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1.
Safavi A  Maleki N  Shahbaazi HR 《Talanta》2006,68(4):1113-1119
A sensitive method for the determination of chromium ion(VI) in complex matrices such as crude oil and sludge is presented based on the decreasing effect of Cr(VI) on cathodic adsorptive stripping peak height of Cu-adenine complex. Under the optimum experimental conditions (pH 7.5 Britton-Robinson buffer, 5 × 10−5 M copper, 8 × 10−6 M adenine and accumulation potential −250 mV versus Ag/AgCl), a linear decrease of the peak current of Cu-adenine was observed, when the chromium(VI) concentration was increased from 5 μg L−1 to 120 μg L−1. Detection limit of 2 μg L−1 was achieved for 120 s accumulation time. The relative standard deviations (R.S.D., %) were 1.8% and 4% for chromium(VI) concentrations of 18 μg L−1 and 100 μg L−1, respectively. The method was applied to the determination of chromium(VI) in the presence of high levels of chromium(III), in various real samples such as crude oil, crude oil tank button sludge, waste water and tap water samples. Effects of foreign ions and surfactants on the voltammetric peak and the influences of instrumental and analytical parameters were investigated in detail. The accuracy of the results was checked by ICP and/or AA.  相似文献   

2.
Luminescent surface-modified CdSe semiconductor quantum dots (QDs), with nanoparticle (NP) size distribution in the order of 2-7 nm, have been synthesized for optical determination of cyanide ions. The nanoparticles have been functionalised with tert-butyl-N-(2-mercaptoethyl)-carbamate (BMC) groups and exhibit a strong fluorescent emission at about 580 nm with rather long fluorescence lifetimes (several hundred nanoseconds) in aerated methanolic solution. The observed luminescence emitted by the synthesized nanocrystals was tremendously increased by photo-activation under sunlight exposure. The functionalised QDs turned out to exhibit excellent long-term stability when stored in the dark (no significant changes in QDs luminescence emission intensity was observed even after two months from synthesis). The functionalisation of the NPs with carbamate ligand allowed a highly sensitive determination of free cyanide via analyte-induced changes in the photoluminescence (fluorescence quenching of intensity at 580 nm and lifetime changes) of the modified quantum dots (excited at 400 nm). A detection limit of 1.1 × 10−7 M (2.9 μg l−1) of cyanide ions was obtained, while the interfering effect of other inorganic anions (including NO3, Cl or SCN) was negligible even at 200-fold level concentrations in excess of cyanide.  相似文献   

3.
A chemically modified carbon paste electrode with 3,4-tetra pyridinoporphirazinatocobalt(II) (Co(3,4 tppa) was applied to the determination of free cyanide ion. The electrode has a linear range between 1.5 × 10−5 M and 1.0 × 10−2 M with a Nernstian slope of 60 ± 1.5 mV/decade and its detection limit is 9 × 10−6 M. The response time of electrode is 5 min. The proposed electrode was applied successfully for the determination of cyanide in commercially available spring water. Some anions, such as SCN, I, Cl, Br and oxalate that are usually serious interfering species for most of cyanide selective electrodes, did not have any interfering effect for this proposed electrode.  相似文献   

4.
A rapid and sensitive electrospray ionization tandem mass spectrometric (ESI-MS-MS) procedure was developed for the determination of cyanide (CN). CN in biological fluids was reacted with NaAuCl4 to produce dicyanogold, Au(CN)2, which was extracted with methyl isobutyl ketone (MIBK). One microliter of the extract was injected directly into an ESI-MS-MS instrument. Quantification of CN was performed by selected reaction monitoring of the product ion CN at m/z 26 that derived from precursor ion Au(CN)2 at m/z 249. CN could be measured in the quantification range of 10−7 to 5 × 10−5 M with the limit of detection at 4 × 10−8 M using 10 μL of urine within 10 min. A victim's urine and gastric content were diluted with water to 4-fold and 500-fold and measured, respectively.  相似文献   

