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1.
A robust and effective composite film combined the benefits of Nafion, room temperature ionic liquid (RTIL) and multi‐wall carbon nanotubes (MWNTs) was prepared. Hemoglobin (Hb) was successfully immobilized on glassy carbon electrode surface by entrapping in the composite film. Direct electrochemistry and electrocatalysis of immobilized Hb were investigated in detail. A pair of well‐defined and quasi‐reversible redox peaks of Hb was obtained in 0.10 mol·L?1 pH 7.0 phosphate buffer solution (PBS), indicating that the Nafion‐RTIL‐MWNTs film showed an obvious promotion for the direct electron transfer between Hb and the underlying electrode. The immobilized Hb exhibited an excellent electrocatalytic activity towards the reduction of H2O2. The catalysis current was linear to H2O2 concentration in the range of 2.0×10?6 to 2.5×10?4 mol·L?1, with a detection limit of 8.0×10?7 mol·L?1 (S/N=3). The apparent Michaelis‐Menten constant (Kmapp) was calculated to be 0.34 mmol·L?1. Moreover, the modified electrode displayed a good stability and reproducibility. Based on the composite film, a third‐generation reagentless biosensor could be constructed for the determination of H2O2.  相似文献   

2.
Titanium dioxide (TiO2) nanowires were synthesized and used for the realization of direct electrochemistry of hemoglobin (Hb) with carbon ionic liquid electrode (CILE) as the substrate electrode. TiO2‐Hb composite was casted on the surface of CILE with a chitosan film and spectroscopic results confirmed that Hb retained its native structure in the composite. Direct electron transfer of Hb on the modified electrode was realized with a pair of quasi‐reversible redox waves appeared, indicating that the presence of TiO2 nanowires could accelerate the electron transfer rate between the electroactive center of Hb and the substrate electrode. Electrochemical behaviors of Hb on the modified electrode were carefully investigated with the values of the electron transfer coefficient (α), the electron transfer number and the heterogeneous electron transfer rate constant (ks) as 0.58, 0.98 and 1.62 s‐1. The Hb modified electrode showed excellent electrocatalytic activity to the reduction of trichloroacetic acid and NaNO2 with wider linear range and lower detection limit, indicating the successful fabrication of a new third‐generation biosensor.  相似文献   

3.
In this paper, a Fe3O4@SiO2 core-shell structure microsphere was synthesized and used to investigate the direct electron transfer of myoglobin (Mb) with a 1-butylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE) as the substrate electrode. The mixture of Mb and Fe3O4@SiO2 microsphere could form an organic–inorganic composite, which was immobilized on the surface of CILE with a chitosan (CS) film. Cyclic voltammetric experiments indicated that a pair of well-defined quasi-reversible redox peaks appeared on CS/Mb-Fe3O4@SiO2/CILE with the formal peak potential (E 0′) located at ?0.31 V (vs. saturated calomel electrode), which was corresponded to the electroactive center of Mb heme Fe(III)/Fe(II) redox couples. Direct electrochemical behaviors of Mb in CS-Fe3O4@SiO2 composite film were carefully investigated with the electrochemical parameters calculated. The CS/Mb-Fe3O4@SiO2/CILE showed good electrocatalytic behaviors to the reduction of trichloroacetic acid in the concentration range from 0.2 to 11.0 mmol L?1 with the detection limit of 0.18 mmol L?1 (3σ). Based on CS/Mb-Fe3O4@SiO2/CILE, a new third-generation reagentless electrochemical biosensor was constructed with higher sensitivity and reproducibility.  相似文献   

4.
A graphene (GR) and multi-walled carbon nanotubes (MWCNT) hybrid was prepared and modified on a 1-hexylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE). Hemoglobin (Hb) was immobilized on GR-MWCNT/CILE surface with Nafion as the film forming material and the modified electrode was denoted as Nafion/Hb-GR-MWCNT/CILE. Spectroscopic results revealed that Hb molecules retained its native structure in the GR-MWCNT hybird. Electrochemical behaviors of Hb were carefully investigated by cyclic voltammetry with a pair of well-defined redox peaks obtained, which indicated that direct electron transfer of Hb was realized in the hybrid modified electrode. The result could be attributed to the synergistic effects of GR-MWCNT hybrid with enlarged surface area and improved conductivity through the formation of a three-dimensional network. Electrochemical parameters of the immobilized Hb on the electrode surface were further calculated with the results of the electron transfer number (n) as 1.03, the charge transfer coefficient (a) as 0.58 and the electron-transfer rate constant (ks) as 0.97 s−1. The Hb modified electrode showed good electrocatalytic ability toward the reduction of different substrates such as trichloroacetic acid in the concentration range from 0.05 to 38.0 mmol L−1 with a detection limit of 0.0153 mmol L−1 (3σ), H2O2 in the concentration range from 0.1 to 516.0 mmol L−1 with a detection limit of 34.9 nmol/L (3σ) and NaNO2 in the concentration range from 0.5 to 650.0 mmol L−1 with a detection limit of 0.282 μmol L−1 (3σ). So the proposed electrode had the potential application in the third-generation electrochemical biosensors without mediator.  相似文献   

