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1.
A new bean sprout peroxidase was immobilized on a gold electrode modified with self-assembled monolayers (SAM) of l-cysteine for the determination of dopamine in pharmaceutical samples using square wave voltammetry. In the bean sprout–(SAM)–Au electrode, the peroxidase, in the presence of hydrogen peroxide, catalyzes the oxidation of dopamine to the corresponding quinone, which is electrochemically reduced back to dopamine at +0.15 V vs. Ag/AgCl. The performance and the factors influencing the response of this biosensor were studied in detail. The best performance was obtained using 0.1 mol L−1 phosphate buffer solution (pH 6.0), 6.0 × 10−5 mol L−1 hydrogen peroxide, frequency of 100 Hz, pulse amplitude of 80 mV and scan increment of 4.0 mV. The analytical curve was linear for dopamine concentrations from 9.91 × 10−6 to 2.21 × 10−4 mol L−1 and the detection limit was 4.78 × 10−7 mol L−1. The recovery of dopamine ranged from 98.0 to 111.8% and the relative standard deviation was 3.1% for a solution containing 1.30 × 10−5 mol L−1 dopamine (n = 6). The lifetime of this biosensor was 15 days (at least 300 determinations). The results obtained for dopamine determination in pharmaceutical formulations using the proposed bean sprout–SAM–Au electrode were in agreement with those obtained with the standard method at the 95% confidence level.  相似文献   

2.
An electrochemical sensor for hydroperoxides determination was investigated. The sensor was based on the electrocatalytic reduction of hydroperoxides on Prussian blue (PB)-modified glassy carbon electrode. The modified electrode possesses a high electrocatalytic effect towards all studied peroxides with the highest effect obtained with H2O2 followed by tert-butyl hydroperoxide (TBH), cumene hydroperoxide (CH) and linoleic acid hydroperoxide (LAH). In addition, the modified electrode showed a good stability and a fast response time (<20 s). The lower detection limits of H2O2, TBH, CH and LAH were found to be 10−7 mol L−1, 2 × 10−7 mol L−1, 3.5 × 10−7 mol L−1 and 4 × 10−7 mol L−1, respectively. The electrochemical sensor was then applied for amperometric determination of peroxide value (PV) in edible oil at an applied potential of 50 mV (vs. Ag/AgCl (1 M KCl)). A good linearity has been found in the range 0.02–1.0 mequiv. O2/kg, with a detection limit (S/N = 3) of 0.001 mequiv. O2/kg. The precision of the method (R.S.D., n = 9) for within and between-days is better than 1.9% and 2.7%, respectively at 0.1 mequiv. O2/kg. The method was successfully applied to the determination of PV in real edible oil samples with an excellent agreement with results obtained with the official standard procedure. The proposed method is accurate, simple, cheap and could be used to control edible oil rancidity with a high sample throughputs (more than 120 samples/h).  相似文献   

3.
A disposable hydrogen peroxide biosensor was developed based on the direct electron transfer of myoglobin (Mb) on mesopores KIT-6 modified screen-printed electrode (SPE) which was manually performed to fabricate the planar carbon electrodes. KIT-6 is a new material which can absorb abundant of Mb molecules. A mixture of Mb and KIT-6 was immobilized with nafion on electrode. The cyclic voltammetry experiment indicated that a pair of stable and well-defined reduction peaks with a formal potentials of −0.35, and −0.28 V versus saturated calomel electrode (SCE) was obtained, using the present modified electrode in phosphate buffer saline (0.05 M, pH 7.0) at scan rate of 100 mV s−1, characteristic of Mb heme Fe(III)/Fe(II) redox couple. The heterogeneous electron transfer rate constant ks was estimated to be 16.93 s−1. And the formal potential was pH-dependent, having two slopes of −54.7 and −49.3 mV/pH which illustrated one electron transfer. This modified electrode was applied to detect H2O2 with sensitivity of 55.68 mA M−1 cm−2. Infrared spectrum and UV–vis absorption spectra of immobilized Mb film were recorded. In conclusion, KIT-6 increases the electron transfer activity of Mb and this kind of H2O2 biosensor is low cost for using disposable.  相似文献   