5.
A simple, fast, low cost and sensitive direct β-correction spectrophotometric assay of cyanide ions based on its reaction with the reagent 4-hydroxy-3-(2-oxoindolin-3-ylideneamino)-2-thioxo-2H-1,3-thiazin-6(3H)-one, abbreviated as HOTT in aqueous media of pH 7-10 is described. The electronic spectrum of the produced brown-red colored species showed well defined and sharp peak at λmax = 466 nm. The effective molar absorptivity for the produced cyano compound was 2.5 × 104 L mol−1 cm−1. Beer's law and Ringbom's plots were obeyed in the concentration range 0.05-2.0 and 0.30-1.5 μg mL−1 cyanide ions, respectively. The proposed method offers 16.0 and 50.3 μg L−1 lower limits of detection (LOD) and quantification (LOQ) of the cyanide ion, respectively. The analytical utility of the method for the analysis of cyanide ions in tap and drinking water samples was demonstrated and the results were compared successfully with the conventional cyanide ion selective electrode. The short time response and the detection by the naked eye make the method available for the detection and quantitative determination of cyanide in a variety of samples e.g. fresh and drinking water. Moreover, the structure of the produced colored species was determined with the aid of spectroscopic measurements (UV-Vis, IR, 1H and 13C NMR) and elemental analysis.  相似文献   

6.
A new and simple flow injection system procedure has been developed for the indirect determination of cyanide. The method is based on insertion of aqueous cyanide solutions into an on-line cadmium carbonate packed column (25% m/m suspended on silica gel beads) and a sodium hydroxide with pH 10 is used as the carrier stream. The eluent containing the analyte as cadmiumcyanide complexes, produced from reaction between cadmium carbonate and cyanide, measured by flame atomic absorption spectrometry. The absorbance is proportional to the concentration of cyanide in the sample. The linear range of the system is up to 15 mg L−1 with a detection limit 0.2 mg L−1 and sampling rate 72 h−1. The method is suitable for determination of cyanide in industrial waste waters with a relative standard deviation better than 1.22%.  相似文献   

7.
Jun Kato  Michihito Chiba 《Talanta》2009,79(4):1154-1160
Trace amounts of l-cysteine can function as a trigger, i.e., reaction initiator, in the autocatalytic sodium sulfite/hydrogen peroxide reaction system. Rapidly changing of pH after induction time is visually confirmed by color changing of bromothymol blue in this autocatalytic reaction. Based on this finding, μg L−1 levels of l-cysteine were measured over time using the autocatalytic reaction system. The determination range using the above method was 5.0 × 10−8-2.5 × 10−6 M, the detection limit (3σ) was 1.8 × 10−8 M (1.94 μg L−1), and the relative standard deviation was 2.41% at an l-cysteine concentration of 5 × 10−7 M (n = 5). This method was also applied to length detection-flow injection analysis. The determination range for the flow injection analysis was 2.0 × 10−7-1.0 × 10−5 M. The detection limit (3σ) was 1.4 × 10−7 M (17.0 μg L−1), and the relative standard deviation was 0.91% at an initial l-cysteine concentration of 10−6 M (n = 5).  相似文献   

8.
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   

9.
Uranium (VI) (U(VI)) forms a complex with dipicolinic acid (2, 6-pyridinedicarboxylic acid).This complex can be used for a highly sensitive and selective determination of uranium by adsorptive cathodic stripping voltammetry (ACSV) using a hanging mercury drop electrode (HMDE) as working electrode. Influence of effective parameters such as pH, concentration of ligand, accumulation potential and accumulation time on the sensitivity and selectivity were studied. The detection limit (3σ of the blank value) obtained under the optimal experimental conditions is 0.27 × 10−9 M after 150 s of the accumulation time. The peak current is proportional to the concentration of U(VI) in the range of 1 × 10−9 to 1.2 × 10−7 M. The relative standard deviation of 2.5% at the 3.5 × 10−8 M level was obtained. The interference of some metal ions and anions were studied. The application of this method was tested in the determination of uranium in synthetic and natural water samples.  相似文献   

10.
Li J  Yu J  Zhao F  Zeng B 《Analytica chimica acta》2007,587(1):33-40
The direct electrochemistry of glucose oxidase (GOD) entrapped in nano gold particles (NAs)-N,N-dimethylformamide (DMF)-1-butyl-3-methylimidazolium hexafluophosphate (BMIMPF6) composite film on a glassy carbon electrode (NAs-DMF-GOD (BMIMPF6)/GC) has been investigated for first time. The immobilized GOD exhibits a pair of well-defined reversible peaks in 0.050 M pH 5 phosphate solutions (PS), resulting from the redox of flavin adenine dinucleotide (FAD) in GOD. The peak currents are three times as large as those of GOD-NAs-DMF film coated GC electrode (i.e. NAs-DMF-GOD (water)/GC). In addition, the NAs-DMF-GOD (BMIMPF6) composite material has higher thermal stability than NAs-DMF-GOD (water). Results show that ionic liquid BMIMPF6, DMF and NAs are requisite for GOD to exhibit a pair of stable and reversible peaks. Without any of them, the peaks of GOD become small and unstable. Upon the addition of glucose, the peak currents of GOD decrease and a new cathodic peak occurs at −0.8 V (versus SCE), which corresponds to the reduction of hydrogen peroxide (H2O2) generated by the catalytic oxidation of glucose. The peak current of the new cathodic peak and the glucose concentration show a linear relationship in the ranges of 1.0 × 10−7 to 1.0 × 10−6 M and 2.0 × 10−6 to 2.0 × 10−5 M. The kinetic parameter Imax of H2O2 is estimated to be 1.19 × 10−6 A and the apparent Km (Michaelis-Menten constant) for the enzymatic reaction is 3.49 μM. This method has been successfully applied to the determination of glucose in human plasma and beer samples, and the average recoveries are 97.2% and 99%, respectively.  相似文献   

