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1.
A study was performed to assess the performance of aminoacids immobilized on carbon nanotubes (CNTs) for their employment as a sorbent for solid phase extraction systems. An immobilization method is introduced and the aminoacid l-tyrosine was chosen as a case study. A spectrophotometric study revealed the amount of aminoacid immobilizated on CNTs surface, and it turned to be of 3174 μmol of l-tyr g−1. The material was tested for Co retention using a minicolumn inserted in a flow system. At pH 7.0, the amount of Co retained by the column was of 37.58 ± 3.06 μmol Co g−1 of CNTs. A 10% (v/v) HNO3 solution was chosen as eluent. The pH study revealed that Co binding increased at elevated pH values. The calculation of the mol ratio (moles of Co bound at pH 9 to moles of l-tyr) turned to be 3:1. The retention capacity was compared to other bivalent cations and showed the following tendency: Cu2+ > Ni2+ > Zn2+ ? Co2+. The analytical performance was evaluated and an enrichment factor of 180 was obtained when 10 mL of 11.37 μg L−1 Co solution was loaded onto the column at pH 9.0; reaching a limit of detection (LoD) of 50 ng L−1. The proposed system was successfully applied to Co determination in QC-LL2 standard reference material (metals in natural water).  相似文献   

2.
A solid phase extraction system for separation and preconcentration of trace amounts of Pb(II), Ni(II), Cd(II) and Cu(II) is proposed. The procedure is based on the adsorption of Pb2+, Ni2+, Cd2+ and Cu2+ ions on a column of 1-(2-pyridylazo)-2-naphthol (PAN) immobilised on surfactant-coated clinoptilolite prior to their determinations by Flame Atomic Absorption Spectroscopy (FAAS). The effective parameters including pH, sample volume, sample flow rate and eluent flow rate were also studied. The analytes collected on the column were eluted with 5 mL of 1 mol L?1 nitric acid. A concentration factor of 180 can be achieved by passing 900 mL of sample through the column. The detection limits (3 s) for Cd, Cu, Pb and Ni were found to be 0.28, 0.12, 0.44 and 0.46 µg L?1, respectively. The relative SDs at 10 µg L?1 (n = 10) for analytes were in the range of 1.2–1.4%. The method was applied to the determination of Pb, Ni, Cd and Cu in water samples.  相似文献   

3.
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   

4.
A novel Cd(II)-imprinted polymer was prepared with chemical immobilization using N-methacryloyl-L-Histidine as a vinylated chelating agent for online solid-phase extraction of Cd(II) for determination by inductively coupled plasma mass spectrometry. The Cd(II)–monomer complex was synthesized and copolymerized through bulk polymerization method in the presence of ethyleneglycoldimethacrylate cross-linker. The resulting polymer was leached with 1.0?mol?L?1 HNO3 to generate the cavities in the polymer for Cd(II) ions. The experimental conditions, including load pH, solution flow rate, and eluent concentration for effective sorption of Cd(II), were optimized using a minicolumn of the imprinted polymer. A volume of 5.0?mL sample 5?µg?L?1 Cd(II) solution at pH 6.5 was loaded on the column at 2.0?mL?min?1 using a sequential injection system followed by elution with 1.0?mL of 0.75?mol?L?1 HNO3. The relative selectivity coefficients of the imprinted polymer for Cd(II) were 38.5, 3.5, 3.0, 2.5, and 6.0 in the presence of Cu(II), Ni(II), Zn(II), Co(II), and Pb(II), respectively. Computational calculations revealed that the selectivity of the imprinted polymer was mediated by the stability of Cd(II)–N-methacryloyl-L-Histidine complex which was more stable than commonly used monomers including 4-vinyl pyridine, methacrylic acid, and vinylimidazole. The detection limit and relative standard deviation were 0.004?µg?L?1 and 3.2%, respectively. The method was validated by the analysis of seawater certified reference material (CASS-4) and successfully used for the determination of Cd(II) in coastal seawater and estuarine water.  相似文献   

