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1.
Hu Z  Tong C 《Analytica chimica acta》2007,587(2):187-193
The fluorescence intensity of methylene blue (MB) quenched by DNA in the pH range of 6.5-8.0 was studied with synchronous fluorescence technology. A novel method for detecting single-stranded and double-stranded DNA was developed. The decreased fluorescence intensity at 664 nm is in proportion to the concentration of DNA in the range of 0.28-11.0 μmol L−1 for ctDNA, 0.14-8.25 μmol L−1 for thermally denatured ctDNA and 0.28-8.25 μmol L−1 for hsDNA. The detection limits (S/N = 3) are 0.11, 0.04 and 0.04 μmol L−1, respectively. The method is rapid, selective, and the reagents are lower toxic. It has been used for the determination of DNA in synthetic samples with good satisfaction. In addition, the interaction modes between MB and ctDNA and the mechanism of the fluorescence quenching were also discussed in detail. The experimental results from absorption spectra and fluorescence polarization indicate that the possible interaction modes between MB and DNA are the electrostatic binding and the intercalation binding.  相似文献   

2.
A novel chemiluminescence gas-diffusion flow injection system for the determination of arsenic(III) in aqueous samples is described. The analytical procedure involves injection of arsenic(III) samples and standards into a 0.3 mol L−1 hydrochloric acid carrier stream which is merged with a reagent stream containing 0.2% (w/v) sodium borohydride and 0.015 mol L−1 sodium hydroxide. Arsine, generated in the combined carrier/reagent donor stream, diffuses across the hydrophobic Teflon membrane of the gas-diffusion cell into an argon acceptor stream and then reacts with ozone in the flow-through chemiluminescence measuring cell of the flow system. Under optimal conditions, the method is characterized by a wide linear calibration range from 0.6 μg L−1 to 25 mg L−1, a detection limit of 0.6 μg L−1 and a sample throughput of 300 samples per hour at 25 mg L−1 and 450 samples per hour at 25 μg L−1.  相似文献   

3.
Liu C  Mo YY  Chen ZG  Li X  Li OL  Zhou X 《Analytica chimica acta》2008,621(2):171-177
A new dual detection system for microchip is reported. Both fluorescence detector (FD) and contactless conductivity detector (CCD) were combined together and integrated on a microfluidic chip. They shared a common detection position and responded simultaneously. A blue light-emitting diode was used as excitation source and a small planar photodiode was used to collect the emitted fluorescence in fluorescence detection, which made the device more compact and portable. The coupling of the fluorescence and contactless conductivity modes at the same position of a single separation channel enhanced the detection characterization of sample and offered simultaneous detection information of both fluorescent and charged specimen. The detection conditions of the system were optimized. K+, Na+, fluorescein sodium, fluorescein isothiocyanate (FITC) and FITC-labeled amino acids were used to evaluate the performance of the dual detection system. The limits of detection (LOD) of FD for fluorescein Na+, FITC, FITC-labeled arginine (Arg), glycine (Gly) and phenylalanine (Phe) were 0.02 μmol L−1, 0.05 μmol L−1, 0.16 μmol L−1, 0.15 μmol L−1, 0.12 μmol L−1 respectively, and the limits of detection (LOD) of CCD achieved 0.58 μmol L−1 and 0.39 μmol L−1 for K+ and Na+ respectively.  相似文献   

4.
A new method is developed for the catalytic oxidation of ascorbic acid at graphite zeolite-modified electrode, doped with copper(II) (Cu2+A/ZCME). Copper(II) exchanged in zeolite type A acts as catalyst to oxidize ascorbic acid. The modified electrode lowered the overpotential of the reaction by ∼400 mV. First, the electrochemical behavior of copper(II), incorporated in the zeolite type A modified electrode, was studied. The results illustrate that diffusion can control the copper(II)/copper(0) redox process at the Cu2+A/ZCME. Then, the behavior of electrocatalytic oxidation reaction for ascorbic acid was researched. The electrode was employed to study electrocatalytic oxidation of ascorbic acid, using cyclic voltammetry and chronoamperometry as diagnostic techniques. The diffusion coefficient of ascorbic acid was equal to 1.028 × 10−5 cm2 s−1. A linear calibration graph was obtained over the ascorbic acid with a concentration range of 0.003-6.00 mmol L−1. The detection limit (DL) of ascorbic acid was estimated as 2.76 × 10−7 mol L−1. The relative standard deviations of 10 replicate measurements (performed on a single electrode at several ascorbic acid concentrations between 3.0 and 200 μmol L−1) were measured between 1.0 and 2.4%.  相似文献   