4.
The non-enzymatic voltammetric and amperometric detection of glucose using a gold nanowire array electrode is described. The voltammetric detection of glucose was performed by cyclic and differential-pulse voltammetry. The detection of glucose by partial and direct oxidation of glucose during the anodic and cathodic potential sweeps was shown in cyclic voltammetry. An unusual decrease in overpotential for partial oxidation of glucose on a Au NW array electrode was observed. A linear differential-pulse voltammetric response for partial oxidation of glucose was observed up to a glucose concentration of at least 20 mM with a sensitivity of 41.9 μA mM−1 cm−2 and detection limit below 30 μM (signal-to-noise ratio of 3) for glucose oxidation at low potentials, where the influence of possible intermediates can be avoided. The amperometric response was also linear up to a glucose concentration of 10 mM with a sensitivity of 309.0 μA mM−1 cm−2. The wide dynamic range and high sensitivity, selectivity and stability, as well as good biocompatibility of the Au NW electrode make it promising for the fabrication of non-enzymatic glucose sensors.  相似文献   

5.
R.  S.M.  K.   《Sensors and actuators. B, Chemical》2007,120(2):745-753
The glassy carbon electrode (GCE) modified with Mo(CN)84−-incorporated-poly(4-vinylpyridine) (PVP/Mo(CN)84−), which has been recently shown to possess several attractive attributes as an efficient electrocatalytic electrode for l-ascorbic acid oxidation and its estimation, is used for l-ascorbic acid estimation directly in orange fruit juice and Celin tablet in a 0.1 M H2SO4 acid solution without any special treatment. Constant potential amperometry at 570 mV (saturated calomel electrode, SCE) in stirred solutions is used for this purpose. A good correlation is attained with the official titrametric method. To understand the possible electrocatalytic reaction mechanism for the electro-oxidation of l-ascorbic acid, calibration graphs over the range 1 × 10−5 to 1 × 10−2 mol dm−3 l-ascorbic acid are compared for the three electrodes, ca. PVP/Mo(CN)84−, undoped PVP, and GCE; the curvature at high ascorbic acid concentration for the PVP/Mo(CN)84− electrode is explained in terms of Michaelis–Menten (MM) saturation kinetics. The apparent MM constant (KM), the maximum catalytic current (iM), the complex decomposition rate constant (kc), and the heterogeneous modified electrode rate constant (kME) are calculated from three different approaches. A reasonably high value of ≈1 × 10−2 cm s−1 is obtained for kME, indicating efficient l-ascorbic acid mediation at the PVP/Mo(CN)84− electrode, thus accounting for quite a high sensitivity of this modified film electrode compared to several other modified electrodes.  相似文献   

6.
Glucose oxidase (GOx) was immobilized on entangled and high surface area carbon nanotubes (CNTs) grown on an alumina substrate, and direct electron transfer reaction between GOx and the electrode was revealed. Fe/MgO catalyst layer was spin-coated on the insulating alumina substrate and the CNT layer was grown on the catalyst by chemical vapor deposition of methane at 950 °C for 15 min. About 20–30 nm bundles of about 1 nm single-wall as well as 10 nm multiwall CNTs are formed. The redox process was surface-controlled and electron transfer coefficient and the rate constant were estimated to be 0.35 and 0.64 s−1, respectively. In addition GOx immobilized on CNT layer showed a linear response range between 12 and 62 μM of glucose concentration. A detection limit and sensitivity of 0.1 μM and 635 μA mM−1 cm−2, respectively, were obtained for the biosensor.  相似文献   

7.
A new amperometric ethanol sensor has been developed. The sensor uses the silicon nanowires covered with co-deposited palladium–nickel (Pd–Ni/SiNWs) as the working electrode. The detection of ethanol concentration is based on the response currents resulted from the electro-catalytic oxidation of ethanol. The performance of the sensor was characterized by cyclic voltammetry and fixed potential amperometry techniques. In 1 M KOH solution containing different ethanol concentrations, the sensor shows a good sensitivity of 7.48 mA mM−1 cm−2 and the corresponding detection limit (signal-to-noise ratio = 3) of 6 μM for cyclic voltammetry. Meanwhile, it also displays a sensitivity of 0.76 mA mM−1 cm−2 and the corresponding detection limit of 10 μM for fixed potential amperometry. The results demonstrate that the Pd–Ni/SiNWs electrodes are potential as the electrochemical integrated sensors for ethanol detection.  相似文献   