5.
Polytetrafluoroethylene (PTFE) was grafted (g) with acrylic acid (AAc) by γ-ray pre-irradiation method to get PTFE-g-AAc films, then N-isopropylacrylamide (NIPAAm) was grafted onto PTFE-g-AAc films with γ-ray to get (PTFE-g-AAc)-g-NIPAAm. PTFE films were irradiated in air at a dose rate of 3.0 kGy h–1 and different radiation dose. The irradiated films were placed in glass ampoules, which contained aqueous solutions with different monomer concentration (AAc), and then they were heated at different temperatures and reaction time. NIPAAm onto PTFE-g-AAc was carried out with the same procedure with monomer concentration of 1 mol L−1. The thermosensitivity of the samples was defined and calculated as the ratio of the grafted samples swelling at 28 and 35 °C, and pH sensitivity defined as the ratio of the grafted samples swelling at pH 2 and 8.  相似文献   

6.
The electrochemical surface plasmon resonance (ESPR) technique was used to investigate the electrodeposition of the charge-transfer complex (CTC) generated during electrooxidation of o-tolidine (o-TD) in pH 4.5 Britton–Robinson buffers and the effects of coexisting dermatan sulfate (DS). The peak-type surface plasmon resonance (SPR) responses (versus time) observed in the cyclic voltammetric experiments indicated the precipitation and dissolution of a poorly soluble CTC, an oxidation intermediate, formed during the redox switching of o-TD in a weakly acidic medium. The effects of potential scan rate and solution pH were examined. The height of the peak-type SPR response to the redox switching of the o-TD/CTC “couple” was notably enhanced by the introduction of DS, due to the formation of a mass-enhanced CTC-DS adduct, as also supported by UV–vis spectroelectrochemistry. The SPR signal responded linearly to the DS concentration up to 14 μmol L−1, with a limit of detection (LOD) down to 8 nmol L−1 (S/N = 3). The analytical performance of the ESPR technique was found to be better than that of the quartz crystal microbalance technique with an LOD value of 70 nmol L−1. The CTC-based ESPR assay is recommended as a new, highly sensitive and dynamically surface-regenerated biosensing technology for other species.  相似文献   

7.
A fed-batch culture system with constant feeding (glucose 80 g L−1, 0.25 ml min−1) was used to study the influence of glucose on cell dry weight and exopolysaccharides production from submerged Tremella fuciformis spores in a 5-L stirred-tank bioreactor. The results showed that high levels of cell mass (9.80 g L−1) and exopolysaccharides production (3.12 g L−1) in fed-batch fermentation were obtained after 1 h of feeding, where the specific growth rate (μ) and exopolysaccharides yield on substrate consumed (YP/S) were 0.267 d−1 and 0.14 g g−1. Unlike batch fermentation, maximal cell mass and exopolysaccharides production merely reached 7.11 and 2.08 g L−1; the specific growth rate (μ) and exopolysaccharides yield on substrate consumed (YP/S) were 0.194 d−1 and 0.093 g g−1, respectively. It is concluded that the synthesis of exopolysaccharides can be promoted effectively when feeding glucose at a late exponential phase.  相似文献   

8.
This contribution describes use of a separation method based on on-line coupling of a multisyringe flow system with a chromatographic monolithic column for simultaneous determination of hydrochlorothiazide and losartan potassium in tablets. The system comprised a multisyringe module, three low-pressure solenoid valves, a monolithic C18 column (25 mm × 4.6 mm i.d.), and a diode-array detector. The mobile phase was 10 mmol L−1 potassium dihydrogen phosphate (pH 3.1)-acetonitrile-methanol (65:33:2 v/v/v) at a flow rate 0.8 mL min−1. UV detection was carried out at 226 nm. The multi-syringe chromatographic (MSC) method with UV spectrophotometric detection was optimized and validated. Results from validation were very good. The analysis time was about 400 s. The method was found to be applicable to routine analysis of both compounds in tablets. The coupling of the monolithic columns with a multi-syringe flow-injection analysis manifold provides an excellent and inexpensive tool to solve the separation problems without use of HPLC instrumentation.  相似文献   

9.
A new method for simultaneous determination of organic acids in red wine and must by liquid chromatography was studied. The determination of organic acids in wines can be achieved in less than 13 min, preceded only by a simple sample dilution and filtration step. With this method, the chromatographic separation of eight organic acids and interfering peaks present in red wine, required only one reversed phase column (Waters Atlantis dC18 column, 4.6 × 150 mm ID, 5 μm). As mobile phase, isocratic acetonitrile–0.01 mol L−1 KH2PO4 at pH 2.7 5:95 (v/v) at a flow rate of 0.8 mL min−1 was used. Detection wavelength was set at 210 nm except for ascorbic acid which was detected at 243 nm. Application to red wine and must confirmed good repeatability and showed a wide variation range for concentrations of organic acids.  相似文献   

