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1.
A simple procedure was developed to prepare a glassy carbon (GC) electrode modified with single wall carbon nanotubes (SWCNTs) and phenazine derivative of Mn-complex. With immersing the GC/CNTs modified electrode into Mn-complex solution for a short period of time 20–100 s, a stable thin layer of the complex was immobilized onto electrode surface. Modified electrode showed a well defined redox couples at wide pH range (1–12). The surface coverages and heterogeneous electron transfer rate constants (ks) of immobilized Mn-complex were approximately 1.58 × 10−10 mole cm−2 and 48.84 s−1. The modified electrode showed excellent electrocatalytic activity toward H2O2 reduction. Detection limit, sensitivity, linear concentration range and kcat for H2O2 were, 0.2 μM and 692 nA μM−1 cm−2, 1 μM to 1.5 mM and 7.96(±0.2) × 103 M−1 s−1, respectively. Compared to other modified electrodes, this electrode has many advantageous such as remarkable catalytic activity, good reproducibility, simple preparation procedure and long term stability.  相似文献   

2.
A novel platform, which hemoglobin (Hb) was immobilized on core–shell structurally Fe3O4/Au nanoparticles (simplified as Fe3O4@Au NPs) modified glassy carbon electrode (GCE), has been developed for fabricating the third biosensors. Fe3O4@Au NPs, characterized using transmission electron microscope (TEM), scanning electron microscope (SEM) and energy dispersive spectra (EDS), were coated onto GCE mediated by chitosan so as to provide larger surface area for anchoring Hb. The thermodynamics, dynamics and catalysis properties of Hb immobilized on Fe3O4@Au NPs were discussed by UV–visible spectrum (UV–vis), electrochemical impedance spectroscopy (EIS), electrochemical quartz crystal microbalance technique (EQCM) and cyclic voltammetry (CV). The electrochemical parameters of Hb on Fe3O4@Au NPs modified GCE were further carefully calculated with the results of the effective working area as 3.61 cm2, the surface coverage concentration (Γ) as 1.07 × 10−12 mol cm−2, the electron-transfer rate constant (Ks) as 1.03 s−1, the number of electron transferred (n) as 1.20 and the standard entropy of the immobilized Hb (ΔS0′) as calculated to be −104.1 J mol−1 K−1. The electrocatalytic behaviors of the immobilized Hb on Fe3O4@Au NPs were applied for the determination of hydrogen peroxide (H2O2), oxygen (O2) and trichloroacetic acid (TCA). The possible functions of Fe3O4 core and Au shell as a novel platform for achieving Hb direct electrochemistry were discussed, respectively.  相似文献   

3.
Nano-γ-Al2O3 is dispersed onto the glass carbon electrode (GCE) by polishing. This nanostructured modified GCE exhibits a great enhancement to the redox responses of 3-nitrobenzaldehyde thiosemicarbazone (3-NBT). In comparison with bare GCE, 3-NBT gives a more sensitive voltammetric response because of the nanoparticle’s unique properties. The lowest detectable concentration (3σ) of 3-NBT is estimated to be 1.18 × 10−6 M (accumulation for 4 min). The linear relationship between peak current and concentration of 3-NBT holds in the range 1.0 × 10−5 M to 1.0 × 10−4 M (r = 0.9981). The electrochemical properties of 3-NBT on this modified electrode have been investigated with various electrochemical methods. The results indicate that the transference of one electron and one proton involves electrode radical reaction processes I and II, respectively. The coverage value (Γ) of 1.62 × 10−9 mol cm−2 was calculated and the electrochemical parameters, diffusion coefficient D (2.54 × 10−3 cm2 s−1, 2.03 × 10−3 cm2 s−1) and reaction rate constant ks (5.9573 s−1, 7.15 × 10−2 cm s−1) were obtained for quasi-reversible system I and irreversible system II, respectively.  相似文献   