8.
Glucose oxidase (GOx) has been immobilized in platinum-multiwalled carbon nanotube-alumina-coated silica (Pt-MWCNT-ACS) nanocomposite modified glassy carbon electrode by adsorption to provide a novel amperometric glucose biosensor. The morphology, nature, and performance of the resulting GOx-Pt-MWCNT-ACS nanobiocomposite modified glassy carbon electrode were characterized by field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, cyclic voltammetry, and amperometry. The influence of various experimental conditions was examined for the determination of the optimum analytical performance. The optimized glucose biosensor displayed a wide linear range of up to 10.5 mM, a high sensitivity of 113.13 mA M−1 cm−2, and a response time of less than 5 s. The sensitivity for the determination of glucose at the GOx-Pt-MWCNT-ACS nanobiocomposite modified glassy carbon electrode is better than at common GOx-Pt-CNT nanobiocomposite modified electrodes. The proposed biosensor has good anti-interferent ability and long-term storage stability after coating with Nafion, and it can be used for the determination of glucose in synthetic serum.  相似文献   

9.
In this paper, DNA–Cu2+ complex was electrodeposited onto the surface of glassy carbon (GC) electrode, which fabricated a DNA–Cu2+/GC electrode sensor to detect H2O2 with nonenzyme. Cyclic voltammogram of DNA–Cu2+/GC electrode showed a pair of well-defined redox peaks for Cu2+/Cu+. Moreover, the electrodeposited DNA–Cu2+ complex exhibited excellent electrocatalytic behavior and good stability for the detection of H2O2. The effects of Cu2+ concentration, electrodeposition time and determination conditions such as pH value, applied potential on the current response of the DNA–Cu2+/GC electrode toward H2O2 were optimized to obtain the maximal sensitivity. The linear range for the detection of H2O2 is 8.0 × 10−7 M to 4.5 × 10−3 M with a high sensitivity of −40.25 μA mM−1, a low detection limit of 2.5 × 10−7 M and a fast response time of within 4 s. In addition, the sensor has good reproducibility and long-term stability and is interference free.  相似文献   

10.
A novel approach to construct a second-generation amperometric biosensor is described. The classical redox dye nile blue (NB) as mediator and horseradish peroxidase as a base enzyme were coimmobilized into the multiwalled carbon nanotubes (MWCNTs) modified ormosil matrix. Nafion was dispersed into the matrix to enhance the rate of the electron transfer and prevent the cracking of the ormosil film. The surface morphology of MWCNT/NB/NAF/HRP nanocomposite was characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS). Cyclic voltammetry and amperometry measurements were used to study and optimize the performance of the resulting peroxide biosensor. The apparent Michaelis–Menten constant was determined to be 1.1 mM. The effect of pH, applied potential and amount of the HRP enzyme on the electrochemical biosensor has been systematically studied. The fabricated biosensor demonstrated significant electrocatalytic activity for the reduction of hydrogen peroxide with wide linear range from 2 × 10−7 to 3.8 × 10−4 M, and low detection limit 1 × 10−7 M (S/N = 3) with fast response time <3 s. The facile procedure of immobilizing HRP and MWCNTs into the ormosil used in the present work can promote the development of electrochemical research for enzymes, proteins, biosensors, biofuel cells and other bioelectrochemical devices.  相似文献   