10.
In this paper, a time-based multicommutated flow system is proposed for appropriate selection and modulation of mobile phase composition in flow-injection (FI)/sequential-injection (SI) chromatography. The novel flow assembly involves the on-line coupling of a short monolithic reversed-phase chromatographic column with a multisyringe flow injection set-up furnished with a set of solenoid valves. The proposed hyphenated technique was applied to the simultaneous spectrophotometric determination of thiamine (B1), pyridoxine (B6) and cyanocobalamin (B12) which were taken as model analytes. The separation method capitalizes on a dual isocratic elution protocol involving the use of a single forward stroke of the multisyringe pump for initial delivery of 50 mmol L−1 ammonium acetate (pH 7.0) for 2.4 min followed by 50 mmol L−1 ammonium acetate–methanol (80:20, v/v) for 6.4 min at 0.5 mL min−1 and room temperature. Detection was performed at the maximum wavelength for each target vitamin—280 nm for B1, 325 nm for B6, and 360 nm for B12. A first-order, two-level full-factorial design was utilized to ascertain the significant variables influencing the chromatographic separation and the magnitude of the interaction effects. The experimental design method revealed that resolution of the target vitamins is highly dependent on the pH, percentage of organic modifier, and their second-order interaction. The multisyringe flow-injection-based monolithic column separation method, which should be viewed as an expeditious and cost-effective alternative to the high-performance liquid chromatography counterpart, was applied to the separation and determination of B1, B6, and B12 in different pharmaceutical dosage forms in less than 9 min. Statistical comparison of the results from the proposed procedure with those from the HPLC method endorsed by the US Pharmacopeia revealed there were no significant differences at the 95 % confidence level.  相似文献   

11.
An automated solid phase extraction method by flow analysis on-line inductively coupled plasma mass spectrometry (FI-ICP-MS) for the determination of cobalt, chromium, nickel, cadmium, manganese, zinc, copper and lead in sea-water and other natural waters is described. The system is based on retention of the analytes onto a minicolumn packed with a chelating resin, 1,5-bis (2-pyridyl)-3-sulphophenyl methylene thiocarbonohydrazide immobilized on aminopropyl-controlled pore glass, placed in the injection valve of a simple flow manifold. The effects of chemical and flow variables were investigated and selected as a compromise between sensitivity and sampling frequency. So, the sample solutions (adjusted to pH 8.0 ± 0.5) were passed through the column. After washing the column with water, the adsorbed metals were subsequently eluted into the plasma with 4% m/m nitric acid. Detection limits of the trace metals (180 s sample loading time at a sample flow rate of 0.7 mL min? 1; sampling frequency 8.6 h? 1) were 0.002 μg L? 1 for Co, 0.057 μg L? 1 for Cr, 0.117 μg L? 1 for Ni, 0.004 μg L? 1 for Cd, 0.210 μg L? 1 for Mn, 0.260 μg L? 1 for Zn, 0.030 μg L? 1 for Cu and 0.020 μg L? 1 for Pb, with enrichment factors between 2.2 and 6.8. The accuracy of the proposed method was checked with certified reference materials (CRMs) of sea-water SLEW 3, LGC6016 and CASS-5, river water SLRS-5 and fortified lake water TMDA-54.4. The results from the determination of these metals were in agreement with the certified values and recovery values ranged between 92.2 and 110.6%. The method was applied to the determination of these metal ions in sea-water samples collected in the Málaga Bay in order to realize a pilot study necessary to generate preliminary information on which to base a more detailed pollution study by heavy metals of the Bay.  相似文献   