5.
A simple, rapid and sensitive synchronous fluorescence method is put forward for the determination of enrofloxacin (ENRO) in the pharmaceutical formulation and its residue in milk based on the yttrium (III)-perturbed luminescence. When Y3+ is added into the ENRO solution, the fluorescence of ENRO is significantly enhanced. The synchronous fluorescence technology is employed in the method to determine trace amount of ENRO residue in milks. The synchronous fluorescence intensity of the system is measured in a 1-cm quartz cell with excitation wavelength of 328 nm, Δλ = 80 nm. A good linear relationship between the fluorescence intensity and the ENRO concentration is obtained in the range of 1.0 × 10−9 to 2.0 × 10−6 mol L−1 (r2 = 0.9992). The limit of detection (LOD) of this method attains as low as 3.0 × 10−10 mol L−1 (S/N = 3). The selectivity of this method is also very good. Common metal ions, rare-earth ions and some pharmaceuticals, which are usually used together with ENRO, do not interfere with the determination of ENRO under the actual conditions. The proposed method can be applied to determine ENRO residue in milks, and limit of quantification (LOQ) determined in the spiked milk is estimated to be 2.8 × 10−8 mol L−1 (10 μg L−1). Moreover, this method can be used as a rapid screening for judging whether the ENRO residues in milks exceed Minimal Risk Levels (MRLs) or not. In addition, the mechanism of the fluorescence enhancement is also discussed in detail.  相似文献   

6.
A simple and sensitive spectrophotometric flow method for determination of low concentrations of the flotation collector O-ethyldithiocarbonate (ethyl xanthate, CH3CH2-O-CS2) in solutions is described. The method is based on ethyl xanthate detection at 301 nm in medium of NaOH 50 mmol L−1. By injection of 200 μL of sample, the analytical method shows linear response for the ethyl xanthate concentration from 0.5 up to 500 μmol L−1. Successive injections of 4 μmol L−1 ethyl xanthate (n = 23) show a coefficient of variation lower than 0.6%, denoting high repeatability. The detection limit is 0.3 μmol L−1. At a flow rate of 2.0 mL min−1, a frequency of 120 injections/h of ethyl xanthate can be attained. By introduction of a tangential dialysis cell in the FIA system, the manual sample filtration step with 0.22 μm filter was eliminated and the residual interference of suspended material, was completely overcome even for unfiltered sludge suspension samples, an important advantage that compensates for the frequency reduction to 25 injections/h elevation and detection limit elevation to 2 μmol L−1, still outreaching for many applications. Potential applications of the method embrace the at line determination of ethyl xanthate in the ore processing industry, control of the concentration at its optimal level during the flotation process, as well as monitoring of residues in the effluents.  相似文献   

7.
A compact, reliable and low cost flow injection chemiluminescence system is described. The flow system consists of a set of solenoid micro-pumps that can dispense reproductive micro-volumes of solutions. The luminometer was based on a coiled cell constructed from polyethylene tubing that was sandwiched between two large area photodiodes. The whole equipment costs about US$ 750 and weights ca. 3 kg. Equipment performance was evaluated by measuring low concentrations of hydrogen peroxide by oxidation of luminol and for the determination of ammonium, based on its inhibition of the luminescence provided by the reaction of luminol and sodium hypochlorite. Linear responses were achieved within 1.0-80 μmol L−1 H2O2 and 0.6-60 μmol L−1 NH4+ with detection limits estimated as 400 nmol L−1 H2O2 and 60 nmol L−1 NH4+ at the 99.7% confidence level. Coefficients of variation were 1.0 and 1.8%, estimated for 20 μmol L−1 H2O2 and 15 μmol L−1 NH4+ (n = 20), respectively. Reagent consumption of 55 μg luminol, effluent volume of 950 μL per determination and sampling rate of 120 samples per hour were also achieved.  相似文献   

