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1.
CeO2 nanoparticles approximately 12 nm in size were synthesized and subsequently characterized by XRD, TEM and UV-vis spectroscopy. Then, a gold electrode modified with CeO2 nanoparticles was constructed and characterized by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The modified electrode demonstrated strong catalytic effects with high stability towards electrochemical oxidation of rutin. The anodic peak currents (measured by differential pulse voltammetry) increased linearly with the concentration of rutin in the range of 5.0 × 10−7–5.0 × 10−4 mol · L−1. The detection limit (S/N = 3) was 2.0 × 10−7 mol · L−1. The relative standard deviation (RSD) of 8 successive scans was 3.7% for 5.0 × 10−6 mol · L−1 rutin. The method showed excellent sensitivity and stability, and the determination of rutin in tablets was satisfactory.  相似文献   

2.
The Fe3O4-Prussian blue (PB) nanoparticles with core-shell structure have been in situ prepared directly on a nano-Fe3O4-modified glassy carbon electrode by cyclic voltammetry (CV). First, the magnetic nano-Fe3O4 particles were synthesized and characterized by X-ray diffraction. Then, the properties of the Fe3O4-PB nanoparticles were characterized by CV, electrochemical impedance spectroscopy, and superconducting quantum interference device. The resulting core-shell Fe3O4-PB-modified electrode displays a dramatic electrocatalytic ability toward H2O2 reduction, and the catalytic current was a linear function with the concentration of H2O2 in the range of 1 × 10−7~5 × 10−4 mol/l. A detection limit of 2 × 10−8 (s/n = 3) was determined. Moreover, it showed good reproducibility, enhanced long-term stability, and potential applications in fields of magnetite biosensors.  相似文献   

3.
Sensitive fluorescent probes for the determination of hydrogen peroxide and glucose were developed by immobilizing enzyme horseradish peroxidase (HRP) on Fe3O4/SiO2 magnetic core–shell nanoparticles in the presence of glutaraldehyde. Besides its excellent catalytic activity, the immobilized enzyme could be easily and completely recovered by a magnetic separation, and the recovered HRP-immobilized Fe3O4/SiO2 nanoparticles were able to be used repeatedly as catalysts without deactivation. The HRP-immobilized nanoparticles were able to activate hydrogen peroxide (H2O2), which oxidized non-fluorescent 3-(4-hydroxyphenyl)propionic acid to a fluorescent product with an emission maximum at 409 nm. Under optimized conditions, a linear calibration curve was obtained over the H2O2 concentrations ranging from 5.0 × 10−9 to 1.0 × 10−5 mol L−1, with a detection limit of 2.1 × 10−9 mol L−1. By simultaneously using glucose oxidase and HRP-immobilized Fe3O4/SiO2 nanoparticles, a sensitive and selective analytical method for the glucose detection was established. The fluorescence intensity of the product responded well linearly to glucose concentration in the range from 5.0 × 10−8 to 5.0 × 10−5 mol L−1 with a detection limit of 1.8 × 10−8 mol L−1. The proposed method was successfully applied for the determination of glucose in human serum sample.  相似文献   

4.
A simple, rapid and specific chemiluminescence (CL) method for the determination of glutathione has been developed. The method is based on the enhanced CL of the reaction between Ru(phen)3 2+ (phen = 1,10-phenanthroline) and KMnO4 by glutathione in HCl medium. Under the optimum conditions, the response is linearly proportional to the concentration of glutathione between 1.5 × 10−7 and 1.0 × 10−5 mol L−1. The dection limit for glutathione (5.8 × 10−8 mol L−1) is about 10 and 200 times better than those of the spectrophotometric method using Ellman regent and the Lucigenin – CL method, respectively. The final procedure allows the determination of glutathione in human serum with recoveries of 92%–108%. A satisfactory agreement was obtained with a mean relative difference of 2.5% compared to the HPLC method.  相似文献   

