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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.
Solid solutions of spinel-type oxides with the composition (x = 0.0, 0.3, 0.5, 0.6, 1.0) were prepared with the glycine-nitrate combustion synthesis (x = 0.0, 0.3, 0.5, 0.6) and the citric-acid combustion synthesis (x = 1.0). The oxides were used as electrode materials in a pseudo-three-electrode setup in the temperature range of 400–600
°C. Cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the electrochemical behavior in
1% NO and 10% O2. Measurements show that NiFe2O4 has relatively high cathodic activity in both NO and O2, whereas MgFe2O4 shows much higher activity in NO compared to O2. MgFe2O4 was also measured with cyclic voltammetry in 1% NO2 and different gas mixtures of NO and O2 at 300 and 400 °C. Results show that the cathodic activities (−0.6 V) are relatively high with current ratios, , ranging from 10.1–167.7 and with a maximum at 400 °C. Dilatometry measurements were performed on the materials in air up
to 1,000 °C, and they showed that the Curie temperature could be detected for all samples. Four-point DC resistivity measurements
at elevated temperatures show that Ni0.4Mg0.6Fe2O4 has the highest conductivity, whereas Ni0.7Mg0.3Fe2O4 and NiFe2O4 have the highest conductivity at lower temperatures. 相似文献
3.
Sensitive fluorescent probes for determination of hydrogen peroxide and glucose based on enzyme-immobilized magnetite/silica nanoparticles 总被引:2,自引:0,他引:2
Qing Chang Lihua Zhu Guodong Jiang Heqing Tang 《Analytical and bioanalytical chemistry》2009,395(7):2377-2385
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.
Eduardo Marafon Lauro T. Kubota Yoshitaka Gushikem 《Journal of Solid State Electrochemistry》2009,13(3):377-383
SiO2/ZrO2/C carbon ceramic material with composition (in wt%) SiO2 = 50, ZrO2 = 20, and C = 30 was prepared by the sol–gel-processing method. A high-resolution transmission electron microscopy image
showed that ZrO2 and the graphite particles are well dispersed inside the matrix. The electrical conductivity obtained for the pressed disks
of the material was 18 S cm−1, indicating that C particles are also well interconnected inside the solid. An electrode modified with flavin adenine dinucleotide
(FAD) prepared by immersing the solid SiO2/ZrO2/C, molded as a pressed disk, inside a FAD solution (1.0 × 10−3 mol L−1) was used to investigate the electrocatalytic reduction of bromate and iodate. The reduction of both ions occurred at a peak
potential of −0.41 V vs. the saturated calomel reference electrode. The linear response range (lrr) and detection limit (dl)
were: BrO3
−, lrr = 4.98 × 10−5–1.23 × 10−3 mol L−1 and dl = 2.33 μmol L−1; IO3
−, lrr = 4.98 × 10−5 up to 2.42 × 10−3 and dl = 1.46 μmol L−1 for iodate. 相似文献
5.
A novel hydrogen peroxide (H2O2) biosensor was developed by immobilizing hemoglobin on the gold colloid modified electrochemical pretreated glassy carbon
electrode (PGCE) via the bridging of an ethylenediamine monolayer. This biosensor was characterized by UV-vis reflection spectroscopy
(UV-vis), electrochemical impendence spectroscopy (EIS) and cyclic voltammetry (CV). The immobilized Hb exhibited excellent
electrocatalytic activity for hydrogen peroxide. The Michaelis–Menten constant (K
m) was 3.6 mM. The currents were proportional to the H2O2 concentration from 2.6 × 10−7 to 7.0 × 10−3 M, and the detection limit was as low as 1.0 × 10−7 M (S/N = 3). 相似文献
6.
Günter Grampp Stephan Landgraf Tomasz Wesierski Beata Jankowska Ewa Kalisz Dana-Maria Sabou Boryana Mladenova 《Monatshefte für Chemie / Chemical Monthly》2002,133(10):1363-1372
Summary. The kinetics of the CrO(O2)2 formation by H2O2 and Cr2O7
2− in aqueous acidic media was measured at 293 ± 2 K in a pH range between 2.5 and 3.3. Using the stopped-flow method with rapid scan UV-VIS detection, the rate law of the formation
of CrO(O2)2 was determined. For the media HClO4, HNO3 and CH3COOH, the reaction order in the Cr2O7
2− concentration was found to be 0.5. For [H2O2] as well as for [H+], the reaction was first order in all acids used. In HCl and H2SO4 media the reaction was first order in Cr2O7
2−. At T = 293 ± 2 K the rate constant for the formation of Cr(O)(O2)2 was found to be (7.3 ± 1.9) · 102 M−3/2 s−1 in HClO4.