11.
J. Ballesta Claver 《Talanta》2009,79(2):499-506
This paper presents an application of chromatographic separation based on an ultra-short monolithic column and chemiluminescent detection in an FIA type instrument manifold for the determination of four paraben mixtures: methylparaben (MP), ethylparaben (EP), propylparaben (PP) and butylparaben (BP). The separation is achieved in 150 s using two consecutive carriers: first 12% ACN:water that changes 75 s after injection to 27% ACN:water. The detection is based on the oxidation of the hydrolysis product of parabens, p-hydroxybenzoic acid, with Ce(IV) in the presence of Rhodamine 6G which evokes chemiluminescence of sufficient intensity to enable a sensitive determination of these species. After optimization of the variables involved, the analytical method is characterized, displaying the following values for concentration ranges, detection limits and precision, as relative standard deviation at low concentration (0.15 mg l−1)—MP: from 9.9 × 10−7 to 3.3 × 10−4 M; 1.9 × 10−8; 5.6%; EP: from 9.0 × 10−7 to 3.3 × 10−4 M; 2.8 × 10−8; 3.5%; PP: from 8.3 × 10−7 to 9.9 × 10−5 M; 2.3 × 10−8; 4.2%; and BP: from 7.7 × 10−7 to 9.9 × 10−5 M; 4.2 × 10−8 M; 6.2%. The method was applied and validated satisfactorily for the determination of these parabens in cosmetic samples, comparing the results against a liquid chromatography reference method.  相似文献   

12.
Shervedani RK  Babadi MK 《Talanta》2006,69(3):741-746
Fabrication and application of a voltammetric sensor based on gold 2-mercaptobenzothiazole self-assembled monolayer (Au-MBT SAM) for determination of silver ion is described. Preliminary experiments were performed to characterize the monolayer. The surface pKa determined for the MBT monolayer is 7.0. This value was obtained by impedimetric titration of the monolayer in the presence of Fe(CN)63−/4− as a redox probe. The extent of surface coverage was evaluated as 1.52 × 10−9 mol cm−2 based on charged consumed for reductive desorption of the monolayer in the 0.50 M NaOH solution. Then the sensor was used for determination of Ag(I) by square wave voltammetry. The parameters affecting the sensor response, such as pH and supporting electrolyte, were optimized. A dynamic calibration curve with two linear parts was obtained in the concentration ranges of 5 × 10−8-8 × 10−7 and 1 × 10−6-1 × 10−5 M of Ag(I). The detection limit adopted from cathodic striping square wave voltammetry was as 1 × 10−8 M for n = 7. Furthermore, the effect of potential interfering ions on the determination of Ag(I) was studied, and an appropriate method was used for the elimination of this effect.  相似文献   

13.
In this work, a highly selective and sensitive monohydrogen phosphate membrane sensor based on a molybdenum bis(2-hydroxyanil) acetylacetonate complex (MAA) is reported. The sensor shows a linear dynamic range between 1.0 × 10−1 and 1.0 × 10−7 M, with a nice Nernstian behavior (−29.5 ± 0.3 mV decade−1) in pH of 8.2. The detection limit of the electrode is 6.0 × 10−8 M (∼6 ppb). The best performance was obtained with a membrane composition of 32% poly(vinyl chloride), 58% benzyl acetate, 2% hexadecyltrimethylammonium bromide and 8% MAA. The sensor possesses the advantages of short response time, low detection limit and especially, very good selectivity towards a large number of organic and inorganic anions including salicylate, citrate, tartarate, acetate, oxalate, fluoride, chloride, bromide, iodide, sulfite, sulfate, nitrate, nitrite, cyanide, thiocyanate, perchlorate, metavanadate, and bicarbonate ions. The electrode can be used for at least 10 weeks without any considerable divergence in its slope and detection limit. It was used as an indicator electrode in potentiometric titration of monohydrogenphosphate ion with barium chloride. The proposed sensor was successfully applied to direct determination of monohydrogenphosphate in two fertilizer samples (NPK).  相似文献   