11.
A novel biocompatible polyquaternium (QY)-manganese oxide nanosheet (MNS) nanocomposite has been prepared and shown to be a promising matrix for horseradish peroxidase (HRP) immobilization. The resulting HRP-QY-MNS film was characterized by Fourier transform infrared (FTIR) and circular dichroism (CD) spectroscopy, which indicated that HRP retained its native structure in the nanocomposite film. An HRP-QY-MNS film-modified glassy carbon electrode exhibited a pair of well-defined and quasi-reversible cyclic voltammetric peaks centered at −0.272 V (vs. Ag/AgCl) in pH 7.0 phosphate buffer solution. The direct electrochemical behavior of HRP was greatly enhanced in the QY-MNS nanocomposite film compared with that in single-component QY or MNS films. The immobilized HRP showed excellent electrocatalysis in the reduction of hydrogen peroxide (H2O2), which was exploited in the construction of an H2O2 biosensor. The linear range of the biosensor for H2O2 was found to be from 1.0 × 10−7 to 3.2 × 10−5 M with a correlation coefficient of 0.998. The detection limit was 7.8 × 10−8 M at a signal-to-noise ratio of 3. The biosensor exhibited rapid response and good long-term stability.  相似文献   

12.
A simple and highly sensitive method is described for direct voltammetric determination of noscapine in blood and pharmaceutical sample. Glassy carbon electrode with effective method is modified with multiwall carbon nanotubes (MWNTs) to cause activation of multiwall carbon nanotubes structures for electrocatalyzes of noscapine oxidation. The cyclic voltammetric (CV) results indicated that MWNTs remarkably enhances electrocatalytic activity toward the oxidation of noscapine, which is leading to considerable improvement of anodic peak current for noscapine, and allows the development of a highly sensitive voltammetric sensor for detection of noscapine in pharmaceutical and clinical samples. Under the optimum condition, the calibration curve was linear in the concentration range 4.0 × 10−7–1.0 × 10−4 mol L−1 with the detection limit of 8.0 × 10−8 mol L−1 and relative standard deviation (R.S.D.%) lower than 1.0% (n = 5). Finally, some kinetic parameters were determined and multistep mechanism for oxidation of noscapine for first time was proposed.  相似文献   

13.
A carbon ionic liquid electrode (CILE) was constructed using graphite powder mixed with N-butylpyridinium hexafluorophosphate (BPPF6) in place of paraffin as the binder, which showed strong electrocatalytic activity to the direct oxidation of catechol. In pH 3.0 phosphate buffer solution (PBS) a pair of redox peaks appeared on the CILE with the anodic and the cathodic peak potential located at 387 and 330 mV (vs. SCE), respectively. The electrochemical behaviors of catechol on the CILE were carefully investigated, and the electrochemical parameters were calculated with the results of the electrode reaction standard rate constant ks as 1.27 s−1, the charge-transfer coefficient α as 0.58 and the electron transferred number n as 2. Under the selected conditions, the anodic peak current increased linearly with the catechol concentration over the range from 1.0 × 10−6 to 8.0 × 10−4 mol L−1 by cyclic voltammetry at the scan rate of 100 mV s−1. The detection limit was calculated as 6.0 × 10−7 mol L−1 (3σ). The CILE showed good ability to separate the electrochemical responses of catechol and ascorbic acid (AA) with the anodic peak potential separation as 252 mV (vs. SCE). The proposed method was further applied to the synthetic samples determination with satisfactory results.  相似文献   

14.
The catechol biosensor is constructed by cross-linking between polyphenol oxidase (PPO) and polyaniline (PANI) using glutaraldehyde as a cross-linking agent. The PANI, which is electrochemically synthesized in a solution containing ionic liquid, 1-ethyl-3-methylimidazolium ethyl sulfate, possesses good electroactivity and high conductivity above pH 6. In the presence of catechol as a substrate, the biosensor exhibits a linear range from 0.2 to 80 μmol dm−3. The maximum response current (Imax) and the Michaelis–Menten constant (km) are 9.44 μA and 117 μmol dm−3, respectively. The effects of pH and operating potential are also explored to optimize measurement conditions. The activation energy (Ea) of the PPO catalytic reaction is 30.23 kJ mol−1 in the B–R buffer. Electrochemical impedance spectroscopy (EIS), UV–vis and SEM are used to characterize the PANI–PPO biosensor. The biosensor exhibits good long-term stability.  相似文献   