12.
Behavior of cadmium(II) in aqueous solutions irradiated by accelerated electrons was studied. A concentration of 8.8 × 10−4 mol L−1 of cadmium dissolved from Cd(NO3)2 requires dose of 15 kGy to be effectively removed from the system containing 1 × 10−2 mol L−1 of HCOOK as a scavenger of OH radicals. The positive effect of deaeration with N2O or N2 was observed in the range of lower doses. The addition of solid modifiers (bentonite, active carbon, zeolite, Cu2O, NiO, TiO2 and CuO) reduced the effectivity of radiation removal of cadmium. Product of irradiation is CdCO3. On the contrary, in the system with cadmium dissolved from CdCl2 radiation reduction takes place. Systems contained organic complexants (ethylene diamine tetraacetic acid–EDTA, citric acid) were also studied. The solutions of Cd(NO3)2 containing initial concentration 2.37 × 10−4 mol L−1 of CdII were mixed with 3 × 10−4 mol L−1 EDTA. In this system the efficient degradation proceeds up to 90% at a dose of 45 kGy with addition of 5 × 10−3 mol L−1 carbonate (pH 10.5). The product of irradiation is CdCO3. The presence of 1 × 10−2 mol L−1 of HCOOK in the solution is necessary for radiation removal of cadmium complexed with citric acid (1 × 10−3 mol L−1) at pH 8. With increasing concentration of HCOOK (up to 5 × 10−2 mol L−1) decreases the pH value necessary for the radiation induced precipitation of cadmium. The best result was obtained in the system containing zeolite as a solid modifier.  相似文献   

13.
With the objective of determining the kinetic behavior (growth, substrate, pH, and carotenoid production) and obtain the stoichiometric parameters of the fermentative process by Sporidiobolus salmonicolor in synthetic and agroindustrial media, fermentations were carried out in shaken flasks at 25°C, 180 rpm, and initial pH of 4.0 for 120 h in the dark, sampling every 6 h. The maximum concentrations of total carotenoids in synthetic (913 μg/L) and agroindustrial (502 μg/L) media were attained approximately 100 h after the start of the fermentative process. Carotenoid bioproduction is associated with cell growth and the ratio between carotenoid production and cell growth (Y P/X) is 176 and 163 μg/g in the synthetic and agroindustrial media, respectively. The pH of the agroindustrial fermentation medium varied from 4.2 to 8.5 during the fermentation. The specific growth rate (μ X) for S. salmonicolor in synthetic and agroindustrial media was 0.07 and 0.04 h−1, respectively. The synthetic medium allowed for greater productivity, obtaining maximum cell productivity (P x) of 0.08 g L−1 h−1 and maximum total carotenoid productivity (P car) of 14.2 μg L−1 h−1. Knowledge of the kinetics of a fermentative process is of extreme importance when transposing a laboratory experiment to an industrial scale, as well as making a quantitative comparison between different culture conditions.  相似文献   

14.
The preparation and electrochemical characterization of a carbon paste electrode modified with copper(II) hexacyanoferrate(III) (CuHCF) as well as its behavior as electrocatalyst toward the oxidation of N-acetylcysteine were investigated. The electrochemical behavior of the modified electrode and the electrooxidation of N-acetylcysteine were explored using sweep linear voltammetry. The best voltammetric response was observed for a paste composition of 20% (w/w) copper(II) hexacyanoferrate(III) complex, acetate buffer solution at pH of 6.0 as the electrolyte and scan rate of 10 mV s− 1. A linear voltammetric response for N-acetylcysteine was obtained in the concentration range from 1.2 × 10− 4 to 8.3 × 10− 4 mol L− 1, with a detection limit of 6.3 × 10− 5 mol L− 1. The proposed electrode is useful for the quality control and routine analysis of N-acetylcysteine in pharmaceutical formulations.  相似文献   

15.
Silica gel was chemically modified with anN-acyl-N-benzoylthiourea group. This material behaved as a selective means of preconcentrating Cu(II), Zn(II) and Cd(II) from ethanol by the column technique. Ethanolic solutions having 6 mol of the metal ions were percolated through the column and retentions of 100% were achieved for all metals. Zinc and copper were eluted quantitatively from the column bed with 5mL of ethanolic O.1molL–1 (for Zn) and 0.9 mol L–1 (for Cu) citric acid. Cadmium was recovered totally with 60 mL of ethanolic 2.0 mol L–1 citric acid. The modified silica was shown to be chemically stable after various adsorption-elution cycles (at least twenty).  相似文献   

