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1.
Qian L  Yang X 《Talanta》2006,68(3):721-727
A new amperometric biosensor for hydrogen peroxide was developed based on cross-linking horseradish peroxidase (HRP) by glutaraldehyde with multiwall carbon nanotubes/chitosan (MWNTs/chitosan) composite film coated on a glassy carbon electrode. MWNTs were firstly dissolved in a chitosan solution. Then the morphology of MWNTs/chitosan composite film was characterized by field-emission scanning electron microscopy. The results showed that MWNTs were well soluble in chitosan and robust films could be formed on the surface. HRP was cross-linked by glutaraldehyde with MWNTs/chitosan film to prepare a hydrogen peroxide biosensor. The enzyme electrode exhibited excellent electrocatalytic activity and rapid response for H2O2 in the absence of a mediator. The linear range of detection towards H2O2 (applied potential: −0.2 V) was from 1.67 × 10−5 to 7.40 × 10−4 M with correction coefficient of 0.998. The biosensor had good repeatability and stability for the determination of H2O2. There were no interferences from ascorbic acid, glucose, citrate acid and lactic acid.  相似文献   

2.
A polyaniline (PANI)/carbon nanotubes (CNTs) composite modified electrode was fabricated by galvanostatic electropolymerization of aniline on multi-walled carbon nanotubes (MWNTs)-modified gold electrode. The electrode thus prepared exhibits enhanced electrocatalytic behavior to the reduction of nitrite and facilitates the detection of nitrite at an applied potential of 0.0 V. Although the amperometric responses toward nitrite at MWNTs/gold and PANI/gold electrodes have also been observed in the experiments, these responses are far less than that obtained at PANI/MWNTs/gold electrode. The effects of electropolymerization time, MWNTs concentration and pH value of the detection solution on the current response of the composite modified electrode toward sodium nitrite, were investigated and discussed. A linear range from 5.0 × 10−6 to 1.5 × 10−2 M for the detection of sodium nitrite has been observed at the PANI/MWNTs modified electrode with a sensitivity of 719.2 mA M−1 cm−2 and a detection limit of 1.0 μM based on a signal-to-noise ratio of 3.  相似文献   

3.
α-Fe2O3 nanoparticles prepared using a simple solution-combusting method have been dispersed in chitosan (CH) solution to fabricate nanocomposite film on glass carbon electrode (GCE). The as-prepared α-Fe2O3 nanoparticles were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM). The nanocomposite film exhibits high electrocatalytic oxidation for nitric oxide (NO) and reduction for hydrogen peroxide (H2O2). The electrocatalytic oxidation peak is observed at +0.82 V (vs. Ag/AgCl) and controlled by diffusion process. The electrocatalytic reduction peak is observed at −0.45 V (vs. Ag/AgCl) and controlled by diffusion process. This α-Fe2O3-CH/GCE nanocomposite bioelectrode has response time of 5 s, linearity as 5.0 × 10−7 to 15.0 × 10−6 M of NO with a detection limit of 8.0 × 10−8 M and a sensitivity of −283.6 μA/mM. This α-Fe2O3-CH/GCE nanocomposite bioelectrode was further utilized in detection of H2O2 with a detection limit of 4.0 × 10−7 M, linearity as 1.0 × 10−6 to 44.0 × 10−6 M and with a sensitivity of 21.62 μA/mM. The shelf life of this bioelectrode is about 6 weeks under room temperature conditions.  相似文献   