15.
Cytochrome c (cyt c) was immobilized into a matrix consisting of polyaniline (PANI) and multi-walled carbon nanotubes (MWNT) by a new strategy. First, PANI chains were grafted onto MWNT through electropolymerization. Second, the amine groups in PANI chains were oxidized at an applied potential of +0.80 V to acquire positive charges that would effectively immobilize negatively charged cyt C. The ITO/MWNT-g-PANI(O)/cyt c electrode exhibited a pair of redox peaks with a peak potential separation (anodic to cathodic) of 0.25 V (vs Ag/AgCl) in 0.1 M phosphate buffer (pH 7.0). The results demonstrated that ITO/MWNT-g-PANI(O)/cyt c promoted direct electron transfer between cyt c and electrode with a high electron transfer rate constant (17 s−1). The ITO/MWNT-g-PANI(O)/cyt c electrode catalyzes the reduction of H2O2. The ITO/MWNT-g-PANI(O)/cyt c biosensor displays an amperometric response to H2O2 with a linear concentration range from 0.5 μM to 1.5 mM (r = 0.99, n = 12), a high sensitivity (32.2 μAm M−1) and fast response (9 s) and detection limit of 0.3 μM (S/N = 3).  相似文献   

16.
In this article potential and suitability of enzymatically synthesized conducting polymers polyaniline (PANI) and polypyrrole (PPY) for fabrication of enzymatic amperometric glucose biosensors were evaluated. The polymerisation of these polymers was induced by catalytic activity of glucose oxidase (GOx) from Penicillium vitale cross-linked by glutaraldehyde (GA) on the graphite rod electrode (GOx-electrode) surface. The main precursors for initiation of polymerisation reactions were hydrogen peroxide as an initiator of polymerisation reaction and β-d-gluconic acid as a medium, which reduced the pH towards acidic one is the most suitable for the formation of PANI and PPY. During the polymerisation reactions the immobilized GOx was self-encapsulated within formed PANI or PPY layers in order to form GOx/PANI- and GOx/PPY-modified electrodes (GOx/PANI-electrode and GOx/PPY-electrode, respectively). Kinetic properties of GOx, which is acting as a biocatalyst in GOx/PANI- and GOx/PPY-electrodes, were studied and results were compared with GOx-electrode. The results show that in both GOx/PANI- and GOx/PPY-electrodes self-encapsulated GOx exhibited different parameters of catalysed reaction kinetics due to increasing diffusion limitations if compared with that of the GOx-electrode and it allowed the detection of glucose in a wider concentration interval. Moreover, both GOx/PANI- and GOx/PPY-electrodes exhibited good operational stability and reproducibility of analytical signal. The electrochemical characteristics of formed PANI and PPY in the GOx/PANI- and GOx/PPY-electrodes were also determined. In addition, the influence of temperature, pH and common interfering compounds on the steady-state current response of modified electrodes were investigated and discussed.  相似文献   

17.
The preparation and electrochemical performance of the carbon nanotube-paste electrode modified with salophen complexes of cobalt(III) perchlorate, with various substituents on the salophen ligand, as well as their electrocatalytic activity toward the oxidation of N-acetylcysteine (NAC) is investigated. Several Schiff base complexes containing various nucleophilic and electrophilic functional groups were prepared, and their electrochemical characteristics for the electro-oxidation of NAC were evaluated using cyclic and differential pulse voltammetry (CV and DPV). The results revealed, the modified electrodes show an efficient and selective electrocatalytic activity toward the anodic oxidation of NAC among biologically important compounds in buffered solutions at pH of 7.0. The best voltammetric responses were obtained for a carbon-paste electrode (CPE) modified with a salophen complex containing para-methoxy groups on its salicylaldehyde ring. The analytical response of the modified electrode for response to other sulfhydryl compounds (e.g., cysteine, penicillamine, captopril and mercaptopropionyl glycine) in comparison to NAC was investigated by CV and DPV methods. The DPV method was applied as a sensitive method for the quantitative detection of the trace amounts of NAC. A linear dynamic range from 1 × 10−7 to 1 × 10−4 M with calibration sensitivity of 0.0646 μA/μM is resulted for NAC in DPV measurements. The detection limit was 5 × 10−8 M, which is remarkably lower than those reported previously for NAC using other modified electrodes. The results of voltammetric determinations show a very good reproducibility, and the R.S.D. for the slope of the calibration curve, based on 10 measurements in a period of two months, was <3.9%. The detection system provides very stable electrochemical responses toward NAC, makes it very suitable for using in pharmaceutical and clinical measurements.  相似文献   

