We describe a square wave anodic stripping voltammetric (SWASV) platform for the determination of Cu(II). It is based on the use of amino-reduced graphene oxide (NH2-rGO) and β-cyclodextrin (β-CD) that were self-assembled on the surface of a glassy carbon electrode (GCE). The hydrophilicity and electrochemical performance of the resulting modified GCE were investigated by measurement of static contact angles, cyclic voltammetry and electrochemical impedance spectroscopy. Cu(II) was reduced at −1.1 V and then reoxidized at −0.012 V. Under optimum experimental conditions, the modified GCE exhibited excellent SWASV response in that the stripping peak currents (when sweeping between −0.3 and +0.25 V) depends on the concentration of Cu(II) in the 30 nM to 100 μM range. The limit of detection is 2.8 nM (at 3σ/slope). The modified GCE displaying good reproducibility, is stable, highly sensitive and selective. It was successfully applied to the determination of Cu(II) in synthetic and real water samples. The fast electron transfer rate and simple preparation of the NH2-rGO/β-CD composite makes it a promising electrode material for applications in sensing of heavy metal ions.
相似文献Thin-layered molybdenum disulfide (MoS2) was intercalated, via ultrasonic exfoliation, into self-doped polyaniline (SPAN). This material, when placed on a glassy carbon electrode (GCE), exhibits excellent electrical conductivity and synergistic catalytic activity with respect to the detection of bisphenol A (BPA). The electrochemical response of the modified GCE to BPA was investigated by cyclic voltammetry and differential pulse voltammetry. Under optimal conditions, the oxidation peak current (measured best at 446 mV vs. SCE) is related to the concentration of BPA in the range from 1.0 nM to 1.0 μM, and the detection limit is 0.6 nM.
相似文献We describe an electrochemical sensor for simultaneous determination of hydroquinone (HQ) and catechol (CC). A glassy carbon electrode (GCE) was modified with gold nanoparticles, L-cysteine, and ZnS/NiS@ZnS quantum dots using a layer-by-layer technique. The materials were characterized by X-ray diffractometry, field emission scanning electron microscopy, and electrochemical impedance and Fourier transform infrared spectroscopy. Cyclic voltammetry and differential pulse voltammetry revealed this modified GCE to represent a highly sensitive sensor for the simultaneous determination of HQ and CC. The anodic peak current for HQ at a working voltage of 80 mV (vs. Ag/AgCl) is related to its concentration in the 0.1 to 300 μM range (even in the presence of 0.1 mM of CC). The anodic peak current for CC at a working voltage of 184 mV is related to its concentration in the 0.5 to 400 μM range (even in the presence of 0.1 mM of HQ). The detection limits (at an S/N ratio of 3) are 24 and 71 nM for HQ and CC, respectively. The modified GCE was successfully applied to the determination of HQ and CC in aqueous solutions and gave satisfactory results.
相似文献Reduced graphene oxide (RGO) was used to construct a bienzyme biosensor containing horseradish peroxidase (HRP) and glucose oxidase (GOx). A poly(toluidine blue) (pTB) film containing RGO acted as both enzyme immobilization matrix and electron transfer mediator. The bienzyme biosensor was characterized by electrochemical techniques and displays a highly sensitive amperometric response to glucose and hydrogen peroxide (H2O2) at a potential as low as −0.1 V (vs. SCE). It is shown that use of RGO causes a strong enhancement on the amperometric responses. H2O2 formed by the action of GOx in the presence of oxygen can be further reduced by HRP in the pTB film contacting the RGO modified electrode. In the absence of oxygen, glucose oxidation proceeds by another mechanism in which electron transfer occurs from GOx to the electrode and with pTB acting as the mediator. Amperometric responses to glucose and H2O2 follow Michaelis-Menten kinetics. The experimental conditions were optimized, and under these conditions glucose can be determined in the 80 μM to 3.0 mM range with a detection limit of 50 μM. H2O2, in turn, can be quantified in up to 30.0 μM concentration with a detection limit of 0.2 μM. The bienzyme biosensor is reproducible, repeatable and stable. Finally, it has been successfully applied to the determination of glucose in plasma samples.
相似文献Alloy nanoparticles of the type PtxFe (where x is 1, 2 or 3) were synthesized by coreduction with sodium borohydride in the presence of carbon acting as a chemical support. The resulting nanocomposites were characterized by scanning electron microscopy and X-ray diffraction. The nanocomposite was placed on a glassy carbon electrode, and electrochemical measurements indicated an excellent catalytic activity for the oxidation of glucose even a near-neutral pH values and at a working voltage as low as 50 mV (vs. SCE). Under optimized conditions, the sensor responds to glucose in the 10.0 μM to 18.9 mM concentration range and with a 3.0 μM detection limit (at an S/N ratio of 3). Interferences by ascorbic acid, uric acid, fructose, acetamidophenol and chloride ions are negligible.