4.
A series of spinel-type CoxNi1−xFe2O4 (x = 0, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0) magnetic nanomaterials were solvothermally synthesized as enzyme mimics for the eletroctrocatalytic oxidation of H2O2. X-ray diffraction and scanning electron microscope were employed to characterize the composition, structure and morphology of the material. The electrochemical properties of spinel-type CoxNi1−xFe2O4 with different (Co/Ni) molar ratio toward H2O2 oxidation were investigated, and the results demonstrated that Co0.5Ni0.5Fe2O4 modified carbon paste electrode (Co0.5Ni0.5Fe2O4/CPE) possessed the best electrocatalytic activity for H2O2 oxidation. Under optimum conditions, the calibration curve for H2O2 determination on Co0.5Ni0.5Fe2O4/CPE was linear in a wide range of 1.0 × 10−8–1.0 × 10−3 M with low detection limit of 3.0 × 10−9 M (S/N = 3). The proposed Co0.5Ni0.5Fe2O4/CPE was also applied to the determination of H2O2 in commercial toothpastes with satisfactory results, indicating that CoxNi1−xFe2O4 is a promising hydrogen peroxidase mimics for the detection of H2O2.  相似文献   

5.
In this paper, LaNi0.6Co0.4O3 (LNC) nanoparticles were synthesized by the sol–gel method, and the structure and morphology of LNC nanoparticles were characterized by X-ray diffraction spectrum, scanning electron microscopy and transmitting electron microscopy. And then, LNC was used to modify carbon paste electrode (CPE) without any adhesive to fabricate hydrogen peroxide and glucose sensor, and the results demonstrated that LNC exhibited strong electrocatalytical activity by cyclic voltammetry and amperometry. In H2O2 determination, linear response was obtained in the concentration range of 10 nM–100 μM with a detection limit of 1.0 nM. In glucose determination, there was the linear region of 0.05–200 μM with a detection limit of 8.0 nM. Compared with other reports, the proposed sensor also displayed high sensitivity toward H2O2 (1812.84 μA mM−1 cm−2) and glucose (643.0 μA mM−1 cm−2). Moreover, this prepared sensor was applied to detect glucose in blood serum and hydrogen peroxide in toothpaste samples with satisfied results, indicating its possibility in practical application.  相似文献   

6.
Pentacyanoferrate-bound poly(1-vinylimidazole) (PVI[Fe(CN)5]) was selected as a mediator for amperometric creatinine determination based on the reductive H2O2 detection. Creatinine amidohydrolase (CNH), creatine amidohydrolase (CRH), sarcosine oxidase (SOD), peroxidase (POD), and PVI[Fe(CN)5] were crosslinked with poly(ethylene glycol) diglycidyl ether (PEGDGE) on a glassy carbon (GC) electrode for a creatinine biosensor fabrication. Reduction current was monitored at −0.1 V in the presence of creatinine and O2. It is revealed that PVI[Fe(CN)5] is suitable as a mediator for a bioelectrocatalytic reaction of POD, since PVI[Fe(CN)5] neither reacts with reactants nor works as an electron acceptor of SOD. The amounts of PVI[Fe(CN)5], PEGDGE, and enzymes were optimized toward creatinine detection. Nafion as a protecting film successfully prevented the enzyme layer from interferences. The detection limit and linear range in creatinine determination were 12 μM and 12–500 μM (R2 = 0.993), respectively, and the sensitivity was 11 mA cm−2 M−1, which is applicable for urine creatinine tests. The results of the creatinine determination for four urine samples measured with this proposed method were compared with Jaffe method, and a good correlation was obtained between the results.  相似文献   

7.
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   

8.
Arrays of nanoscopic gold tubes were prepared by electroless plating of the metal within the pores of nanoporous polycarbonate track-etched membranes. A procedure for fabricating an ensemble of enzyme-modified nanoelectrodes has been developed based on the efficient immobilization of horseradish peroxidase (HRP) to the gold nanotubes array using self-assembled monolayers (mercaptoethylamine or mercaptopropionic acid) as anchoring layers. Hydrogen peroxide (H2O2) was determined electrochemically by using gold nanoelectrode ensembles (NEE) functionalized or not in phosphate buffer solution (PB) with or without a mediator (hydroquinone, H2Q). Bare NEE displays a remarkable sensitivity (14 μA mM−1 in H2Q at −0.1 V versus Ag/AgCl) compared to a classical gold macroelectrode (0.41 μA mM−1). The gold nanoparticles that form the tubular structure act as excellent catalytic surfaces towards the oxidation and the reduction of H2O2. The HRP modified NEE presents a slightly lower sensitivity (9.5 μA mM−1) than bare NEE. However, this system presents an enhanced limit of detection (up to 4 × 10−6 M) and a higher selectivity towards the detection of H2O2 over a wide range of potentials. The lifetime, fabrication reproducibility and measurement repeatability of the HRP enzyme electrode were evaluated with satisfactory results.  相似文献   