14.
During the reversible reaction between peroxidase (HRP) and peroxides, several peroxidase intermediate species, showing different molecular absorption spectra, are formed which can be used for their determination. On this basis, a reversible reagentless optical biosensor based on HRP for hydrogen peroxide and peracetic acid determinations has been developed. The biosensor (which can be used for at least 3 months and/or more than 200 measurements) is prepared by HRP entrapment in a polyacrylamide gel matrix. A mathematical model (in which optical, kinetic and transport aspects are considered) relating the measured absorbance with the analyte concentration is also presented. Both peroxides show similar responses in the sensor film. Under the recommended working conditions, the biosensor shows linear response ranges from 6 × 10−7 to 1.0 × 10−4 M using FIA mode, and from 2 × 10−7 to 1.5 × 10−5 M using continuous mode for both peroxides; the precision, expressed as R.S.D., is about 4%. This biosensor has been applied for peroxide determination in waste water samples previously treated with peroxides.  相似文献   

15.
A highly sensitive microchip electrophoresis (MCE) method with chemiluminescence (CL) detection was developed for the determination of biogenic amines including agmatine (Agm), epinephrine (E), dopamine (DA), tyramine, and histamine in human urine samples. To achieve a high assay sensitivity, the targeted analytes were pre-column labeled by a CL tagging reagent, N-(4-aminobutyl)-N-ethylisoluminol (ABEI). ABEI-tagged biogenic amines after MCE separation reacted with hydrogen peroxide in the presence of horseradish peroxidase (HRP), producing CL emission. Since no CL reagent was added to the running buffer, the background of the CL detection was extremely low, resulting in a significant improvement in detection sensitivity. Detection limits (S/N = 3) were in the range from 5.9 × 10−8 to 7.7 × 10−8 M for the biogenic amines tested, which were at least 10 times lower than those of the MCE–CL methods previously reported. Separation of a urine sample on a 7 cm glass/poly(dimethylsiloxane) (PDMS) microchip channel was completed within 3 min. Analysis of human urine samples found that the levels of Agm, E and DA were in the ranges of 2.61 × 10−7 to 4.30 × 10−7 M, 0.81 × 10−7 to 1.12 × 10−7 M, and 8.76 × 10−7 to 11.21 × 10−7 M (n = 4), respectively.  相似文献   

16.
Sulphur containing compounds such as sodium thiosulphate (STS) and thioglycolic acid (TGA) inhibit the rate of cyanide substitution by nitroso-R-salt (NRS) in hexacyanoruthenate(II) catalysed by Hg(II) ions due to their strong binding tendencies with Hg(II) catalyst. This inhibitory effect of sodium thiosulphate and thioglycolic acid is used as the basis for their determination at micro levels. The reaction was followed spectrophotometrically at 525 nm (λmax of [Ru(CN)5NRS]3− complex) under optimised reaction conditions at 8.75 × 10− 5 M [Ru(CN)64−], 3.50 × 10− 4 M [NRS], pH 7.00 ± 0.02, ionic strength (µ) 0.1 M (KCl) and temp 45.0 ±0.1 °C. The modified mechanistic scheme is proposed to understand the inhibition caused by sulphur containing compounds (STS and TGA) on Hg(II) catalysed substitution of cyanide by NRS in [Ru(CN)6]4−. The range of analytical concentration of inhibitor depends upon two factors; the amount of Hg(II) catalyst present in the indicator reaction and the stability of the Hg(II)-inhibitor complex under consideration. Under optimum conditions STS and TGA have been determined in the range of 0.98-7.0 × 10− 6 M and 0.30-7.0 × 10− 6 M. The detection limits for STS and TGA were found to be 3.0 × 10− 7 M and 1.0 × 10− 7 M respectively.  相似文献   