5.
In the presence of carbonate and uranine, the chemiluminescent intensity from the reaction of luminol with hydrogen peroxide was dramatically enhanced in a basic medium. Based on this fact and coupled with the technique of flow-injection analysis, a highly sensitive method was developed for the determination of carbonate with a wide linear range. The method provided the determination of carbonate with a wide linear range of 1.0 × 10−10–5.0 × 10−6 mol L−1 and a low detection limit (S/N = 3) of carbonate of 1.2 × 10−11 mol L−1. The average relative standard deviation for 1.0 × 10−9–9.0 × 10−7 mol L−1 of carbonate was 3.7% (n = 11). Combined with the wet oxidation of potassium persulfate, the method was applied to the simultaneous determination of total inorganic carbon (TIC) and total organic carbon (TOC) in water. The linear ranges for TIC and TOC were 1.2 × 10−6–6.0 × 10−2 mg L−1 and 0.08–30 mg L−1 carbon, respectively. Recoveries of 97.4–106.4% for TIC and 96.0–98.5% for TOC were obtained by adding 5 or 50 mg L−1 of carbon to the water samples. The relative standard deviations (RSDs) were 2.6–4.8% for TIC and 4.6–6.6% for TOC (n = 5). The mechanism of the chemiluminescent reaction was also explored and a reasonable explanation about chemical energy transfer from luminol to uranine was proposed. Figure Chemiluminescence profiles in batch system. 1, Injection of 100 μL of K2CO3 into 1.0 mL luminol-1.0 mL H2O2 solution; 2-3 and 4-5, Injection in sequence of 100 μL of K2CO3 and 100 μL of uranine into 1.0 ml luminol-1.0 mL H2O2 solution; Cluminol = 1.0 × 10−7 mol/L, CH2O2 = 1.0 × 10−5 mol/L, Curanine = 1.0 × 10−5 mol/L, CK2CO3 = 1.0 × 10−7 mol/L except for 4-5 where CK2CO3 = 1.0 × 10−4 mol/L  相似文献   

6.
Hydrogenation of nitrate (NO3 ) in water was studied with 0.8 ×10−3–3.2 ×10−3 mol/dm3 of reactant in the temperature range of 293–313 K over palladium promoted Ag catalysts. Pd-Ag catalysts with a low ratio of Ag/Pd were characterized by high efficiency in the reduction of nitrates. The degradation of nitrates followed approximately first order decay and the estimated apparent activation energy was about 4 kJ/mol.  相似文献   

7.
A kind of erbium hexacyanoferrate (ErHCF)-modified carbon ceramic electrodes (CCEs) fabricated by mechanically attaching ErHCF samples to the surface of CCEs derived from sol–gel technique was proposed. The resulting modified electrodes exhibit well-defined redox responses with the formal potential of +0.215 V [vs saturated calomel electrode (SCE)] at a scan rate of 20 mV s−1 in 0.5 M KCl (pH 7) solution. The voltammetric characteristics of the ErHCF-modified CCEs were investigated by voltammetry. Attractively, the ErHCF-modified CCEs presented good electrocatalytic activity with a marked decrease in the overvoltage about 400 mV for l-cysteine oxidation. The calibration plot for l-cysteine determination was linear at 5.0 × 10−6–1.3 × 10−4 M with a linear regression equation of I(A) = 0.558 + 0.148c (μM) (R 2 = 0.9989, n = 20), and the detection limit was 2 × 10−6 M (S/N = 3). At last, the ErHCF-modified CCEs were used for amperometric detection of l-cysteine in real samples.  相似文献   

8.
A highly sensitive high-performance liquid chromatographic method with fluorescence detection has been developed for determination of vitamin B1. Vitamin B1 was converted into a fluorescent compound by treatment with hydrogen peroxide–horseradish peroxidase and the derivative was subsequently analyzed by HPLC on a Waters Spherisorb ODS2 column (250 mm×4.6 mm ID, 5 μm) with 40:60 methanol–pH 8.5 acetate buffer solution as mobile phase and fluorescence detection at 440 nm (with excitation at 375 nm). The calibration graph was linear from 5.00×10−10 mol L−1 to 5.00×10−7 mol L−1 for vitamin B1 with a correlation coefficient of 0.9991 (n=9). The detection limit was 1.0×10−10 mol L−1. The method was successfully used for determination of vitamin B1 at pg mL−1 levels in microalgal fermentation media and seawater after solid-phase extraction. Recovery was from 89 to 110% and the relative standard deviation was in the range 1.1 to 4.3%.  相似文献   