5.
This research found a cheap and efficient catalyst for electrooxidation of formaldehyde (HCHO). A CuO nano‐crystalline modified glassy carbon electrode (GCE) was fabricated and had an excellent electrocatalytic activity towards the oxidation of HCHO. Both the effect of potential scan rate and the effect of HCHO concentration on the electrocatalytic oxidation performance of the electrode were investigated. The amperometric current response of the electrode was proportional to HCHO concentration in the range of 1.0 µmol·L?1–10.0 mmol·L?1 with a detection limit (s/n=3) of 0.25 µmol·L?1. The electrode was stable, showing the CuO nano‐crystlline is promising for applications in fuel cells and electrochemical sensors.  相似文献   

6.
A new hemoglobin (Hb) and room temperature ionic liquid modified carbon paste electrode was constructed by mixing Hb with 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF6) and graphite powder together. The Hb modified carbon ionic liquid electrode (Hb‐CILE) was further characterized by FT‐IR spectra, scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). Hb in the carbon ionic liquid electrode remained its natural structure and showed good direct electrochemical behaviors. A pair of well‐defined quasireversible redox peaks appeared with the apparent standard potential (E′) as ?0.334 (vs. SCE) in pH 7.0 phosphate buffer solution (PBS). The electrochemical parameters such as the electron transfer number (n), the electron transfer coefficient (α) and the heterogeneous electron transfer kinetic constant (ks) of the electrode reaction were calculated with the results as 1.2, 0.465 and 0.434 s?1, respectively. The fabricated Hb‐CILE exhibited excellent electrocatalytic activity to the reduction of H2O2. The calibration range for H2O2 quantitation was between 8.0×10?6 mol/L and 2.8×10?4 mol/L with the linear regression equation as Iss (μA)=0.12 C (μmol/L)+0.73 (n=18, γ=0.997) and the detection limit as 1.0×10?6 mol/L (3σ). The apparent Michaelis–Menten constant (KMapp) of Hb in the modified electrode was estimated to be 1.103 mmol/L. The surface of this electrochemical sensor can be renewed by a simple polishing step and showed good reproducibility.  相似文献   

7.
In this paper NiMoO4 nanorods were synthesized and used to accelerate the direct electron transfer of hemoglobin (Hb). By using an ionic liquid (IL) 1‐butylpyridinium hexafluorophosphate (BPPF6) modified carbon paste electrode (CILE) as the basic electrode, NiMoO4 nanorods and Hb composite biomaterial was further cast on the surface of CILE and fixed by chitosan (CTS) to establish a modified electrode denoted as CTS/NiMoO4‐Hb/CILE. UV‐vis and FT‐IR spectroscopic results showed that Hb in the film retained its native structures without any conformational changes. Electrochemical behaviors of Hb entrapped in the film were carefully investigated by cyclic voltammetry with a pair of well‐defined and quasi‐reversible redox voltammetric peaks appearing in phosphate buffer solution (PBS, pH 3.0), which was attributed to the direct electrochemistry of the electroactive center of Hb heme Fe(III)/Fe(II). The results were ascribed to the specific characteristic of NiMoO4 nanorods, which accelerated the direct electron transfer rate of Hb with the underlying CILE. The electrochemical parameters of Hb in the composite film were further carefully calculated with the results of the electron transfer number (n) as 1.08, the charge transfer coefficient (α) as 0.39 and the electron‐transfer rate constant (ks) as 0.82 s?1. The Hb modified electrode showed good electrocatalytic ability toward the reduction of trichloroacetic acid (TCA) in the concentration range from 0.2 to 26.0 mmol/L with a detection limit of 0.072 mmol/L (3σ), and H2O2 in the concentration range from 0.1 to 426.0 µmol/L with a detection limit of 3.16×10?8 mol/L (3σ).  相似文献   

8.
Copper nanoparticles (Cu-NPs) were incorporated into chitosan hydrogel to form a film on the surface of a glassy carbon electrode (GCE) leading to a sensing element for D-arabinitol with excellent oxidative catalytic activity. The electrochemical response to D-arabinitol was studied by cyclic voltammetry and differential pulse voltammetry. Operational parameters affecting the response were examined and optimized, and a simple and sensitive method was established for the determination of D-arabinitol. Response is linear in the concentration range from 10 μmol·L?1 to 10 mmol·L?1, and the limit of detection is 1.0 μmol·L?1. The method may be combined with separation techniques in order to analyze for the ratio of D- and L-arabinitol which is a diagnostic marker for candidiasis.  相似文献   