Corresponding author. E-mail: grampp@ptc.tu-graz.ac.at
Received January 30, 2002; accepted (revised) June 5, 2002 相似文献
7.
Kumar S. Ashok Wang Sea-Fue Yeh Chun-Ting Lu His-Chuan Yang Jen-Chang Chang Yu-Tsern 《Journal of Solid State Electrochemistry》2010,14(11):2129-2135
In this study, stable and homogenous thin films of multiwalled carbon nanotubes (MWCNTs) were obtained on conducting surface
using ciprofloxacin (CF, fluoroquinolone antibiotic) as an effective-dispersing agent. Further, MWCNTs/CF film modified electrodes
(glassy carbon and indium tin oxide-coated glass electrode) are used successfully to study the direct electrochemistry of
proteins. Here, cytochrome C (Cyt-C) was used as a model protein for investigation. A MWCNTs/CF film modified electrode was
used as a biocompatible material for immobilization of Cyt-C from a neutral buffer solution (pH 7.2) using cyclic voltammetry
(CV). Interestingly, Cyt-C retained its native state on the MWCNTs/CF film. The Cyt-C adsorbed MWCNTs/CF film was characterized
by scanning electron microscopy (SEM), UV–visible spectrophotometry (UV-vis) and CV. SEM images showed the evidence for the
adsorption of Cyt-C on the MWCNTs/CF film, and UV–vis spectrum confirmed that Cyt-C was in its native state on MWCNTs/CF film.
Using CV, it was found that the electrochemical signal of Cyt-C was highly stable in the neutral buffer solution and its redox
peak potential was pH dependent. The formal potential (−0.27 V) and electron transfer rate constant (13 ± 1 s−1) were calculated for Cyt-C on MWCNTs/CF film modified electrode. A potential application of the Cyt-C/MWCNTs/CF electrode
as a biosensor to monitor H2O2 has been investigated. The steady-state current response increases linearly with H2O2 concentration from 2 × 10−6 to 7.8 × 10−5 M. The detection limit for determination of H2O2 has been found to be 1.0 × 10−6 M (S/N = 3). Thus, Cyt-C/MWCNTs/CF film modified electrode can be used as a biosensing material for sensor applications. 相似文献
8.
M. H. Pournaghi-Azar H. Dastangoo M. Ziaei 《Journal of Solid State Electrochemistry》2007,11(9):1221-1227
The electrocatalytic activity of a Prussian blue (PB) film on the aluminum electrode by taking advantage of the metallic palladium
characteristic as an electron-transfer bridge (PB/Pd–Al) for electrooxidation of 2-methyl-3-hydroxy-4,5-bis (hydroxyl–methyl)
pyridine (pyridoxine) is described. The catalytic activity of PB was explored in terms of FeIII [FeIII (CN)6]/FeIII [FeII (CN)6]1− system. The best mediated oxidation of pyridoxine (PN) on the PB/Pd–Al-modified electrode was achieved in 0.5 M KNO3 + 0.2 M potassium acetate of pH 6 at scan rate of 20 mV s−1. The mechanism and kinetics of the catalytic oxidation reaction of PN were monitored by cyclic voltammetry and chronoamperometry.
The results were explained using the theory of electrocatalytic reactions at chemically modified electrodes. The charge transfer-rate
limiting reaction step is found to be a one-electron abstraction, whereas a two-electron charge transfer reaction is the overall
oxidation reaction of PN by forming pyridoxal. The value of α, k, and D are 0.5, 1.2 × 102 M−1 s−1, and 1.4 × 10−5 cm2 s−1, respectively. Further examination of the modified electrodes shows that the modifying layers (PB) on the Pd–Al substrate
have reproducible behavior and a high level of stability after posing it in the electrolyte or Pyridoxine solutions for a
long time. 相似文献
9.