4.
Platinum nanoparticles (Ptnano) were prepared and used in combination with single-wall carbon nanotube (SWNT) for fabricating electrochemical sensors with remarkably improved sensitivity toward diethylstilbestrol (DES). The glassy carbon (GC) electrode modified with SWNT/Ptnano composite film exhibited excellent electrochemical behaviors toward the redox of DES. Compared with the bare GC electrode and SWNTs film modified GC electrode, the redox peak currents at the SWNTs/Ptnano composite film modified GC electrode was enhanced greatly. The experimental parameters, which influence the peak current of DES, were optimized. Under optimal conditions, a linear response of DES was obtained in the range from 1.0 × 10−7 to 2.0 × 10−5 mol L−1 (R = 0.997) and with a limit of detect (LOD) of 1.5 × 10−8 mol L−1. The proposed procedure was successfully applied to determine the active ingredient in the DES tablet with satisfactory results.  相似文献   

5.
A novel graphene oxide (GO)/Prussian blue (PB) hybrid film was constructed by electropolymerizing Prussian blue onto the GO modified glassy carbon electrode, and its electrochemical behaviors were studied. Raman spectra were used to investigate the successful formation of the GO/PB hybrid film. Electrochemical experiments showed that the graphene oxide greatly enhanced electrochemical reactivity of the PB. Moreover, a much higher Prussian blue (PB) loading (6.388 × 10−8 mol cm−2) is obtained as compared to the bare glass carbon surface (3.204 × 10−9 mol cm−2). The GO/PB hybrid film modified electrode was used for the sensitive detection of hydrogen peroxide. The sensor exhibited a wide linearity range from 5.0 × 10−6 to 1.2 × 10−3 M with a detection limit of 1.22 × 10−7 M (S/N = 3), high sensitivity of 408.7 μA mM−1 cm−2 and good reproducibility. Furthermore, with glucose oxidase (GOD) as a model, the GO/PB/GOD/chitosan composite-modified electrode was also constructed.The resulting biosensor exhibited good amperometric response to glucose with linear range from 0.1 to 13.5 mM at 0.1 V, good reproducibility and detection limit of 3.43 × 10−7 M (S/N = 3). In addition, the biosensor presented high selectivity and long-term stability. Therefore, the PB/GO hybrid films-based modified electrode may hold great promise for electrochemical sensing and biosensing applications.  相似文献   

6.
Diazonium ion chemistry has been used to electrochemically graft aminophenyl layers onto p-type silicon (1 0 0) substrates. A condensation reaction was used to immobilise single-walled carbon nanotubes with high carboxylic acid functionality directly to this layer. Electrochemical monitoring of the aminophenyl groups confirmed the formation of an amide linkage between the single-walled carbon nanotubes and the aminophenyl layer. The carbon nanotube electrode showed high stability and good electrochemical performance in aqueous solution. At moderate scan rates the Ru(NH3)6+3/+2 couple exhibited quasi-reversible electron transfer kinetics with a standard heterogenous rate constant of 1.2 × 10−3 cm s−1 at the covalently-linked carbon nanotube surface. The electrode thus combines the advantages of a silicon substrate for easy integration into sophisticated electrical and electronic devices, carbon nanotubes for desirable electrochemical properties, and stability in aqueous medium for future applications in environmental sensing.  相似文献   

7.
A multi-walled carbon nanotubes (MWCNTs) modified carbon ionic liquid electrode (CILE) was fabricated and used to investigate the electrochemical behavior of guanosine. CILE was prepared by mixing hydrophilic ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF4), graphite powder and liquid paraffin together. The fabricated MWCNTs/CILE showed great electrocatalytic ability to the oxidation of guanosine and an irreversible oxidation peak appeared at 1.067 V (vs. SCE) with improved peak current. The electrochemical behavior of guanosine on the MWCNTs/CILE was carefully studied by cyclic voltammetry and the electrochemical parameters such as the charge transfer coefficient (α) and the electrode reaction standard rate constant (ks) were calculated with the result as 0.66 and 2.94 × 10−4 s−1, respectively. By using differential pulse voltammetry (DPV) as the detection method, a linear relationship was obtained between the oxidation peak current and the guanosine concentration in the range from 1.0 × 10−7 to 4.0 × 10−5 mol/L with the detection limit as 7.8 × 10−8 mol/L (3σ). The common coexisting substances showed no interferences to the guanosine detection and the modified electrode showed good ability to distinguish the electrochemical response of guanosine and adenosine.  相似文献   