9.
Hydroboration reactions of 1-octene and 1-hexyne with H2BBr·SMe2 in CH2Cl2 were studied as a function of concentration and temperature, using 11B NMR spectroscopy. The reactions exhibited saturation kinetics. The rate of dissociation of dimethyl sulfide from boron at 25 °C was found to be (7.36 ± 0.59 and 7.32 ± 0.90) × 10−3 s−1 for 1-octene and 1-hexyne, respectively. The second order rate constants, k2, for hydroboration worked out to be 7.00 ± 0.81 M s−1 and 7.03 ± 0.70 M s−1, while the overall composite second order rate constants, k K, were (3.30 ± 0.43 and 3.10 ± 0.37) × 10−2 M s−1, respectively at 25 °C. The entropy and enthalpy values were found to be large and positive for k1, whilst for k2 these were large and negative, with small values for enthalpies. This is indicative of a limiting dissociative (D) for the dissociation of Me2S and associative mechanism (A) for the hydroboration process. The overall activation parameters, ΔH and ΔS, were found to be 98 ± 2 kJ mol−1 and +56 ± 7 J K−1 mol−1 for 1-octene whilst, in the case of 1-hexyne these were found out to be 117 ± 7 kJ mol−1 and +119 ± 24 J K−1 mol−1, respectively. When comparing the kinetic data between H2BBr·SMe2 and HBBr2·SMe2, the results showed that the rate of dissociation of Me2S from H2BBr·SMe2 is on average 34 times faster than it is in the case of HBBr2·SMe2. Similarly, the rate of hydroboration with H2BBr·SMe2 was found to be on average 11 times faster than it is with HBBr2·SMe2. It is also clear that by replacing a hydrogen substituent with a bromine atom in the case of H2BBr·SMe2 the mechanism for the overall process changes from limiting dissociative (D) to interchange associative (Ia).  相似文献   

10.
M. Ghiaci  R.J. Kalbasi 《Talanta》2007,73(1):37-45
The main purpose of this study is to develop an inexpensive, simple, selective and especially highly selective modified mixed-oxide carbon paste electrode (CPE) for voltammetric determination of Pb(II). For the preliminary screening purpose, the catalyst was prepared by modification of SiO2-Al2O3 mixed-oxide and characterized by TG, CHN elemental analysis and FTIR spectroscopy. Using cyclic voltammetry the electroanalytical characteristics of the catalyst have been determined, and consequently the modified mixed-oxide carbon paste electrode was constructed and applied for determination of Pb(II). The electroanalytical procedure for determination of the Pb(II) comprises two steps: the chemical accumulation of the analyte under open-circuit conditions followed by the electrochemical detection of the preconcentrated species using differential pulse anodic stripping voltammetry. During the preconcentration step, Pb(II) was accumulated on the surface of the modifier by the formation of a complex with the nitrogen atoms of the pyridyl groups in the modifier. The peak currents increases linearly with Pb(II) concentration over the range of 2.0 × 10−9 to 5.2 × 10−5 mol L−1 (r2 = 0.9995).The detection limit (three times signal-to-noise) was found to be 1.07 × 10−9 mol L−1 Pb(II). The chemical and instrumental parameters have been optimized and the effect of the interferences has been determined. The Proposed method was used for determination of lead ion in the real samples.  相似文献   