8.
This paper proposes a new automated spectrophotometric method for the simultaneous determination of phosphate and arsenate without pre-treatment, which is faster, simpler, less expensive and hazardous than other well-known methods used with water samples. Such method is based on the different kinetic characteristics of complex formation of phosphate and arsenate with ammonium molybdate. A flow system was used in order to achieve good mixing and to provide precise time control. All the measurements were performed at the isosbestic point wavelength (885 nm). Chemical variables were optimized by factorial design (ammonium molybdate 0.015 mol L−1, potassium antimony tartrate 1 × 10−4 mol L−1, and sulphuric acid 0.7 mol L−1). An appropriate linear range for both analytes (0.50-8.00 μmol L−1), good inter-day reproducibility (4.9% [P] and 3.3% [P + As]) and a sample throughput of 6 h−1 were obtained. The detection limits are 0.4 μmol L−1 P and 0.19 μmol L−1 [P + As] (3.3 Sy/x). The method was validated.  相似文献   

9.
This work reports the preparation of a molecularly imprinted polymer (MIP) for selective catalytic detection of serotonin (5-hydroxytryptamine, 5-HT). The process is based on the synthesis of polymers with hemin introduced as the catalytic center to mimic the active site of peroxidase. The copolymer MIP, containing artificial recognition sites for 5-HT, has been prepared by bulk polymerization using methacrylic acid (MAA) and hemin as the functional monomers, and ethylene glycol dimethacrylate (EGDMA) as the cross-linker. For the determination of 5-HT, a flow injection analysis system coupled to an amperometric detector was optimized using multivariate analysis. The effects of different parameters, such as pH, buffer flow rate, buffer nature, peroxide concentration and sample volume were evaluated. After optimizing the experimental conditions, a linear response range from 1.0 up to 1000.0 μmol L−1 was obtained with a sensitivity of 0.4 nA/μmol L−1. The detection limit was found to be 0.30 μmol L−1, while the precision values (n = 6) evaluated by relative standard deviation (R.S.D.) were, respectively, 1.3 and 1.7% for solutions of 50 and 750 μmol L−1 of 5-HT. No interference was observed by structurally similar compounds (including epinephrine, dopamine and norepinephrine), thus validating the good performance of the imprinted polymer. The method was applied for the determination of 5-HT in spiked blood serum samples.  相似文献   

10.
In this work, the determination of total As in seawater by hydride generation atomic fluorescence spectrometry was studied. The influence of the chemical, flow and instrumental parameters were investigated and optimized. The pre-reduction of As(V) to As(III) was performed using KI plus ascorbic acid in 3.5 mol L− 1 HCl medium. No multiplicative interference was present and external aqueous calibration could be used. The limit of detection was 36 ng L− 1, while the repeatability was 2% (n = 10), at a 500 ng L− 1 concentration level. The sample throughput was 15 h− 1 if triplicate measurements were made. The accuracy was assessed by the analysis of a seawater certified reference material and excellent agreement between the obtained and certified values was verified. The procedure was used for the analysis of seawater offshore samples collected at the Brazilian coast and results ranging from 860 to 1200 ng L− 1 were found.  相似文献   