8.
A multiwall carbon nanotubes (MWNTs)-chitosan modified glassy carbon electrode (GCE) exhibits attractive ability for highly sensitive cathodic stripping voltammetric measurements of bromide (Br). In pH 1.8 H2SO4 solution, a substantial increase in the stripping peak current of Br (compared to bare GCE and chitosan modified GCE) is observed using MWNTs-chitosan modified electrode. Operational parameters were optimized and the electrochemical behaviors of Br were studied by different electrochemical methods. The kinetics parameters were measured, the number of electron transfer (n) was 1 and the transfer coefficient (α) is 0.17. A wide linear calibration range (3.6 × 10−7-1.4 × 10−5 g mL−1) was achieved, with a detection limit of 9.6 × 10−8 g mL−1. The mechanism of electrode reaction was fully discussed.  相似文献   

9.
Graphene–chitosan composite film modified glassy carbon electrode was prepared and characterized. The fabricated electrode showed excellent electrochemical catalytic activities towards the oxidation of catechol (CT), resorcinol (RS) and hydroquinone (HQ). The oxidation overpotentials of CT, RS and HQ decreased significantly and the corresponding oxidation currents increased remarkably compared with those obtained at the bare GCE and chitosan modified GCE. Some kinetic parameters, such as the electron transfer number (n), proton transfer number (m), charge transfer coefficient (α) and the apparent heterogeneous electron transfer rate constant (ks), were calculated. Differential pulse voltammetry was used for the simultaneous determination of CT, RS and HQ in their ternary mixture. The peak-to-peak potential separations between CT and RS, RS and HQ, and HQ and CT were 0.388, 0.484 and 0.096 V, respectively. The calibration curves for CT, RS and HQ were obtained in the range of 1 × 10−6 to 4 × 10−4, 1 × 10−6 to 5.5 × 10−4 and 1 × 10−6 to 3 × 10−4 mol L−1, respectively. The detection limits were 7.5 × 10−7 mol L−1 (S/N = 3).  相似文献   

10.
A new amperometric glucose biosensor has been developed based on platinum (Pt) nanoparticles/polymerized ionic liquid-carbon nanotubes (CNTs) nanocomposites (PtNPs/PIL-CNTs). The CNTs was functionalized with polymerized ionic liquid (PIL) through directly polymerization of the ionic liquid, 1-vinyl-3-ethylimidazolium tetrafluoroborate ([VEIM]BF4), on carbon nanotubes and then used as the support for the highly dispersed Pt nanoparticles. The electrochemical performance of the PtNPs/PIL-CNTs modified glassy carbon (PtNPs/PIL-CNTs/GC) electrode has been investigated by typical electrochemical methods. The PtNPs/PIL-CNTs/GC electrode shows high electrocatalytic activity towards the oxidation of hydrogen peroxide. Taking glucose oxidase (GOD) as the model, the resulting amperometric glucose biosensor shows good analytical characteristics, such as a high sensitivity (28.28 μA mM−1 cm−2), wide linear range (up to 12 mM) and low detection limit (10 μM).  相似文献   