9.
The electrochemical behaviors of metol on an ionic liquid N-butylpyridinium hexafluorophosphate modified carbon paste electrode (IL-CPE) were studied in this paper. The results indicated that a pair of well-defined quasi-reversible redox peaks of metol appeared with the decrease of overpotential and the increase of redox peak current, which was the characteristics of electrocatalytic oxidation. The electrocatalytic mechanism was discussed and the electrochemical parameters were calculated with results of the charge-transfer coefficient (α) as 0.45, the electrode reaction rate constant (k s) as 4.02 × 10−3 s−1, and the diffusion coefficient (D) as 6.35 × 10−5 cm2/s. Under the optimal conditions, the anodic peak current was linear with the metol concentration in the range of 5.0 × 10−6 ∼ 1.0 × 10−3 mol/L (n = 11, γ = 0.994) and the detection limit was estimated as 2.33 × 10−6 mol/L (3σ). The proposed method was successfully applied to determination of metol content in synthetic samples and photographic solutions.  相似文献   

10.
Aqueous solution of water soluble colloidal MnO2 was prepared by Perez-Benito method. Kinetics of l-methionine oxidation by colloidal MnO2 in perchloric acid (0.93 × 10−4 to 3.72 × 10−4 mol dm−3) has been studied spectrophotometrically. The reaction follows first-order kinetics with respect to [H+]. The first-order kinetics with respect to l-methionine at low concentration shifts to zero order at higher concentration. The effects of [Mn(II)] and [F] on the reaction rate were also determined. Manganese (II) has sigmoidal effect on the rate reaction and act as auto catalyst. The exact dependence on [Mn(II)] cannot be explained due to its oxidation by colloidal MnO2. Methionine sulfoxide was formed as the oxidation product of l-methionine. Ammonia and carbon dioxide have not been identified as the reaction products. The mechanism with the observed kinetics has been proposed and discussed.  相似文献   

11.
A new electrochemical biosensor for determination of hydrogen peroxide (H2O2) has been developed by immobilizing horseradish peroxidase (HRP) on silver colloids (nanosilver) and use of a DNA-functionalized interface. In the presence of the DNA and the nanosilver the immobilized HRP gives a pair of well-defined redox peaks with an electron-transfer rate constant of 3.27 ± 0.91 s−1 in pH 7.0 PBS. The presence of DNA also provides a biocompatible microenvironment for enzyme molecules, greatly amplifies the amount of HRP molecules immobilized on the electrode surface, and improves the sensitivity of the biosensor. Under optimum conditions the biosensor has electrocatalytic activity in the reduction of hydrogen peroxide with linear dependence on H2O2 concentration in the range 1.5 × 10−6 to 2.0 × 10−3 mol L−1; the detection limit is 5.0 × 10−7 mol L−1 at a signal-to-noise ratio of 3. The value of HRP in the composite membrane was found to be 1.62 mmol L−1. These results suggest that the properties of the complex film, with its bioelectrochemical catalytic activity, could make it useful for development of bioelectronic devices and for investigation of protein electrochemistry at functional interfaces.  相似文献   

12.
A mesoporous SiO2-modified carbon paste electrode for the determination of uric acid is described. Owing to the regular and specific mesoporous channels, numerous active sites and a large surface area, the mesoporous SiO2-modified electrode greatly increases the oxidation peak current of uric acid. Based on this, a highly sensitive, rapid and convenient electrochemical method was developed for the determination of uric acid after optimizing the experimental parameters (supporting electrolyte, content of mesoporous SiO2, accumulation potential and time). The linear range is from 2.5 × 10−7 to 2.0 × 10−5 mol L−1, and the limit of detection is estimated to be 8.0 × 10−8 mol L−1. The relative standard deviation for 10 mesoporous SiO2-modified electrodes is 5.8%. The method was used to determine uric acid in human serum samples. Correspondence: Kangbing Wu, Department of Chemistry, Huazhong University of Science and Technology, Wuhan 430074, P.R. China  相似文献   

13.
 An electrochemical study of the doxazosin oxidative process at carbon paste electrodes using different voltammetric techniques has been carried out. The process is irreversible and controlled by adsorption, giving rise to an oxidation wave around 1.0 V in citric acid-citrate buffer (pH 3.0). A mechanism based on the oxidation of the amine group is postulated. Two methods based on adsorptive stripping (AdS) of doxazosin at the C8-modified carbon paste electrode (C8-MCPE), before its voltammetric determination, are studied, using differential pulse voltammetry (DPV) and square wave voltammetry (SWV) as redissolution techniques. By means of AdS-DPV and C8-MCPE, doxazosin can be determined over the 1.0 × 10−9 to 3.0 × 10−8 mol L−1 range with a variation coefficient of 2.2% (2.0 × 10−8 mol L−1) and a limit of detection of 7.4 ×10−10 mol L−1. If AdS-SWV is used, a linear range from 1.0 × 10−9 to 4.0 × 10−8 mol L−1 is obtained, the variation coefficient being 2.8% (2.0 × 10−8 mol L−1, and the limit of detection reached 7.7 × 10−10 mol L−1. The AdS-DPV procedure was applied to the determination of doxazosin in urine and formulations. Received March 13, 1999. Revision December 23, 1999.  相似文献   