16.
Salt-tolerant yeast Saccharomyces cerevisiae ARIF KD-003 was applied to highly sensitive and reproducible absorbance-based biochemical oxygen demand (BODAB-ScII) measurement for seawater. In the previous work, we have studied the BODAB-ScI method using normal Baker's yeast S. cerevisiae, and the excellent feature of the Baker's yeast as uniformly sustainable in solution could successfully be utilized. However, the BODAB-ScI responses were disappeared by the existence of chloride ion as well as seawater. In the present method, uniformity in solution was also observed with S. cerevisiae ARIF KD-003, and salt-tolerance of the yeast was observed even in saturate concentration of sodium chloride. Next, characterizations of the influences of pH and incubation temperature were investigated. After optimum conditions were obtained, two calibration curves were made between 0.33 and 22 mg O2 L−1 BOD using standard solution of glucose glutamic acid (GGA) or mixture of GGA and artificial seawater. Then, excellent reproducibility as the averages of relative standard deviation (R.S.D.av) in two calibration curves (nine points each) was successfully obtained at 1.10% at pure water or 1.03% at artificial seawater standard, respectively. In addition, the 3σ lower detection limit was calculated to be 0.07 mg O2 L−1 BOD, and 0.11 mg O2 L−1 BOD was experimentally detected by increase of the sample volume at 1.5-folds. The storage stability of the S. cerevisiae ARIF KD-003 was obtained at least 4 weeks.  相似文献   

17.
An on-line retention and preconcentration system based on a sheep wool-packed microcolumn combined with flame atomic absorption spectrometry is proposed for trace level determination of Cd in wine. A chelating reagent 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol was immobilized onto the wool before retention of the analyte. Several factors influencing the preconcentration efficiency of Cd and his subsequent determination, such as pH, eluent type, sample and eluent flow rates, interfering effects, were studied. A preconcentration factor of 39 was obtained with only 20 mL of sample. The relative standard deviation for five determinations of 1 μg L−1 Cd was 3.4%. The calibration graph was linear with a correlation coefficient of 0.998 at levels near the detection limit and up to at least 25 μg L−1. The limit of detection was 37 ng L−1. The accuracy of the proposed methodology was tested by comparison of the results with those obtained by electrothermal atomic absorption spectrometry analysis along with a recovery study. Finally, the method was employed for evaluating Cd levels in different wines including, blank, rose, and red.  相似文献   

18.
A simple and sensitive high‐performance liquid chromatographic procedure for the determination of the trans isomer of glimepiride is reported. Chromatography accomplished direct separation of the cis and trans isomers of glimepiride on a Dikmonsil C18 (250×4.6 mm, 5 μm) column with a mobile phase consisting of methanol‐acetonitrile‐NH4Ac buffer solution (1.5 mol L–1, pH = 4.5) (1.1 : 1.3 : 1.0, v/v) at a flow rate 0.5 mL min–1. The resolution (RS) was 1.73 with a retention time of 24.885 and 23.018 min for the cis and the trans isomer, respectively. A standard linear calibration curve was established for the trans isomer of glimepiride over the range of 4.95–198.00 μg mL–1 with a correlation coefficient of 0.99997. This method has been successfully used to analyze four different kinds of glimepiride product.  相似文献   

19.
《Analytical letters》2012,45(9):1430-1441
A new column loaded with modified silica gel-chitosan is proposed as a preconcentration system for adsorption of trace cadmium (II) and copper (II). The optimization steps were performed under dynamic conditions, involving pH, sample flow rate, eluent selection, concentration, volume, and flow rate. Trace Cd(II) and Cu(II) were quantitatively adsorbed by the modified silica gel-chitosan. The metal ions adsorbed on the separation column were eluted with 0.1 M HNO3 and determined by flame atomic absorption spectrometry. Under the optimum conditions, this method allowed the determination of cadmium and copper with limits of detection (LOD) of 20 ng L?1 and 38 ng L?1, respectively. The relative standard deviation values (RSDs) for 1.0 mg L?1 of cadmium and 1.0 mg L?1 of copper were 2.62% and 2.85%, respectively.  相似文献   

20.
This paper reports silica gel loaded with p-tert-butylcalix[8]arene as a new solid phase extractor for determination of trace level of uranium. Effective extraction conditions were optimized in column methods prior to determination by spectrophotometry using arsenazo(III). The results showed that U(VI) ions can be sorbed at pH 6 in a mini-column and quantitative recovery of U(VI) (>95–98%) was achieved by stripping 0.4 mol L−1 HCl. The sorption capacity of the functionalized sorbent is 0.072 mmol uranium(VI) g−1 modified silica gel. The relative standard deviation and detection limit were 1.2% (n = 10) for 1 μg uranium(VI) mL−1 solution and 0.038 μg L−1, respectively. The method was employed to the preconcentration of U(VI) ions from spiked ground water samples.  相似文献   

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