11.
We have developed a polyaniline/carboxy-functionalized multiwalled carbon nanotube (PAn/MWCNTCOOH) nanocomposite by blending the emeraldine base form of polyaniline (PAn) and carboxy-functionalized multiwalled carbon nanotubes (MWCNT) in dried dimethyl sulfoxide (DMSO) at room temperature. The conductivity of the resulting PAn/MWCNTCOOH was 3.6 × 10−3 S cm−1, mainly as a result of the protonation of the PAn with the carboxyl group and the radical cations of the MWCNT fragments. Horseradish peroxidase (HRP) was immobilized within the PAn/MWCNTCOOH nanocomposite modified Au (PAn/MWCNTCOOH/Au) electrode to form HRP/PAn/MWCNTCOOH/Au for use as a hydrogen peroxide (H2O2) sensor. The adsorption between the negatively charged PAn/MWCNTCOOH nanocomposite and the positively charged HRP resulted in a very good sensitivity to H2O2 and an increased electrochemically catalytical current during cyclic voltammetry. The HRP/PAn/MWCNTCOOH/Au electrode exhibited a broad linear response range for H2O2 concentrations (86 μM–10 mM). This sensor exhibited good sensitivity (194.9 μA mM−1 cm−2), a fast response time (2.9 s), and good reproducibility and stability at an applied potential of −0.35 V. The construction of the enzymatic sensor demonstrated the potential application of PAn/MWCNTCOOH nanocomposites for the detection of H2O2 with high performance and excellent stability.  相似文献   

12.
The construction by sequential self-assembly process of reproducible, highly stable and pH-responsive redox-active nanostructured arrays of single-walled carbon nanotubes (SWCNTs) integrated with octa(hydroxyethylthio)phthalocyaninatoiron(II) (FeOHETPc) via ester bonds on a gold surface (Au-Cys-SWCNT-FeOHETPc) is investigated and discussed. The successful construction of this electrode is confirmed using atomic force microscopy and X-ray photoelectron spectroscopy as well as from the distinct cyclic voltammetric and electrochemical impedance spectroscopic profiles. The Au-Cys-SWCNT-FeOHETPc electrode exhibited strong dependence on the reaction of the head groups and the pH of the working electrolytes, the surface pKa is estimated as 7.3. The high electron transfer capability of the Au-Cys-SWCNT-FeOHETPc electrode over other electrodes (Au-Cys-SWCNT or the Au-Cys-FeOHETPc or the Au-FeOHETPc) suggests that SWCNT greatly improves the electronic communication between FeOHETPc and the bare gold electrode. The electron transfer rate constant (kapp) of Au-Cys-SWCNT-FeOHETPc in pH 4.8 conditions (∼1.7 × 10−2 cm−2 s−1) over that of the electrode obtained from SWCNT integrated with tetraaminophthalocyninatocobalt(II) (Au-Cys-SWCNT-CoTAPc) (5.1 × 10−3 cm−2 s−1) is attributed to the possible effect of the central metal on the phthalocyanine core and substituents on the peripheral positions of the phthalocyanine rings. We also prove that aligned SWCNT arrays exhibit much faster electron transfer kinetics to redox-active species in solutions compared to the randomly dispersed (drop-dried) SWCNTs.  相似文献   

13.
A tyrosinase (Tyr) biosensor was developed based on Fe3O4 magnetic nanoparticles (MNPs)-coated carbon nanotubes (CNTs) nanocomposite and further applied to detect the concentration of coliforms with flow injection assay (FIA) system. Negatively charged MNPs were absorbed onto the surface of CNTs which were wrapped with cationic polyelectrolyte poly(dimethyldiallylammonium chloride) (PDDA). The Fe3O4 MNPs-coated CNTs nanocomposite was modified on the surface of the glassy carbon electrode (GCE), and Tyr was loaded on the modified electrode by glutaraldehyde. The immobilization matrix provided a good microenvironment for retaining the bioactivity of Tyr, and CNTs incorporated into the nanocomposite led to the improved electrochemical detection of phenol. The Tyr biosensor showed broad linear response of 1.0 × 10−8-3.9 × 10−5 M, low detection limit of 5.0 × 10−9 M and high sensitivity of 516 mA/M for the determination of phenol. Moreover, the biosensor integrated with a FIA system was used to monitor coliforms, represented by Escherichia coli (E. coli). The detection principle was based on determination of phenol which was produced by enzymatic reaction in the E. coli solution. Under the optimal conditions, the current responses obtained in the FIA system were proportional to the concentration of bacteria ranging from 20 to 1 × 105 cfu/mL with detection limit of 10 cfu/mL and the overall assay time of about 4 h. The developed biosensor with the FIA system was well suited for quick and automatic clinical diagnostics and water quality analysis.  相似文献   