A new H2O2 biosensor was fabricated on the basis of nanocomposite films of hemoglobin (Hb), silver nanoparticles (AgNPs), and multiwalled
carbon nanotubes (MWNTs)–chitosan (Chit) dispersed solution immobilized on glassy carbon electrode (GCE). The immobilized
Hb displayed a pair of well-defined and reversible redox peaks with a formal potential (E
θ′) of −22.5 mV in 0.1 M pH 7.0 phosphate buffer solution. The apparent heterogeneous electron transfer rate constants (k
s) in the Chit–MWNTs film was evaluated as 2.58 s−1 according to Laviron’s equation. The surface concentration (Γ*) of the electroactive Hb in the Chit–MWNTs film was estimated to be (2.48 ± 0.25) × 10−9 mol cm−2. Meanwhile, the Chit–MWNTs/Hb/AgNPs/GCE demonstrated excellently electrocatalytical ability to H2O2. Its apparent Michaelis–Menten constant (K
Mapp) for H2O2 was 0.0032 mM, showing a good affinity. Under optimal conditions, the biosensors could be used for the determination of H2O2 ranging from 6.25 × 10−6 to 9.30 × 10−5 mol L−1 with a detection limit of 3.47 × 10−7 mol L−1 (S/N = 3). Furthermore, the biosensor possessed rapid response to H2O2 and good stability, selectivity, and reproducibility. 相似文献
10.
The kinetics of Li2SO4·H2O dehydration in static air atmosphere was studied on the basis of nonisothermal measurements by differential scanning calorimetry.
Dehydration data were subjected to an integral composite procedure, which includes an isoconversional method, a master plots
method and a model-fitting method. Avrami-Erofeev equation was found to describe all the experimental data in the range of
conversion degrees from 0.1 to 0.9. The determined activation energy equals 65.45 kJ·mol−1 with standard deviation ±0.47 kJ·mol−1. The estimated value of parameter m in Avrami-Erofeev equation is 2.15 with standard deviation ±0.11. Also, the obtained pre-exponential factor is 7.79×105 s−1 with standard deviation ±0.55×105 s−1. The results show that the present integral composite procedure gives self-consistent kinetic parameters. 相似文献
11.
Jadwiga Walczak Izabella Rychłowska-Himmel Elżbieta Mikos-Nawłatyna 《Journal of Thermal Analysis and Calorimetry》1995,43(2):427-431
The phase equilibria established up to the solidus line in the system Fe2V4O13−WO3, one of the intersections of the three-component system Fe2O3−V2O5−WO3, have been studied. The system appears not to be a real two-component system.
Zusammenfassung Es wurde eine Untersuchung des Phasengleichgewichtes durchgeführt, welches bezüglich der Solidus-Linie im System Fe2V4O13−WO3, einer der Zwischenbereiche im Dreikomponentensystem Fe2O3−V2O5−WO3, nachgewiesen wurde. Dieses System scheint kein echtes Zweikomponentensystem zu sein.相似文献
12.
Audrey Sassolas Loïc J. Blum Béatrice D. Leca-Bouvier 《Analytical and bioanalytical chemistry》2009,394(4):971-980
Performant reagentless electrochemiluminescent (ECL) (bio)sensors have been developed using polymeric luminol as the luminophore.
The polyluminol film is obtained by cyclic voltammetry (CV) on a screen-printed electrode either in a commonly used H2SO4 medium or under more original near-neutral buffered conditions. ECL responses obtained after performing polymerization either
at acidic pH or at pH 6 have been compared. It appears that polyluminol formed in near-neutral medium gives the best responses
for hydrogen peroxide detection. Polymerization at pH 6 by cyclic voltammetry gives a linear range extending from 8 × 10−8 to 1.3 × 10−4 M H2O2 concentrations. Based on this performant sensor for hydrogen peroxide detection, an enzymatic biosensor has been developed
by associating the polyluminol film with an H2O2-producing oxidase. Here, choline oxidase (ChOD) has been chosen as a model enzyme. To develop the biosensor, luminol has
been polymerized at pH 6 by CV, and then an enzyme-entrapping matrix has been formed on the above modified working electrode.