11.
Boron-doped diamond (BDD) films are excellent electrode materials, whose electrochemical activity for some analytes can be tuned by controlling their surface termination, most commonly either to predominantly hydrogen or oxygen. This tuning can be accomplished by e.g. suitable cathodic or anodic electrochemical pretreatments. Recently, it has been shown that amorphous carbon nitride (a-CNx) films may present electrochemical characteristics similar to those of BDD, including the influence of surface termination on their electrochemical activity toward some analytes. In this work, we report for the first time a complete electroanalytical method using an a-CNx electrode. Thus, an a-CNx film deposited on a stainless steel foil by DC magnetron sputtering is proposed as an alternative electrode for the simultaneous determination of dopamine (DA) and ascorbic acid (AA) in synthetic biological samples by square-wave voltammetry. The obtained results are compared with those attained using a BDD electrode. For both electrodes, a same anodic pretreatment in 0.1 mol L−1 KOH was necessary to attain an adequate and equivalent separation of the DA and AA oxidation potential peaks of about 330 mV. The detection limits obtained for the simultaneous determination of these analytes using the a-CNx electrode were 0.0656 μmol L−1 for DA and 1.05 μmol L−1 for AA, whereas with the BDD electrode these values were 0.283 μmol L−1 and 0.968 μmol L−1, respectively. Furthermore, the results obtained in the analysis of the analytes in synthetic biological samples were satisfactory, attesting the potential application of the a-CNx electrode in electroanalysis.  相似文献   

12.
Haghighi B  Bozorgzadeh S 《Talanta》2011,85(4):2189-2193
ZnO nanoparticles (nanoZnO) were decorated on multiwalled carbon nanotubes (MWCNTs) and then the prepared nano-hybrids, nanoZnO-MWCNTs, were immobilized on the surface of a glassy carbon electrode (GCE) to fabricate nanoZnO-MWCNTs modified GCE. The prepared electrode, GCE/nanoZnO-MWCNTs, showed excellent electrocatalytic activity towards luminol electrochemiluminescence (ECL) reaction. The electrode was then further modified with lactate oxidase and Nafion to fabricate a highly sensitive ECL lactate biosensor. Two linear dynamic ranges of 0.01-10 μmol L−1 and 10-200 μmol L−1 were obtained for lactate with the correlation coefficient better than 0.9996. The detection limit (S/N = 3) was 4 nmol L−1 lactate. The relative standard deviation for repetitive measurements (n = 6) of 10 μmol L−1 lactate was 1.5%. The fabrication reproducibility for five biosensors prepared and used in different days was 7.4%. The proposed ECL lactate biosensor was used for determination of lactate in human blood plasma samples with satisfactory results.  相似文献   

13.
Zhen Hai Li  Koji Oshita 《Talanta》2010,82(4):1225-637
Flow-injection analysis system (FIA system), which was based on Fe(II)-catalyzed oxidation of chromotropic acid with hydrogen peroxide, was developed for the determination of hydrogen peroxide. The chromotropic acid has a fluorescence measured at λem = 440 nm (emission wavelength) with λex = 235 nm (excitation wavelength), and the fluorescence intensity at λem = 440 nm quietly decreased in the presence of hydrogen peroxide and Fe(II), which was caused by Fe(II)-catalyzed oxidation of chromotropic acid with hydrogen peroxide. By measuring the difference of fluorescence intensity, hydrogen peroxide (1.0 × 10−8-1.0 × 10−3 mol L−1) could be determined by the proposed FIA system, whose analytical throughput was 40 samples h−1. The relative standard deviation (RSD) was 1.03% (n = 10) for 4.0 × 10−8 mol L−1 hydrogen peroxide. The proposed FIA technique could be applied to the determination of hydrogen peroxide in rain water samples.  相似文献   

14.
A silver hexacyanoferrate nanoparticles/carbon nanotubes modified glassy carbon electrode was fabricated and then successfully used for the simultaneous determination of ascorbic acid, dopamine and uric acid by cyclic voltammetry. A detailed investigation by transmission electron microscopy (TEM) and electrochemistry was performed in order to elucidate the preparation process and properties of the nanocomposites. The size of silver hexacyanoferrate nanoparticles was examined by TEM around 27 nm. Linear calibration plots were obtained over the range of 4.0 × 10−6-7.8 × 10−5, 2.4 × 10−6-1.3 × 10−4 and 2.0 × 10−6-1.5 × 10−4 mol L−1 with detection limits of 4.2 × 10−7,1.4 × 10−7 and 6.0 × 10−8 mol L−1 for ascorbic acid, dopamine and uric acid, respectively. The practical analytical utilities of the modified electrode were demonstrated by the determination of ascorbic acid, dopamine and uric acid in urine and human blood serum samples.  相似文献   

