimum extraction conditions were obtained using sample pH in the range of 7.3-8.3 buffered with tris(hydroxymethyl)aminomethane at 50 mmol L−1, a sample flow rate of 4.5 mL min−1 and 160 mg of sorbent mass. With the optimized conditions, the preconcentration factor, limit of detection and sample throughput were estimated as 32 (for preconcentration of 10 mL sample), 1.7 μg L−1 and 20 samples per hour, respectively. The analytical curve was linear from 5 up to at least 50 μg L−1, with a correlation coefficient of 0.998 and a relative standard deviation of 2.4% (35 μg L−1, n = 7). The developed method was successfully applied to spiked fuel alcohol, and accuracy was assessed through recovery tests, with recovery ranging from 94% to 100%.  相似文献   

15.
A simple chiral high-performance liquid chromatography (HPLC) method with ultraviolet (UV) and circular dichroism (CD) detection was developed and validated for measuring benalaxyl enantiomers using (R,R) Whelk-O 1 column. The effects of mobile phase composition and column temperature on the entioseparation were investigated. A CD detector was used to determine the elution order of the enantiomers. Excellent resolution was easily obtained using n-hexane-polar organic alcohols mobile phase. The chiral recognition mechanism was also discussed. Based on the developed chiral HPLC method, enantioselective analysis methods for this fungicide in environment matrix (soil and water) were developed and validated. Good linearities were obtained over the concentration range of 0.25-25 mg L−1 for both enantiomers. Liquid-liquid extraction and solid phase extraction (SPE) were used for the enrichment and cleanup of soil and water samples. Recoveries for the two enantiomers were 79-91% at 0.02, 0.04 and 0.2 mg kg−1 levels from soil, and 89-101% at 0.0025, 0.01 and 0.05 mg L−1 levels from water. Run-to-run and day-to-day assay precisions were below 10% for both enantiomers at concentrations of 0.5, 1 and 5 mg L−1. Individual detection limits of the two enantiomers were both 2 ng. Limits of detection (LOD) were 0.004 mg kg−1 in soil and 0.001 mg L−1 in water.  相似文献   

16.
A flow injection (FI) method with flame atomic absorption spectrometry (FAAS) detection was developed for the determination and speciation of nitrite and nitrate in foodstuffs and wastewaters. The method is based on the oxidation of nitrite to nitrate using a manganese(IV) dioxide oxidant microcolumn where the flow of the sample through the microcolumn reduces the MnO2 solid phase reagent to Mn(II), which is measured by FAAS. The absorbance of Mn(II) are proportional to the concentration of nitrite in the samples. The injected sample volume was 400 μL with a sampling rate of analyses was 90 h−1 with a relative standard deviation better than 1.0% in a repeatability study. Nitrate is reduced to nitrite in proposed FI-FAAS system using a copperized cadmium microcolumn and analyzed as nitrite. The calibration curves were linear up to 20 mg L−1 and 30 mg L−1 with a detection limit of 0.07 mg L−1 and 0.14 mg L−1 for nitrite and nitrate, respectively. The results exhibit no interference from the presence of large amounts of ions. The method was successfully applied to the speciation of nitrite and nitrate in spiked natural water, wastewater and foodstuff samples. The precision and accuracy of the proposed method were comparable to those of the reference spectrophotometric method.  相似文献   

17.
An analytical procedure with improved sensitivity was developed for cyanide determination in natural waters, exploiting the reaction with the complex of Cu(I) with 2,2′-biquinoline 4,4′-dicarboxylic acid (BCA). The flow system was based on the multi-pumping approach and long pathlength spectrophotometry with a flow cell based on a Teflon AF 2400® liquid core waveguide was exploited to increase sensitivity. A linear response was achieved from 5 to 200 μg L−1, with coefficient of variation of 1.5% (n = 10). The detection limit and the sampling rate were 2 μg L−1 (99.7% confidence level), and 22 h−1, respectively. Per determination, 48 ng of Cu(II), 5 μg of ascorbic acid and 0.9 μg of BCA were consumed. As high as 100 mg L−1 thiocyanate, nitrite or sulfite did not affect cyanide determination. Sulfide did not interfere at concentrations lower than 40 and 200 μg L−1 before or after sample pretreatment with hydrogen peroxide. The results for natural waters samples agreed with those obtained by a fluorimetric flow-based procedure at the 95% confidence level. The proposed procedure is then a reliable, fast and environmentally friendly alternative for cyanide determination in natural waters.  相似文献   