11.
Santos LS  Landers R  Gushikem Y 《Talanta》2011,85(2):1213-1216
This work describes the in situ immobilization of Mn(II) phthalocyanine (MnPc) in a porous SiO2/SnO2 mixed oxide matrix obtained by the sol gel processing method. The chemically modified matrix SiO2/SnO2/MnPc, possessing an estimated amount of 8 × 10−10 mol cm−2 of MnPc on the surface, was used to prepare an electrode to analyze dissolved oxygen in water by an electrochemical technique. The electrode was prepared by mixing the material with ultrapure graphite and evaluated using differential pulse voltammetry. Dissolved O2 was reduced at −0.31 V with a limit of detection (LOD) equal to 7.0 × 10−4 mmol L−1. A mechanism involving four electrons in O2 reduction was determined by the rotating disk electrode technique.  相似文献   

12.
Gui-Fen Jie 《Talanta》2007,71(4):1476-1480
Electrogenerated chemiluminescence (ECL) of CdS nanotubes in aqueous solution and its sensing application were studied by entrapping the CdS nanotubes in carbon paste electrode. Two ECL peaks were observed at −0.9 V (ECL-1) and −1.2 V (ECL-2), respectively, when the potential was cycled between 0 and −1.6 V. The electrochemically reduced nanocrystal species of CdS nanotubes could collide with the oxidized species in an annihilation process to produce the peak of ECL-1. The electron-transfer reaction between the reduced CdS nanocrystal species and oxidant coreactants such as S2O82−, H2O2, and reduced dissolved oxygen led to the appearance of the ECL-2 peak. Based on the enhancing effect of H2O2 on ECL-2 intensity, a novel CdS ECL sensor was developed for H2O2 detection. The sensor exhibited a detection limit of 0.1 μM and a linear range from 0.5 μM to 0.01 mM. The relative standard deviations of five replicate determinations of 5 μM H2O2 was 2.6%. In addition, the ECL spectrum in aqueous solution also exhibited two peaks at 500 and 640 nm, respectively.  相似文献   

13.
This article reports on carbon nanotube/manganese dioxide (CNT–MnO2) composites as electrochemical tags for non-enzymatic signal amplification in immunosensing. The synthesized CNT–MnO2 composites showed good electrochemical activity, electrical conductivity and stability. The electrochemical signal of CNT–MnO2 composites coated glassy carbon electrode (GCE) increased by nearly two orders of magnitude compared to bare GCE in hydrogen peroxide (H2O2) environment. CNT–MnO2 composite was subsequently validated as electrochemical tags for sensitive detection of α-fetoprotein (AFP), a tumor marker for diagnosing hepatocellular carcinoma. The electrochemical immunosensor demonstrated a linear response on a log-scale for AFP concentrations ranging from 0.2 to 100 ng mL−1. The limit of detection (LOD) was estimated to be 40 pg mL−1 (S/N = 3) in PBS buffer. Further measurements using AFP spiked plasma samples revealed the applicability of fabricated CNT–MnO2 composites for clinical and diagnostic applications.  相似文献   