18.
A one-step enzyme immobilization process with silica sol–gel/polyvinyl alcohol was described to achieve direct electrochemistry of glucose oxidase on screen-printed electrodes. The immobilized glucose oxidase displays a couple of stable and well-defined redox peaks with an electron transfer rate constant of 8.38 s−1 and a formal potential of −460 mV (versus SCE) in phosphate buffer (0.05 M, pH 7.0) at a scan rate of 300 mV s−1. The results suggested that conformation and bioactivity of glucose oxidase could be retained efficiently using the proposed immobilization method and the porous structure of screen-printed electrode surface was helpful for electron communication of glucose oxidase and the electrode. Furthermore, the modified electrode was used as a glucose biosensor, exhibiting a linear response to glucose concentration ranging from 0 to 4.13 mM and a sensitivity of 3.47 μA mM−1 cm−2 at an applied potential of −0.5 V. The detection limit of the biosensor is 9.8 μM, based on a signal-to-noise ratio of 3. The present work provided a promising strategy for fabricating a novel and disposable mediatorless glucose biosensor, which could be mass-produced through further development.  相似文献   

19.
The development and application of a functionalized carbon nanotubes paste electrode (CNPE) modified with crosslinked chitosan for determination of Cu(II) in industrial wastewater, natural water and human urine samples by linear scan anodic stripping voltammetry (LSASV) are described. Different electrodes were constructed using chitosan and chitosan crosslinked with glutaraldehyde (CTS-GA) and epichlorohydrin (CTS-ECH). The best voltammetric response for Cu(II) was obtained with a paste composition of 65% (m/m) of functionalized carbon nanotubes, 15% (m/m) of CTS-ECH, and 20% (m/m) of mineral oil using a solution of 0.05 mol L−1 KNO3 with pH adjusted to 2.25 with HNO3, an accumulation potential of −0.3 V vs. Ag/AgCl (3.0 mol L−1 KCl) for 300 s and a scan rate of 100 mV s−1. Under these optimal experimental conditions, the voltammetric response was linearly dependent on the Cu(II) concentration in the range from 7.90 × 10−8 to 1.60 × 10−5 mol L−1 with a detection limit of 1.00 × 10−8 mol L−1. The samples analyses were evaluated using the proposed sensor and a good recovery of Cu(II) was obtained with results in the range from 98.0% to 104%. The analysis of industrial wastewater, natural water and human urine samples obtained using the proposed CNPE modified with CTS-ECH electrode and those obtained using a comparative method are in agreement at the 95% confidence level.  相似文献   

20.
The measurement of ascorbic acid (AA), uric acid (UA) and xanthine (XA) is very important in the clinical diagnosis because many diseases have been found to be associated with their concentrations. Herein, an electrochemical sensor using mesoporous SiO2 as sensing material was firstly developed for the simultaneous detection of AA, UA and XA. With distinctive properties such as uniform porous networks, large surface area and high sorption ability, the mesoporous SiO2 sensor exhibits remarkable surface enhancement effect, and greatly increases the response signals of AA, UA and XA. In addition, the electrochemical responses of coexistence of AA, UA and XA were studied, and three well-shaped oxidation peaks were observed at 0.00, 0.25 and 0.63 V. Further studies suggest that their oxidation takes place independently and has no mutual interference. This sensor possesses high sensitivity, and the limit of detections are 3.0 × 10−6 mol L−1, 1.0 × 10−7 mol L−1 and 7.5 × 10−7 mol L−1 for AA, UA and XA. Finally, the mesoporous SiO2 sensor was successfully employed to detect AA, UA and XA in the urine and blood serum samples.  相似文献   

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