15.
This work reports the development of a selective, sensitive and rapid spectrofluorimetric method for the determination of reduced glutathione (GSH) in the presence of relatively high levels of cysteine (Cys) in clinical and biological samples using 1,3,5,7-tetramethyl-8-phenyl-(2-maleimide)-difluoroboradiaza-s-indacene (TMPAB-o-M). The fluorescence from TMPAB-o-M is strongly quenched by its maleimide moiety, but after reaction with thiol, the fluorescence is restored with a 350-fold intensity increase (fluorescence quantum yield from 0.002 to 0.73). In H3Cit-Na2HPO4 buffer (pH 7.40), the derivatization is completed in just 5 min under 37 °C. The linear range is 0.005-0.2 μmol L−1, with detection limit of 1.1 × 10−10 mol L−1 (signal-to-noise ratio = 3). Almost all amino acids, including Cys, impose no interference even if present at relatively high concentrations (amino acids:GSH = 100:1, Cys:GSH = 1:1, molar ratio, CGSH = 3 × 10−7 mol L−1). The sample can be used directly without further treatment after the protein is removed. The developed method is precise with a relative standard deviation (R.S.D.) lower than 5.0% (n = 6) and has been applied to the determination of GSH in human blood and pig’s liver with recoveries between 94.4 and 105.6%.  相似文献   

16.
Wei J  He JB  Cao SQ  Zhu YW  Wang Y  Hang GP 《Talanta》2010,83(1):190-196
A nonionic poly(2-amino-5-mercapto-thiadiazole) film was electrodeposited on a solid carbon paste electrode via a potential scanning procedure, and used for amperometric sensing of ascorbic acid (AA), dopamine (DA) and serotonin (ST). The highly electrocatalytic activity of the sensor to the three analytes was demonstrated from the sensitive and well separated voltammetric signals. The polymer film did not show significant accumulation effect on all the three species, reducing the fouling and deactivation of the electrode surface as well as the mutual interference among the analytes. The sensor achieved amperometric sensitivities of 1.92 nA (nmol L−1)−1 cm−2 to AA in the linear range of 0.025-1.95 μmol L−1, 3.76 nA (nmol L−1)−1 cm−2 to DA and 7.00 nA (nmol L−1)−1 cm−2 to ST both in the linear range of 0.02-1.56 μmol L−1. The lowest detection limits were found to be 1.5, 0.7 and 0.4 nmol L−1 for AA, DA and ST, respectively. This sensor was successfully employed for the successive determination of AA, DA and ST in pharmaceutical samples. The good antifouling property and reproducibility of the proposed sensor can be attributed to the nonionic polymer film without electrostatic attraction to the ionized species in the solutions.  相似文献   

17.
A flow injection analysis (FIA) method using on-line separation and preconcentration with a novel metal scavenger beads, QuadraSil™ TA, has been developed for the ICP-OES determination of traces of palladium. QuadraSil TA contains diethylenetriamine as a functional group on spherical silica beads and shows the highest selectivity for Pd(II) at pH 1 (0.1 mol l−1 hydrochloric acid) solution. An aliquot of the sample solution prepared as 0.1 mol l−1 in hydrochloric acid was passed through the QuadraSil TA column. After washing the column with the carrier solution, the Pd(II) retained on the column was eluted with 0.05 mol l−1 thiourea solution and the eluate was directly introduced into an ICP-OES. The proposed method was successfully applied to the determination of traces of palladium in JSd-2 stream sediment certified reference material [0.019 ± 0.001 μg g−1 (n = 3); provisional value: 0.0212 μg g−1] and SRM 2556 used auto catalyst certified reference material [315 ± 4 μg g−1 (n = 4); certified value: 326 μg g−1]. The detection limit (3σ) of 0.28 ng ml−1 was obtained for 5 ml of sample solution. The sample throughputs for 5 ml and 100 μl of the sample solutions were 10 and 15 h−1, respectively.  相似文献   