17.
《Analytica chimica acta》2003,491(1):27-35
The determination of cyanide ions in water samples by room temperature phosphorescence (RTP) detection is described. The method is based on the measurement of the RTP emission of α-bromonaphthalene (BrN). The principle of the RTP cyanide determination involves the energy transfer (ET) from the BrN phosphor molecule insensitive to the presence of cyanide (acting as a donor) to a cyanide-sensitive dye (acceptor).The RTP emission spectrum of BrN overlaps significantly with the absorption spectrum of the complex formed between copper and Cadion 2B, giving rise to a non-radiative ET from the phosphor molecules to the metal complex. The sensing of cyanide ions is based on the displacement by cyanide of the copper ions from its complex with Cadion 2B (the free chelating molecule presents a low absorbance in the region of maximum emission of the BrN phosphor). An increase in the concentration of cyanide causes a decrease on the concentration of the Cadion 2B-copper complex (acceptor) with the subsequent decrease of the absorbance in the overlapping region with the RTP spectra, resulting in higher RTP emission signals measured. Both, RTP intensities and triplet lifetimes of the BrN increased with the increase of the cyanide concentration.The calibration graphs were linear up to a concentration of 500 mg l−1 cyanide and a precision of ±2 and ±0.5% for five replicates of 50 μg l−1 of cyanide has been obtained when measuring intensities and triplet lifetimes values, respectively. A detection limit of 3 μg l−1 of cyanide was achieved under optimal reaction conditions and pH 11. The use of phosphorescence measurements (low background noise signals) resulted in an important improvement on the sensitivity of the cyanide detection higher than eight times as compared to the molecular absorption spectrophotometric method for cyanide detection based on the use of Cadion 2B-copper as cyanide-indicator.Interference studies were performed with cations and anions present in drinking water samples which could affect the analytical response. Finally, the method has been successfully applied to the determination of trace levels of labile cyanide in spiked drinking water samples.  相似文献   

18.
Titanium phosphate grafted on the surface of silica gel (devoted briefly as Si-TiPH) was synthesized and used as bulk modifier to fabricate a renewable three-dimensional chemically modified electrode. The Si-TiPH bulk modified carbon paste electrode was used for the selective determination of dopamine (DA) in the presence of ascorbic acid (AA). The modified electrode offers an excellent and stable response for the determination of DA in the presence of AA. The differential pulse voltammetry peak current was found to be linear with the DA concentration in the range 2 × 10−7 to 1 × 10−6 and 2 × 10−6 to 6 × 10−5 mol L−1. The detection limit of the proposed method in the presence of 2.0 × 10−5 M of AA was found to be 4.3 × 10−8 mol L−1 for DA determination. The proposed method was successfully applied for the determination of DA in injections.  相似文献   

19.
Cu2+-mediated salbutamol-imprinted polymer nanoparticles, synthesized by precipitation polymerization, were mixed with graphite powder and n-eicosane in order to fabricate a modified carbon paste electrode. This electrode was then applied for indirect differential pulse voltammetry determination of salbutamol. In the presence of Cu2+ ions, the formed Cu2+–salbutamol complex was adsorbed in to the pre-designed cavities of the MIP particles, situated on the electrode surface. Since the electrochemical signal of salbutamol was intrinsically small, the oxidation peak of the participant Cu2+, after reduction step, was recorded and used as an indication of salbutamol amount, adsorbed in the electrode. Different variables influencing the sensor performance were studied and the best conditions were chosen for the determination purpose. Correlation between the sensor response to salbutamol and its concentration was linear in the range of 1.0 × 10−9–5.5 × 10−8 M. Detection limit was calculated equal to 6.0 × 10−10 M (S/N). Five replicated determination of salbutamol (1 × 10−8 M) resulted in standard error of 3.28%, meaning a satisfactory precision of the determination method. The prepared sensor was applied for real sample analysis. In order to minimize the interference effect, the synthesized polymer was successfully used as a solid phase sorbent for salbutamol extraction, before analysis of real samples by the developed sensor.  相似文献   

20.
Somer G  Yılmaz UT 《Talanta》2005,65(2):598-602
When selenite was added into solutions of some ions such as copper, lead, cadmium, zinc, chromium and arsenic their DPP peak decreased. This kind of interference was observed in all acids and in wide range of pH values, causing at least 50% error when both ions (the ion present and selenite) were in similar quantities. It was found that this interference was not taking place at pH 8.5 in the presence of large amounts of selenite. A synthetic sample containing these elements in 10−5 M in the presence of 50 times selenite has been analyzed at pH 8.5 without any interference. The detection limit in this medium was 3 × 10−7 M for cadmium and lead, 1 × 10−6 M for copper and zinc and it was 3 × 10−7 M for selenite.  相似文献   

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