18.
A new flow injection (FIA) procedure for the preconcentration of cadmium in urine using multiwalled carbon nanotubes (MWCNT) as sorbent and posterior electrothermal atomization atomic absorption spectrometry (ETA-AAS) Cd determination has been developed. Cadmium was retained in a column filled with previously oxidized MWCNTs and it was quantitatively eluted with a nitric acid solution. The parameters influencing the adsorption-elution process such as pH of the sample solution, amount of sorbent and flow rates of sample as well as eluent solutions have been studied. Cd concentration in the eluent was measured by ETA-AAS under the optimized conditions obtained. The results indicated the elimination of urine matrix effect as a consequence of the preconcentration process performed. Total recovery of cadmium from urine at pH 7.2 using a column with 45 mg of MWCNTs as sorbent and employing a HNO3 0.5 mol L−1 solution for elution was attained. The detection limit obtained was 0.010 μg L−1 and the preconcentration factor achieved was 3.4. The method showed adequate precision (RSD: 3.4-9.8%) and accuracy (mean recovery: 97.4-100%). The developed method was applied for the determination of cadmium in real urine samples from healthy people (in the range of 0.14-2.94 μg L−1) with satisfactory results.  相似文献   

19.
A novel flow injection analysis (FIA) system based on liquid-liquid microextraction and fluorimetric determination was developed for the determination of traces of the Zn2+ ion using 5-(8-hydroxy-2-quinolinylmethyl)-2,8-dithia-5-aza-2,6-pyridinophane (L) as a sensitive and selective fluorimetric sensor, with λex = 373 nm and λem = 530 nm, and hexanol as the extracting organic solvent. In the designed FIA system, the phase separation takes place via gravitation forces in the absence of any segmenter. The influence of pH and ionic strength of the solution, amount of ligand, nature of counter ion, volume of organic solvent, extraction time and coil length was investigated. Under optimized experimental conditions, the calibration curve found to be liner over a concentration range of 0.025-4.53 μg mL−1 (R2 = 0.9951) with a limit of detection of 2.3 ng mL−1. The enrichment factor was 45 and relative standard deviation for 7 replicate determinations was 2.43%. The method is very fast and uses low levels of organic solvents. The proposed method was applied successfully to the determination of zinc(II) in human hair, human serum and two inorganic sludge samples.  相似文献   

20.
In this study a method for the determination of low concentrations of silver in waters using solid-phase extraction with a flow injection analysis system and detection by flame atomic absorption spectrometry (FAAS) was developed. Moringa oleifera seeds were used as a biosorbent material. Chemical and flow variables of the on-line preconcentration system such as sample pH and flow rate, preconcentration time, eluent concentration and sorbent mass were studied. The optimum preconcentration conditions were obtained using sample pH in the range of 6.0-8.0, preconcentration time of 4 min at a flow rate of 3.5 mL min− 1, 0.5 mol L− 1 HNO3 eluent at a flow rate of 4.5 mL min− 1 and 35 mg of sorbent mass. With the optimized conditions, the preconcentration factor, precision, detection limit and sample throughput were estimated as 35 (for preconcentration of 14 mL sample), 3.8% (5.0 μg L− 1, n = 7), 0.22 μg L− 1 and 12 samples per hour, respectively. The developed method was successfully applied to mineral water and tap water, and accuracy was assessed through analysis of a certified reference material for water (APS-1071 NIST) and recovery tests, with recovery ranging from 94 to 101%.  相似文献   

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