14.
No thermodynamic data for Th complexes with aqueous Si are available. To obtain such data, extensive studies on ThO2(am) solubility were carried out as functions of: (1) a wide range of aqueous silica concentrations (0.0004 to 0.14 mol⋅L−1) at fixed pH values of about 10, 11, 12, and 13; and (2) and variable pH (ranging from 10 to 13.3) at fixed aqueous Si concentrations of about 0.006 mol⋅L−1 or 0.018 mol⋅L−1. The samples were equilibrated over long periods (ranging up to 487 days), and the data showed that steady-state concentrations were reached in < 29 days. X-ray diffraction, FTIR, and Raman analyses of the equilibrated solid phases showed that the Th solids were amorphous ThO2(am) containing some adsorbed Si. The solubility of ThO2(am) at pH values ranging from 10 to 13.3 at fixed 0.018 mol⋅L−1 aqueous Si concentrations decreases rapidly with an increase in pH, and increases dramatically with an increase in Si concentrations beyond about 0.003 mol⋅L−1 at fixed pH values > 10. The data were interpreted using both the Pitzer and SIT models, and required only the inclusion of one mixed-hydroxy-silica complex of Th [Th(OH)3(H3SiO4)32−]. Both models provided similar complexation constant values for the formation of this species. Density functional theory calculations predict complexes of this stoichiometry, having six-fold coordination of the Th cation, to be structurally stable. Predictions based on the fitted value of log 10 K 0=−18.5±0.7 for the ThO2(am) solubility reaction involving Th(OH)3(H3SiO4)32−[ThO2(am)+3H4SiO4+H2OTh(OH)3(H3SiO4)32−+2H+], along with the thermodynamic data for aqueous Si species reported in the literature, agreed closely with the extensive experimental data and showed that under alkaline conditions aqueous Si makes very strong complexes with Th.  相似文献   

15.
This paper described the determination of p-nitroaniline in a double organic substrate oscillating system of tartrate-acetone-Mn2+-KBrO3-H2SO4. Under the optimum conditions, temperature was chosen as a control parameter to design the bifurcation point and proposed a convenient method for determination of p-nitroaniline. Results showed that the system consisting of 3.5 mL 0.06 mol L−1 tartrate, 4.0 mL 0.7 mol L−1 H2SO4, 1.5 mL 1.5×10−4 mol L−1 MnSO4, 4.0 mL 0.4 mol L−1 acetone and 7.0 mL 0.05 mol L−1 KBrO3 was very sensitive to the surrounding at 33.5°C. A good linear relationship between the potential difference and the negative logarithm concentration of p-nitroaniline was obtained to be in the range of 2.50×10−7∼3.75×10−5 mol L−1 with a lower detection limit of 2.50×10−8 mol L−1.   相似文献   

16.
Synthesis, characterization and thermal analysis of polyaniline (PANI)/ZrO2 composite and PANI was reported in our early work. In this present, the kinetic analysis of decomposition process for these two materials was performed under non-isothermal conditions. The activation energies were calculated through Friedman and Ozawa-Flynn-Wall methods, and the possible kinetic model functions have been estimated through the multiple linear regression method. The results show that the kinetic models for the decomposition process of PANI/ZrO2 composite and PANI are all D3, and the corresponding function is ƒ(α)=1.5(1−α)2/3[1−(1-α)1/3]−1. The correlated kinetic parameters are E a=112.7±9.2 kJ mol−1, lnA=13.9 and E a=81.8±5.6 kJ mol−1, lnA=8.8 for PANI/ZrO2 composite and PANI, respectively.  相似文献   