18.
A sensitive and robust analytical method for spectrophotometric determination of ethyl xanthate, CH3CH2OCS2 at trace concentrations in pulp solutions from froth flotation process is proposed. The analytical method is based on the decomposition of ethyl xanthate, EtX, with 2.0 mol L−1 HCl generating ethanol and carbon disulfide, CS2. A gas diffusion cell assures that only the volatile compounds diffuse through a PTFE membrane towards an acceptor stream of deionized water, thus avoiding the interferences of non-volatile compounds and suspended particles. The CS2 is selectively detected by UV absorbance at 206 nm (? = 65,000 L mol−1 cm−1). The measured absorbance is directly proportional to EtX concentration present in the sample solutions. The Beer's law is obeyed in a 1 × 10−6 to 2 × 10−4 mol L−1 concentration range of ethyl xanthate in the pulp with an excellent correlation coefficient (r = 0.999) and a detection limit of 3.1 × 10−7 mol L−1, corresponding to 38 μg L−1. At flow rates of 200 μL min−1 of the donor stream and 100 μL min−1 of the acceptor channel a sampling rate of 15 injections per hour could be achieved with RSD < 2.3% (n = 10, 300 μL injections of 1 × 10−5 mol L−1 EtX). Two practical applications demonstrate the versatility of the FIA method: (i) evaluation the free EtX concentration during a laboratory study of the EtX adsorption capacity on pulverized sulfide ore (pyrite) and (ii) monitoring of EtX at different stages (from starting load to washing effluents) of a flotation pilot plant processing a Cu-Zn sulfide ore.  相似文献   

19.
A high-pressure microwave digestion was applied for microwave-assisted extraction (MAE) of mercury species from sediments and zoobenthos samples. A mixture containing 3 mol L−1 HCl, 50% aqueous methanol and 0.2 mol L−1 citric acid (for masking co-extracted Fe3+) was selected as the most suitable extraction agent. The efficiency of proposed extraction method was better than 95% with R.S.D. below 6%. A preconcentration method utilizing a “homemade” C18 solid phase extraction (SPE) microcolumns was developed to enhance sensitivity of the mercury species determination using on-column complex formation of mercury-2-mercaptophenol complexes. Methanol was chosen for counter-current elution of the retained mercury complexes achieving a preconcentration factor as much as 1000. The preconcentration method was applied for the speciation analysis of mercury in river water samples. The high-performance liquid chromatography-cold vapour atomic fluorescence spectrometric (HPLC/CV-AFS) method was used for the speciation analysis of mercury. The complete separation of four mercury species was achieved by an isocratic elution of aqueous methanol (65%/35%) on a Zorbax SB-C18 column (4.6 mm × 150 mm, 5 μm) using the same complexation reagent (2-mercaptophenol). The limits of detection were 4.3 μg L−1 for methylmercury (MeHg+), 1.4 μg L−1 for ethylmercury (EtHg+), 0.8 μg L−1 for inorganic mercury (Hg2+), 0.8 μg L−1 for phenylmercury (PhHg+).  相似文献   

20.
Three Mn(III) porphyrins were used for the design of carbon paste and diamond paste based microelectrodes, which were employed for the determination of dopamine in pharmaceutical and biological samples using differential pulse voltammetry (DPV). The limits of detection lie between 1.6 × 10−13 and 2.0 × 10−6 mol L−1 while the sensitivities were between 230 pA μmol L−1 and 3.24 μA mol L−1. Dopamine was recovered reliable from pharmaceutical and biological samples in percentages higher than 91.00% and 92.00%, respectively. The surface of the microelectrodes can easily be renewed by simple polishing, obtaining a fresh surface ready for use in a new assay.  相似文献   

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