Different biological (chitosan, agarose, and alginate) and chemical (silica gels, photopolymers, or reticulated matrices)
gels have been tested. Best performances have been obtained by associating a ChOD-immobilizing photopolymer with the polyluminol
film. In this case, choline can be detected with a linear range extending from 8 × 10−8 to 1.3 × 10−4 M.
This paper is based on the results presented in a poster that received a Poster Award on the occasion of XIII International
Symposium on Luminescence Spectrometry in Bologna, Italy, on September, 7th-11th, 2008. 相似文献
13.
Zhi-Heng Zhang Guo-Yin Yin Zhi-Cheng Tan Yan Yao Li-Xian Sun 《Journal of solution chemistry》2006,35(10):1347-1355
The molar heat capacities of an aqueous Li2B4O7 solution were measured with a precision automated adiabatic calorimeter in the temperature range from 80 to 356 K at a concentration of 0.3492 mol⋅kg−1. The occurrence of a phase transition was determined based on the changes in the curve of the heat capacity with temperature. A phase transition was observed at 271.72 K corresponding to the solid-liquid phase transition; the enthalpy and entropy of the phase transition were evaluated to be Δ H
m = 4.110 kJ⋅mol−1 and Δ S
m = 15.13 J⋅K−1⋅mol−1, respectively. Using polynomial equations and thermodynamic relationship, the thermodynamic functions [H
T
−H
298.15] and [S
T
−S
298.15] of the aqueous Li2B4O7 solution relative to 298.15 K were calculated in temperature range 80 to 355 K at intervals of 5 K. Values of the relative apparent molar heat capacities of the aqueous Li2B4O7 solution, C
p,φ, were calculated at every 5 K in temperature range from 80 to 355 K from the experimental heat capacities of the solution and the heat capacities of pure water. 相似文献
14.
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
15.
通过一定体积比的CdS和普鲁士蓝(PB)胶体纳米溶液的简单混合,制备了PB/CdS纳米复合物。在共反应剂存在条件下,PB纳米粒子含量较低时,在ITO电极上CdS纳晶的电致化学发光(ECL)强度可以增强3倍左右。PB纳米粒子含量较高时,CdS纳晶的ECL强度则显著降低。详细讨论了PB纳米粒子对CdS纳晶ECL影响的机理。PB纳米粒子对CdS纳晶的ECL增强可用于H2O2传感。该传感器对H2O2响应的线性范围为3.3×10-8~6.5×10-3 mol.L-1(R=0.999 2),检测限为12 nmol.L-1(S/N=3),传感器具有良好的稳定性和重现性。 相似文献
16.
V. L. E. Simonsen L. Nørskov A. Hagen K. Kammer Hansen 《Journal of Solid State Electrochemistry》2009,13(10):1529-1534
The series La2 − x
Sr
x
NiO4 (x = 0.0, 0.05, 0.15, 0.25, 0.35, and 1.0) was tested for functionality as electrode materials for direct electrochemical reduction
of NO. The materials were tested using cyclic voltammetry in 1% NO and 10% O2 in Ar on a cone-shaped electrode. The best materials for the electrochemical reduction of NO are La2NiO4 and LaSrNiO4, which have current densities for NO reduction 1.82 and 7.09 times higher, respectively, than for O2 at 400 °C. Increasing the temperature decreased the ability to reduce NO before O2 while the activity increased. The adsorbed species during direct decomposition was attempted, clarified using X-ray absorption
near-edge structure experiments and thermogravimetry, but no conclusive results were obtained. 相似文献
17.
Ji-min Yang Yan Yao Run-zhi Zhang Ai-de Sun Bao-hui Li Hong-zhi Lu Qi-ying Xia 《Journal of solution chemistry》2009,38(4):429-439
Osmotic coefficients and water activities for the Li2B4O7+LiCl+H2O system have been measured at T=273.15 K by the isopiestic method, using an improved apparatus. Two types of osmotic coefficients, φ
S and φ
E, were determined. φ
S is based on the stoichiometric molalities of the solute Li2B4O7(aq), and φ
E is based on equilibrium molalities from consideration of the equilibrium speciation into H3BO3,B(OH)4− and B3O3(OH)4−. The stoichiometric equilibrium constants K
m
for the aqueous speciation reactions were estimated. Two types of representations of the osmotic coefficients for the Li2B4O7+LiCl+H2O system are presented with ion-interaction models based on Pitzer’s equations with minor modifications: model (I) represents
the φ
S data with six parameters based on considering the ion-interactions between three ionic species of Li+, Cl−, and B4O72−, and model (II) for represents the φ
E data based on considering the equilibrium speciation. The parameters of models (I) and (II) are presented. The standard deviations
for the two models are 0.0152 and 0.0298, respectively. Model (I) was more satisfactory than model (II) for representing the
isopiestic data. 相似文献
18.