14.
The reduced C60-[dimethyl-(β-cyclodextrin)]2/Nafion chemically modified electrode is demonstrated to catalyze the electrochemical response of norepinephrine (NE) by cyclic voltammetry. A pair of well-defined redox waves were obtained and the calculated standard rate constant (ks) is 4.4×10−3 cm s−1 at this reduced CME, indicating that the reduced C60-[dimethyl-(β-cyclodextrin)]2 can act as promoter to the electron transfer of NE.  相似文献   

15.
A more stably dispersing of multi-wall carbon nanotube composite (noted as PDDA-MWNT), which was obtained by wrapping the MWNT with poly(diallydimethylammonium) chloride (PDDA), was used for the immobilization of glucose oxidase (GOD) and its bioelectrochemical studies. The morphologies and structures of the PDDA-MWNT composite were characterized by environment scanning electron microscopy (ESEM) and X-ray photoelectron spectroscopy (XPS). Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry were used to feature the GOD adsorbed onto the electrode modified by PDDA-MWNT composite. The immobilized GOD at the PDDA-MWNT films exhibited a pair of well-defined nearly reversible redox peaks and a fast heterogeneous electron transfer rate with the rate constant (ks) of 2.76 s−1. In addition, GOD immobilized in this way retained its bioelectrocatalytic activity for the oxidation of glucose. The method of immobilizing GOD without any additional cross-linking agents presented here is easy and facile, which provides a model for other redox enzymes and proteins.  相似文献   

16.
In this paper, a new DNA hybridization detection strategy was developed based on the immobilization of capture probe DNA on a chitosan (CS)–carbon nanotubes (CNTs) composite modified glassy carbon electrode (CS–CNTs/GCE) and the use of a copper complex, [Cu(bpy)(MBZ)2(H2O)] (bpy = 2,2′-bipyridine, MBZ = p-methylbenzoate), as a new redox hybridization indicator. The electrochemical characterization experiments showed that the nanocomposite film of CS–CNTs could effectively immobilize the capture probe DNA and greatly improve the electron-transfer reactions of the electroactive molecules. Electrochemical and fluorescent spectroscopic analysis revealed that the polypyridyl copper complex of [Cu(bpy)(MBZ)2(H2O)] bound to DNA via a typical intercalation mode. Surface studies further showed that the copper complex can discriminate between double-stranded and single-stranded DNA that immobilized on the surface of CS–CNTs/GCE. When being utilized as a redox indicator for the detection of hybridization for short DNA species related to phosphinothricin acetyltransferase (PAT), the indicator showed good specificity for recognizing the complementary, three-base mismatched and non-complementary DNA. Under the optimized conditions, the oxidation peak currents of the copper complex enhanced linearly with increases in the concentration of the complementary sequence in the range from 5.0 × 10−10 to 1.0 × 10−8 M. A detection limit of 5.0 × 10−10 M was also obtained based on the constructed DNA biosensor.  相似文献   