14.
A simple procedure has been used for preparation of modified glassy carbon electrode with carbon nanotubes and copper complex. Copper complex [Cu(bpy)2]Br2 was immobilized onto glassy carbon (GC) electrode modified with silicomolybdate, α-SiMo12O404− and single walled carbon nanotubes (SWCNTs). Copper complex and silicomolybdate irreversibly and strongly adsorbed onto GC electrode modified with CNTs. Electrostatic interactions between polyoxometalates (POMs) anions and Cu-complex, cations mentioned as an effective method for fabrication of three-dimensional structures. The modified electrode shows three reversible redox couples for polyoxometalate and one redox couple for Cu-complex at wide range of pH values. The electrochemical behavior, stability and electron transfer kinetics of the adsorbed redox couples were investigated using cyclic voltammetry. Due to electrostatic interaction, copper complex immobilized onto GC/CNTs/α-SiMo12O404− electrode shows more stable voltammetric response compared to GC/CNTs/Cu-complex modified electrode. In comparison to GC/CNTs/Cu-complex the GC/CNTs/α-SiMo12O404− modified electrodes shows excellent electrocatalytic activity toward reduction H2O2 and BrO3 at more reduced overpotential. The catalytic rate constants for catalytic reduction hydrogen peroxide and bromate were 4.5(±0.2) × 103 M−1 s−1 and 3.0(±0.10) × 103 M−1 s−1, respectively. The hydrodynamic amperommetry technique at 0.08 V was used for detection of nanomolar concentration of hydrogen peroxide and bromate. Detection limit, sensitivity and linear concentration range proposed sensor for bromate and hydrogen peroxide detection were 1.1 nM and 6.7 nA nM−1, 10 nM-20 μM, 1 nM, 5.5 nA nM−1 and 10 nM-18 μM, respectively.  相似文献   

15.
Proton-conducting membranes based on phosphotungstic acid (PWA) and 3-glycidoxypropyl-trimethoxysilane (GPTMS) was investigated as the electrolyte for low temperature H2/O2 fuel cell. Parameters determining the conductivity and elastic modulus of the membranes were characterized by thermogravimetry/differential thermal analysis and infrared spectroscopic measurements. The composite containing 5% of PWA exhibited an elastic modulus below 100 MPa at room temperature and a high proton conductivity of 1.0 × 10−2 S/cm at 80 °C and 100% RH. Low elastic modulus of the membrane was found to be useful for both the reduction of the membrane thickness and the better contact with the electrodes. The performance of the membrane electrode assemblies (MEA) was systematically studied as an effect of preparation conditions. A maximum power density of 45 mW/cm2 and the current density of 175 mA/cm2 at 0.2 V were achieved at 90 °C and 100% RH for the membrane of 5PWA·95GPTMS composition and 0.2 mm thickness.  相似文献   

16.
A pure calcium borate Ca2[B2O4(OH)2]·0.5H2O has been synthesized under hydrothermal condition and characterized by XRD, FT-IR and TG as well as by chemical analysis. The molar enthalpy of solution of Ca2[B2O4(OH)2]·0.5H2O in HC1·54.582H2O was determined. From a combination of this result with measured enthalpies of solution of H3BO3 in HC1·54.561H2O and of CaO in (HCl + H3BO3) solution, together with the standard molar enthalpies of formation of CaO(s), H3BO3(s) and H2O(l), the standard molar enthalpy of formation of −(3172.5 ± 2.5) kJ mol−1 of Ca2[B2O4(OH)2]·0.5H2O was obtained.  相似文献   

17.
Xiang C  Zou Y  Sun LX  Xu F 《Talanta》2007,74(2):206-211
A robust and effective nanohybrid film based on gold nanoparticles (GNPs)/chitosan (Chit)/multi-walled carbon nanotubes (MWNTs) was prepared by a layer-by-layer self-assembly technique. Cytochrome c (Cyt c) was successfully immobilized on the nanohybrid film modified glassy carbon (GC) electrode by cyclic voltammetry. The direct electron transfer between Cyt c and the modified electrode was investigated in detail. Cyt c shows a couple of quasi-reversible and well-defined cyclic voltammetry peaks with a formal potential (E0′) of −0.16 V (versus Ag/AgCl) in pH 7.0 phosphate buffer solution (PBS). The Cyt c/GNPs/Chit/MWNTs modified GC electrode gives an improved electrocatalytic activity towards the reduction of hydrogen peroxide (H2O2). The sensitivity is 92.21 μA mM−1 cm−2 and the calculated apparent Michaelis-Menten constant () is 0.791 mM, indicating a high-catalytic activity of Cyt c. The catalysis currents increase linearly to the H2O2 concentration in a wide range of 1.5 × 10−6 to 5.1 × 10−4 M with a correlation coefficient 0.999. The detection limit is 9.0 × 10−7 M (at the ratio of signal to noise, S/N = 3). Moreover, the modified electrode displays rapid response (5 s) to H2O2, and possesses good stability and reproducibility.  相似文献   