The deuterium-isotope effects on the ionization constants of β-naphthol (2-naphthol) and boric acid, Δlog 10
K=[log 10
K
D2O−log 10
K
H2O], have been determined from measurements in light and heavy water at temperatures from 225 °C≤t≤300 °C and pressures near steam saturation. β-Naphthol is a thermally-stable colorimetric pH indicator, whose ionization constant lies close to that of H2PO4− (aq), the only acid for which Δlog 10
K is accurately known at elevated temperatures. A newly designed platinum flow cell was used to measure UV-visible spectra
of β-naphthol in acid, base, and buffer solutions of H2PO4−/HPO42− and D2PO4−/DPO42−, from which the degree of ionization at known values of pH and pD was determined. Values of the ionization constants of β-naphthol in light and heavy water were calculated from these results, and used to derive a model for
and
over the experimental temperature range with an estimated precision of ±0.02 in log 10
K. The new values of K
H2O and K
D2O allowed us to use β-naphthol as a colorimetric indicator, to measure the equilibrium pH and pD of the buffer solutions B(OH)3/B(OH)4− and B(OD)3/B(OD)4− up to 300 °C, from which the ionization constants of boric acid were calculated. The magnitude of the deuterium isotope effect
for H2PO4− (aq) is known to fall from Δlog 10
K=−0.62 to Δlog 10
K=−0.47, on the “aquamolal” concentration scale, as the temperature rises above 125 °C, but then remains almost constant. Although
the temperature range is more limited, the new results for β-naphthol and boric acid appear to show a similar trend. 相似文献
19.
Gold nanoparticles (nano Au)/titanium dioxide (TiO2) hollow microsphere membranes were prepared on the carbon paste electrode (CPE) for enhancing the sensitivity of DNA hybridization
detection. The immobilization of nano Au and TiO2 microsphere was investigated with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The hybridization
events were monitored with EIS using [Fe(CN)6]3−/4− as indicator. The sequence-specific DNA of the 35S promoter from cauliflower mosaic virus (CaMV35S) gene was detected with
this DNA electrochemical sensor. The dynamic detection range was from 1.0×10−12 to 1.0×10−8 mol/L DNA and a detection limit of 2.3×10−13 mol/L could be obtained. The polymerase chain reaction (PCR) amplification of the terminator of nopaline synthase (NOS) gene
from the real sample of a kind of transgenic soybean was also satisfactorily detected.
Supported by the National Natural Science Foundation of China (Grant Nos. 20635020 and 20375020), Doctoral Foundation of the
Ministry of Education of China (Grant No. 20060426001) and Natural Science Foundation of Qingdao City (Grant No. 04-2-JZP-8) 相似文献
20.
A graphene, chitosan and Fe3O4 nanoparticles (nano-Fe3O4) modified glassy carbon electrode (graphene-chitosan/nano-Fe3O4/GCE) was fabricated. The modified electrode was characterized by scanning electron microscope and electrochemical impedance spectroscopy. The electrochemical oxidation behavior of guanosine was investigated in pH 7.0 phosphate buffer solution by cyclic voltammetry and differential pulse voltammetry. The experimental results indicated that the modified electrode exhibited an electrocatalytic and adsorptive activities towards the oxidation of guanosine. The transfer electron number (n), transfer proton number (m) and electrochemically effective surface area (A) were calculated. Under the optimized conditions, the oxidation peak current was proportional to guanosine concentration in the range of 2.0 × 10−6 to 3.5 × 10−4 mol L−1 with the correlation coefficient of 0.9939 and the detection limit of 7.5 × 10−7 mol L−1 (S/N = 3). Moreover, the modified electrode showed good ability to discriminate the electrochemical oxidation response of guanosine, guanine and adenosine. The proposed method was further applied to determine guanosine in spiked urine samples and traditional Chinese medicines with satisfactory results. 相似文献