相似文献We are presenting an electrochemical immunosensor for the determination of the β-agonist and food additive ractopamine. A glassy carbon electrode (GCE) was modified with gold nanoparticles and a film of a composite made from poly(arginine) and multi-walled carbon nanotubes. Antibody against ractopamine was immobilized on the surface of the modified GCE which then was blocked with bovine serum albumin. The assembly of the immunosensor was followed by electrochemical impedance spectroscopy. Results demonstrated that the semicircle diameter increases, indicating that the film formed on the surface hinders electron transfer due to formation of the antibody-antigen complex on the modified electrode. Under optimal conditions, the peak current obtained by differential pulse voltammetry decreases linearly with increasing ractopamine concentrations in the 0.1 nmol•L−1 to 1 μmol•L−1 concentration range. The lower detection limit is 0.1 nmol•L−1. The sensor displays good stability and reproducibility. The method was applied to the analysis of spiked swine feed samples and gave satisfactory results.
相似文献We describe the electrochemical preparation of bismuth nanoribbons (Bi-NRs) with an average length of 100 ± 50 nm and a width of 10 ± 5 μm by a potentiostatic method. The process occurs on the surface of a glassy carbon electrode (GCE) in the presence of disodium ethylene diamine tetraacetate that acts as a scaffold for the growth of the Bi-NRs and also renders them more stable. The method was applied to the preparation of Bi-NRs incorporated into reduced graphene oxide. This nanocomposite was loaded with the enzyme glucose oxidase onto a glassy carbon electrode. The resulting biosensor displays an enhanced redox peak for the enzyme with a peak-to-peak separation of about 28 mV, revealing a fast electron transfer at the modified electrode. The loading of the GCE with electroactive GOx was calculated to be 8.54 × 10−10 mol∙cm−2, and the electron transfer rate constant is 4.40 s−1. Glucose can be determined (in the presence of oxygen) at a relatively working potential of −0.46 V (vs. Ag|AgCl) in the 0.5 to 6 mM concentration range, with a 104 μM lower detection limit. The sensor also displays appreciable repeatability, reproducibility and remarkable stability. It was successfully applied to the determination of glucose in human serum samples.
相似文献Titanium dioxide nanorods (TNR) were grown on a titanium electrode by a hydrothermal route and further employed as a supporting matrix for the immobilization of nafion-coated horseradish peroxidase (HRP). The strong electrostatic interaction between HRP and TNR favors the adsorption of HRP and facilitates direct electron transfer on the electrode. The electrocatalytic activity towards hydrogen peroxide (H2O2) was investigated via cyclic voltammetry and amperometry. The biosensor exhibits fast response, a high sensitivity (416.9 μA·mM−1), a wide linear response range (2.5 nM to 0.46 mM), a detection limit as low as 12 nM, and a small apparent Michaelis-Menten constant (33.6 μM). The results indicate that this method is a promising technique for enzyme immobilization and for the fabrication of electrochemical biosensors.
相似文献We are presenting a sensor for hydrogen peroxide (H2O2) that is based on the use of a heterostructure composed of Pt nanoparticles (NPs) and carbon nanofibers (CNFs). High-density Pt NPs were homogeneously loaded onto a three-dimensional nanostructured CNF matrix and then deposited in a glassy carbon electrode (GCE). The resulting sensor synergizes the advantages of the conducting CNFs and the nanoparticle catalyst. The porous structure of the CNFs also favor the high-density immobilization of the NPs and the diffusion of water-soluble molecules, and thus assists the rapid catalytic oxidation of H2O2. If operated at a working voltage of −0.2 V (vs. Ag/AgCl), the modified GCE exhibits a linear response to H2O2 in the 5 μM to 15 mM concentration range (total analytical range: 5 μM to 100 mM), with a detection limit of 1.7 μM (at a signal-to-noise ratio of 3). The modified GCE is not interfered by species such as uric acid and glucose. Its good stability, high selectivity and good reproducibility make this electrode a valuable tool for inexpensive amperometric sensing of H2O2.
相似文献We describe a new kind of electrochemical immunoassay for the peptide hormone prolactin. A glassy carbon electrode (GCE) was modified with a hybrid material consisting of graphene, single walled carbon nanotubes and gold nanoparticles (AuNPs) in a chitosan (CS) matrix. The graphene and the single wall carbon nanotubes were first placed on the GCE, and the AuNPs were then electrodeposited on the surface by cyclic voltammetry. This structure results in a comparably large surface for immobilization of the capturing antibody (Ab1). The modified electrode was used in a standard sandwich-type of immunoassay. The secondary antibody (Ab2) consisted of AuNPs with immobilized Ab2 and modified with biotinylated DNA as signal tags. Finally, alkaline phosphatase was bound to the biotinylated DNA-AuNPs-Ab2 conjugate via streptavidin chemistry. The enzyme catalyzes the hydrolysis of the α-naphthyl phosphate to form α-naphthol which is highly electroactive at an operating voltage as low as 180 mV (vs. Ag/AgCl). The resulting immunoassay exhibits high sensitivity, wide linear range (50 to 3200 pg∙mL‾1), low detection limit (47 pg∙mL‾1), acceptable selectivity and reproducibility. The assay provides a pragmatic platform for signal amplification and has a great potential for the sensitive determination of antigens other than prolactine.