17.
Cobalt oxide (Co3O4) nanotubes have been successfully synthesized by chemically depositing cobalt hydroxide in anodic aluminum oxide (AAO) templates and thermally annealing at 500 °C. The synthesized nanotubes have been characterized by scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray diffraction (XRD). The electrochemical capacitance behavior of the Co3O4 nanotubes electrode was investigated by cyclic voltammetry, galvanostatic charge-discharge studies and electrochemical impedance spectroscopy in 6 mol L−1 KOH solution. The electrochemical data demonstrate that the Co3O4 nanotubes display good capacitive behavior with a specific capacitance of 574 F g−1 at a current density of 0.1 A g−1 and a good specific capacitance retention of ca. 95% after 1000 continuous charge-discharge cycles, indicating that the Co3O4 nanotubes can be promising electroactive materials for supercapacitor.  相似文献   

18.
The ability of a Keggin-type polyoxometallate, phosphododecamolybdate (PMo12O403−), to form stable anionic monolayers on carbon nanoparticles and multi-wall nanotubes is explored here to produce stable colloidal solutions of polyoxometallate covered carbon nanostructures and to disperse them within conducting polymer, poly(3,4-ethylenedioxythiophene), i.e. PEDOT, or polyaniline multilayer films. By repeated alternate treatments in the colloidal suspension of PMo12O403−-protected carbon nanoparticles or nanotubes, and in the acid solution of a monomer (3,4-ethylenedioxythiophene or aniline), the amount of the material can be increased systematically (layer-by-layer) to form stable three-dimensional organized arrangements (networks) of interconnected organic and inorganic layers on electrode (e.g. glassy carbon) surfaces. In hybrid films, the negatively charged polyoxometallate-covered carbon nanostructures interact electrostatically with positively charged conducting polymer ultra-thin layers. Consequently, the attractive electrochemical charging properties of conducting polymers, reversible redox behavior of polyoxometallate, as well as the mechanical and electrical properties of carbon nanoparticles or nanotubes can be combined. The films are characterized by fast dynamics of charge transport, and they are of potential importance to electrocatalysis and charge storage in redox capacitors.  相似文献   

19.
Carbon coated Li3V2(PO4)3 cathode material was prepared by a poly(vinyl alcohol) (PVA) assisted sol-gel method. PVA was used both as the gelating agent and the carbon source. XRD analysis showed that the material was well crystallized. The particle size of the material was ranged between 200 and 500 nm. HRTEM revealed that the material was covered by a uniform surface carbon layer with a thickness of 80 Å. The existence of surface carbon layer was further confirmed by Raman scattering. The electrochemical properties of the material were investigated by charge-discharge cycling, CV and EIS techniques. The material showed good cycling performance, which had a reversible discharge capacity of 100 mAh g−1 when cycled at 1 C rate. The apparent Li+ diffusion coefficients of the material ranged between 9.5 × 10−10 and 0.9 × 10−10 cm2 s−1, which were larger than those of olivine LiFePO4. The large lithium diffusion coefficient of Li3V2(PO4)3 has been attributed to its special NASICON-type structure.  相似文献   

20.
Single-walled carbon nanotubes (SWCNTs) derivatized with cobalt phthalocyanine (CoPh) were applied onto screen-printed graphite electrodes (SPEs) to be used for the low-potential electrochemical oxidation of thiocholine (TCh). Covalent attachment of CoPh to SWCNTs via stable sulfonamide bonds was confirmed by Raman/FT-IR spectroscopy and thermogravimetric analysis (TGA) coupled with FT-IR detection. The resulting modified SPE surfaces (CoPh-SWCNT-SPEs) were characterized by cyclic voltammetry and electrochemical impedance spectroscopy (EIS) with the redox probe [F3(CN)6]3−/4−. Detection of TCh was accomplished using cyclic voltammetry and amperometry; a lower overpotential (100 mV vs. Ag/AgCl pseudoreference electrode) was obtained using CoPh-SWCNT-SPEs as compared to unmodified SPEs and SPEs modified with non-functionalized SWCNTs (SWCNT-SPEs). The linear range for TCh detection was 0.077–0.45 mM, with a sensitivity of 5.11 × 10−1 μA mM−1 and a limit of detection of 0.038 mM according to the 3 s/m definition.  相似文献   

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