17.
In this paper, a rapid, simple, and sensitive method was described for detection of the total bacterial count using SiO2-coated CdSe/ZnS quantum dots (QDs) as a fluorescence marker that covalently coupled with bacteria using glutaraldehyde as the crosslinker. Highly luminescent CdSe/ZnS were prepared by applying cadmium oxide and zinc stearate as precursors instead of pyrophoric organometallic precursors. A reverse-microemulsion technique was used to synthesize CdSe/ZnS/SiO2 composite nanoparticles with a SiO2 surface coating. Our results showed that CdSe/ZnS/SiO2 composite nanoparticles prepared with this method possessed highly luminescent, biologically functional, and monodispersive characteristics, and could successfully be covalently conjugated with the bacteria. As a demonstration, it was found that the method had higher sensitivity and could count bacteria in 3 × 102 CFU/mL, lower than the conventional plate counting and organic dye-based method. A linear relationship of the fluorescence peak intensity (Y) and the total bacterial count (X) was established in the range of 3 × 102–107 CFU/mL using the equation Y = 374.82X − 938.27 (R = 0.99574). The results of the determination for the total count of bacteria in seven real samples were identical with the conventional plate count method, and the standard deviation was satisfactory.  相似文献   

18.
The electrode characteristics and selectivities of PVC-based thiocyanate selective polymeric membrane electrode (PME) incorporating the newly synthesized zinc complex of 6,7:14,15-Bzo2-10,11-(4-methylbenzene)-[15]-6,8,12,14-tetraene-9,12-N2-1,5-O2 (I 1 ) and zinc complex of 6,7:14,15-Bzo2-10,11-(4-methylbenzene)-[15]-6,14-diene-9,12-dimethylacrylate-9,12-N2-1,5-O2 (I 2 ) are reported here. The best response was observed with the membrane having a composition of I2:PVC:o-NPOE:HTAB in the ratio of 6:33:59:2 (w/w; milligram). This electrode exhibited Nernstian slope for thiocyanate ions over working concentration range of 4.4 × 10−7 to 1.0 × 10−2 mol L−1 with detection limit of 2.2 × 10−7 mol L−1. The performance of this electrode was compared with coated graphite electrode (CGE), which showed better response characteristics w.r.t Nernstian slope 59.0 ± 0.2 mV decade−1 activity, wide concentration range of 8.9 × 10−8 to 1.0 × 10−2 mol L−1 and detection limit of 6.7 × 10−8 mol L−1. The response time for CGE and PME was found to be 8 and 10 s, respectively. The proposed electrode (CGE) was successfully applied to direct determination of thiocyanate in biological and environmental samples and also as indicator electrode in potentiometric titration of SCN ion.  相似文献   

19.
A simple, sensitive, selective, and low-cost method is proposed for rapidly determining nitric oxide (NO) in some rat tissues. Polymer monolith microextraction (PMME) using a poly(methacrylic acid–ethylene glycol dimethacrylate) (MAA-EGDMA) monolithic column was combined with derivatization of NO using 1,3,5,7-tetramethyl-8-(3′,4′-diaminophenyl)-difluoroboradiaza-s-indacene (TMDABODIPY), and this was used to analyze the derivatives of NO by high-performance liquid chromatography (HPLC) with fluorescence detection at λ ex/λ em = 498/507 nm. The baseline separation of TMDABODIPY and its NO derivative is performed under simple conditions in which a C18 column is used and eluted with 50 mmol L−1 ethanolamine and methanol. The conditions for the extraction of NO derivatives were optimized. The limit of detection of NO was 2 × 10−12 mol L−1 (S/N = 3). The linearity range of the method was 9 × 10−11−4.5 × 10−8 mol L−1. The interday and intraday relative standard deviations were less than 5%. The proposed method was successfully applied to the determination of NO levels in some rat tissue samples including heart, kidney, and liver with recoveries varying from 87.1 to 95.2%.  相似文献   

20.
Bismuth sulfide (Bi2S3) thin films were electrodeposited from non-aqueous dimethyl sulfoxide medium containing Bi(NO3)3 and thiourea as the precursor salts, triethanol amine as the complexing agent, and TritonX-100 as the surface active agent. The prepared films were subjected to rigorous experimentation in order to validate their potential candidature for solar cells. The films exhibited band gap energy of ∼1.3 eV and resistivity of the order of 2 × 106 Ω cm at room temperature as was obtained from UV–Vis spectroscopy and four-probe measurements, respectively. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and energy dispersive analysis of X-ray were employed to reveal the morphology, structure, and chemical composition of the film matrix. The Bi2S3 films were found to be non-decomposable up to the temperature of 1,000 °C with the help of thermogravimetry–differential thermal analysis. The Nyquist and Mott–Schottky plots derived from electrochemical impedance spectroscopy measurements provided important information regarding electrical and semiconducting properties of the films. The n-type film with a donor density of the order of ∼1023 m−3 displayed reasonable photoactivity under illumination and is recommended as a promising candidate for potential photoelectrochemical applications.  相似文献   

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