相似文献We report on a new electrochemical immunosensor for the carcinoembryonic antigen (CEA; a model analyte). First, poly(o-phenylenediamine) nanospheres (PPDNSs) were synthesized by using a wet-chemistry method. The nanospheres were utilized as the support for immobilizing horseradish peroxidase-labeled polyclonal rabbit anti-human CEA antibody (HRP-anti-CEA) on a pretreated glassy carbon electrode (GCE) using glutaraldehyde as a crosslinker. In the presence of target CEA, an antigen-antibody immunocomplex formed on the electrode. This results in a partial inhibition of the active center of HRP and decreases the activity of HRP in terms of H2O2 reduction. The performance and factors influencing the performance of the immunoelectrode were studied. Under optimal conditions, the reduction current obtained from the anti-CEA-conjugated HRP (best at a working voltage of −265 mV vs. Ag/AgCl) is proportional to the CEA concentration in the 0.01 to 60 ng mL−1 range, with a detection limit of 3.2 pg mL−1. Non-specific adsorption was not observed. Relative standard deviations for intra-assay and inter-assay are <8.3 % and <9.7 %, respectively. The method was applied to the analysis of nine human serum samples, and a good relationship was found between the electrochemical immunoassay and the commercialized ELISA kit for human CEA.
相似文献An ultrasensitive electrochemical glucose biosensor has been developed by depositing C60-fullerene functionalized with tetraoctylammonium bromide (C60-TOAB+) on the surface of a glassy carbon electrode (GCE). The glucose-binding protein concanavalin A (Con A) was then linked to the surface. Binding of glucose by Con A affects the electroactivity of the reversible redox couple C60/C60 −, and this finding forms the basis for a quantitative glucose assay over the 10 to 10 mM concentration range and with a lower detection limit of 3.3 nM (at an S/N ratio of 3). The sensitivity of this sensor allowed glucose to be determined in saliva. This biosensor possesses excellent selectivity, outstanding reproducibility and good long-term stability.
相似文献We have developed a method for in-situ construction of a porous network-like silver film on the surface of a glassy carbon electrode (GCE). It is based on a galvanic replacement reaction where a layer of copper nanoparticles is first electrodeposited as a sacrificial template. The silver film formed possesses a porous network-like structure and consists of an assembly of numerous nanoparticles with an average size of 200 nm. The electrode displays excellent electrocatalytic activity, good stability, and fast response (within 2 s) toward the reduction of nitrate at a working potential of −0.9 V. The catalytic currents linearly increase with the nitrate concentrations in the range of 0.08–6.52 mM, with a detection limit of 3.5 μM (S/N = 3) and a repeatability of 3.4 % (n = 5).
相似文献We describe an electrochemical sensor for melamine based on a glassy carbon electrode (GCE) modified with reduced graphene oxide that was decorated with gold nanoparticles (AuNP/rGO). The AuNPs/rGO nanocomposite was synthesized by co-reduction of Au(III) and graphene oxide and characterized by transmission electron microscopy, Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The response of the modified GCE to melamine was investigated by using hexacyanoferrate as an electrochemical reporter. It is found that the electrochemical response to hexacyanoferrate is increasingly suppressed by increasing concentration of melamine. This is attributed to competitive adsorption of melamine at the AuNP/rGO composite through the interaction between the amino groups of melamine and the AuNPs. The presence of rGO, in turn, provides a platform for a more uniform distribution of the AuNPs and enhances the electron transfer rate of the redox reaction. The findings were used to develop a sensitive method for the determination of melamine. Under optimized conditions, the redox peak current of hexacyanoferrate at a working voltage of 171 mV (vs. SCE) is linearly related to the concentration of melamine in 5.0 to 50 nM range. The method was successfully applied to the determination of melamine in food contact materials.