18.
A modified glassy carbon electrode was prepared by depositing a composite of polymer and mediator on a glassy carbon electrode (GCE). The mediator, flavin adenine dinucleotide (FAD) and the polymer, poly(3,4-ethylenedioxythiophene) (PEDOT) were electrochemically deposited as a composite on the GCE by applying cyclic voltammetry (CV). This modified electrode is hereafter designated as GCE/PEDOT/FAD. FAD was found to significantly enhance the growth of PEDOT. Electrochemical quartz crystal microbalance (EQCM) analysis was performed to study the mass changes in the electrode during the electrodeposition of PEDOT, with and without the addition of FAD. The optimal cycle number for preparing the modified electrode was determined to be 9, and the corresponding surface coverage of FAD (ΓFAD) was ca. 5.11 × 10−10 mol cm−2. The amperometric detection of iodate was performed in a 100 mM buffer solution (pH 1.5). The GCE/PEDOT/FAD showed a sensitivity of 0.78 μA μM−1 cm−2, a linear range of 4–140 μM, and a limit of detection of 0.16 μM for iodate. The interference effects of 250-fold Na+, Mg2+, Ca2+, Zn2+, Fe2+, Cl, NO3, I, SO42− and SO32−, with reference to the concentration of iodate were negligible. The long-term stability of GCE/PEDOT/FAD was also investigated. The GCE/PEDOT/FAD electrode retained 82% of its initial amperometric response to iodate after 7 days. The GCE/PEDOT/FAD was also applied to determine iodate in a commercial salt.  相似文献   

19.
A new magnesium borate MgO·3B2O3·3.5H2O has been synthesized by the method of phase transformation of double salt and characterized by XRD, IR and Raman spectroscopy as well as by TG. The structural formula of this compound was Mg[B6O9(OH)2]·2.5H2O. The enthalpy of solution of MgO·3B2O3·3.5H2O in approximately 1 mol dm−3 HCl was determined. With the incorporation of the standard molar enthalpies of formation of MgO(s), H3BO3(s), and H2O(l), the standard molar enthalpy of formation of −(5595.02±4.85) kJ mol−1 of MgO·3B2O33.5H2O was obtained. Thermodynamic properties of this compound was also calculated by group contribution method.  相似文献   

20.
In this report, a highly sensitive amperometric sensor based on MnO2-modified vertically aligned multiwalled carbon nanotubes (MnO2/VACNTs) for determination of hydrogen peroxide (H2O2) was fabricated by electrodeposition. The morphology of the nanocomposite was characterized by scanning electron microscopy, energy-dispersive X-ray spectrometer and X-ray diffraction. Cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy were applied to investigate the electrochemical properties of the MnO2/VACNTs nanocomposite electrode. The mechanism for the electrochemical reaction of H2O2 at the MnO2/VACNTs nanocomposite electrode was also discussed. In borate buffer (pH 7.8, 0.20 M), the MnO2/VACNTs nanocomposite electrode exhibits a linear dependence (R = 0.998) on the concentration of H2O2 from 1.2 × 10−6 M to 1.8 × 10−3 M, a high sensitivity of 1.08 × 106 μA M−1 cm−2 and a detection limit of 8.0 × 10−7 M (signal/noise = 3). Meanwhile, the MnO2/VACNTs nanocomposite electrode is also highly resistant towards typical inorganic salts and some biomolecules such as acetic acid, citric acid, uric acid and d-(+)-glucose, etc. In addition, the sensor based on the MnO2/VACNTs nanocomposite electrode was applied for the determination of trace of H2O2 in milk with high accuracy, demonstrating its potential for practical application.  相似文献   

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