相似文献We have synthesized nitrogen-doped graphene nanoribbons (N-GrNRs) by unzipping multi-walled carbon nanotubes (CNTs) under strongly oxidizing conditions and subsequent doping with nitrogen by a low-temperature hydrothermal method. The N-GNRs were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy, and assembled on a disposable screen-printed carbon electrode to give a sensor for H2O2 that was characterized by cyclic voltammetry, electrochemical impedance spectroscopy, chronocoulometry and chronoamperometry. The nano-modified electrode displays enhanced electron transfer ability, and has a large active surface and a large number of catalytically active sites that originate from the presence of nitrogen atoms. This results in a catalytic activity towards H2O2 reduction at near-neutral pH values that is distinctly improved compared to electrodes modified with CNTs or unzipped (non-doped) CNTs only. At a working potential of −0.4 V (vs. Ag/AgCl), the amperometric responses to H2O2 cover the 5 to 2785 μM concentration range, with a limit of detection as low as 1.72 μM. This enzyme-free electrochemical sensor exhibits outstanding selectivity and long-term stability for H2O2 detection.
相似文献Hemoglobin (Hb) has been demonstrated to endow electrochemical sensors with pH-switchable response because of the presence of carboxyl and amino groups. Hb was deposited in a chitosan matrix on a glassy carbon electrode (GCE) that was previously coated with clustered gold nanoparticles (Au-NPs) by electrodeposition. The switching behavior is active (“on”) to the negatively charged probe [Fe(CN)6 3−] at pH 4.0, but inactive (“off”) to the probe at pH 8.0. This switch is fully reversible by simply changing the pH value of the solution and can be applied for pH-controlled reversible electrochemical reduction of H2O2 catalyzed by Hb. The modified electrode was tested for its response to the different electroactive probes. The response to these species strongly depends on pH which was cycled between 4 and 8. The effect is also attributed to the presence of pH dependent charges on the surface of the electrode which resulted in either electrostatic attraction or repulsion of the electroactive probes. The presence of Hb, in turn, enhances the pH-controllable response, and the electrodeposited Au-NPs improve the capability of switching. This study reveals the potential of protein based pH-switchable materials and also provides a simple and effective strategy for fabrication of switchable chemical sensors as exemplified in a pH-controllable electrode for hydrogen peroxide.
相似文献We describe an anodic stripping voltammetric (ASV) method for glucose sensing that widely expands the typical amperometric i-t response of glucose sensors. The electrode is based on a working electrode consisting of a glassy carbon electrode modified with Pt-Pd nanoparticles (NPs; in an atomic ratio of 3:1) on a reduced graphene oxide (rGO) support. The material was prepared via the spontaneous redox reaction between rGO, PdCl4 2− and PtCl4 2− without any additional reductant or surfactant. Unlike known Pt-based sensors, the use of Pt3Pd NPs results in an ultrasensitive ASV approach for sensing glucose even at near-neutral pH values. If operated at a working voltage as low as 0.06 V (vs. SCE), the modified electrode can detect glucose in the 2 nM to 300 μM concentration range. The lowest detectable concentration is 2 nM which is much lower than the LODs obtained with other amperometric i-t type sensing approaches, most of which have LODs at a μM level. The sensor is not interfered by the presence of 0.1 M of NaCl.
相似文献Novel nanocomposites were prepared from graphene oxide (GO) and octahedral tin dioxide (SnO2) through a facile process that included synthesis of octahedral SnO2 and the reduction of GO with ascorbic acid. The morphology and structure of the nanocomposites were characterized by UV–vis spectroscopy, transmission electron microscopy, and Raman spectroscopy. The nanocomposites were placed on a glassy carbon electrode where they displayed excellent performance in terms of differential pulse voltammetric determination of dopamine (DA). This is attributed to (a) the synergetic interactions between reduced graphene oxide (r-GO) and octahedral SnO2, and (b) the presence of a large number of active sites on the nanocomposites surface. The sensor responds to DA in the concentration range of 0.08 to 30 μM, with a 6 nM detection limit if operated at 0.24 V (vs. Ag/AgCl). The modified electrode also widely suppresses the background current resulting from excess ascorbic acid and uric acids. The method was applied to the determination of DA in spiked human urine and gave satisfactory results, with recoveries in the range from 96.4 to 98.2 %.
相似文献We have studied the direct electrochemistry of glucose oxidase (GOx) immobilized on electrochemically fabricated graphite nanosheets (GNs) and zinc oxide nanoparticles (ZnO) that were deposited on a screen printed carbon electrode (SPCE). The GNs/ZnO composite was characterized by using scanning electron microscopy and elemental analysis. The GOx immobilized on the modified electrode shows a well-defined redox couple at a formal potential of −0.4 V. The enhanced direct electrochemistry of GOx (compared to electrodes without ZnO or without GNs) indicates a fast electron transfer at this kind of electrode, with a heterogeneous electron transfer rate constant (Ks) of 3.75 s−1. The fast electron transfer is attributed to the high conductivity and large edge plane defects of GNs and good conductivity of ZnO-NPs. The modified electrode displays a linear response to glucose in concentrations from 0.3 to 4.5 mM, and the sensitivity is 30.07 μA mM−1 cm−2. The sensor exhibits a high selectivity, good repeatability and reproducibility, and long term stability.
相似文献