9.
Wei Sun  Peng Qin  Ruijun Zhao  Kui Jiao 《Talanta》2010,80(5):2177-138
In this paper a carbon ionic liquid electrode (CILE) was fabricated by using ionic liquid 1-ethyl-3-methylimidazolium ethylsulfate ([EMIM]EtOSO3) as modifier and further gold nanoparticles were in situ electrodeposited on the surface of CILE. The fabricated Au/CILE was used as a new platform for the immobilization of hemoglobin (Hb) with the help of a Nafion film. Electrochemical experimental results indicated that direct electron transfer of Hb was realized on the surface of Au/CILE with a pair of well-defined quasi-reversible redox peaks appeared. The formal peak potential (E0) was obtained as −0.210 V (vs. SCE) in pH 7.0 phosphate buffer solution (PBS), which was the characteristic of Hb heme Fe(III)/Fe(II) redox couple. The fabricated Nafion/Hb/Au/CILE showed excellent electrocatalytic activity to the reduction of trichloroacetic acid (TCA) and the reduction peak current was in proportional to TCA concentration in the range from 0.2 to 18.0 mmol/L with the detection limit as 0.16 mmol/L (S/N = 3). The proposed electrode showed good stability and reproducibility, and it had the potential application as a new third-generation electrochemical biosensor.  相似文献   

10.
合成了水溶性硒化镉(CdSe)量子点,利用组装技术和静电吸附作用,将带正电荷的血红蛋白(Hb)和带负电荷的CdSe量子点层层组装到壳聚糖(chit)修饰的玻碳电极(GCE)表面,构建基于{Hb/CdSe}n多层膜的无电子媒介体的电流型生物传感器({Hb/CdSe}3/chit/GCE).运用紫外-可见吸收光谱、电致化学发光、交流阻抗和循环伏安技术来表征修饰膜,并研究传感器的作用机理、性能及分析应用.结果表明:与量子点薄膜法及量子点/血红蛋白复合物法等固载血红蛋白的其他方法相比,层层组装法能显著提高血红蛋白的固定量,保持血红蛋白的生物活性,增强传感器的灵敏度和稳定性.传感器检测H2O2的线性范围为4.0×10-8~4.8×10-6 mol·L-1(r=0.999 1),检测限为2.0×10-8mol·L-l.多层膜的电致化学发光研究,表明修饰电极有望用于电致化学发光传感器的制备.  相似文献   

11.
In this paper a Mg2Al‐Cl layered double hydroxide (Mg2Al‐LDH) modified carbon ionic liquid electrode (CILE) was prepared and further used for the electrochemical detection of rutin. Cyclic voltammograms of rutin on Mg2Al‐LDH/CILE were recorded with a pair of well‐defined redox peaks appeared in pH 2.5 phosphate buffer solution, which was ascribed to the electrochemical reaction of rutin. Due to the presence of Mg2Al‐LDH on the electrode surface, the redox peak currents increased greatly and the electrochemical parameters were calculated. Under the optimal conditions the oxidation peak current was proportional to rutin concentration in the range from 0.08 μmol L‐1 to 800.0 μmol L‐1 with the detection limit on 0.0255 μmol L‐1 (3σ). The fabricated electrode showed good reproducibility and stability, which was successfully applied to rutin tablet samples determination.  相似文献   

12.
When the concentration of dodecyl benzene sulfonic acid sodium salt (SDBS) is 0.7 mmol·L?1, the electrochemical and electrochemiluminescence (ECL) intensity of Ru(bpy)32+‐chlorpheniramine maleate (CPM) system at the Au electrode were studied. The results showed that compared with the absence of SDBS, enhancement of the ECL intensity was 14‐fold at Au electrode. Base on this, an ECL method was established for efficient and simple determination of CPM at Au electrode. Under the optimum experimental condition, the enhanced ECL intensities had good linear relationship with the concentration of CPM in the range of 1.0×10?4–1.0×10?7 mol·L?1, and a linear regression equation was obtained as follows: I (counts)=48.805×106c+394.03 (r=0.9975), the detection limit for CPM was 1.4×10?8 mol·L?1. The RSD for 5 times determinations of 1.0×10?5 mol·L?1 CPM was 3.2%. The results of recovery test were between 96.3%–102.5%, and the RSD of recovery test (n=5) was 2.7%. In addition, eleven kinds of tertiary amines‐Ru(bpy)32+ systems were investigated in the absence and presence of SDBS. The results showed that the enhancement of SDBS on ECL intensity of tertiary amines‐Ru(bpy)32+ systems was universal.  相似文献   

13.
A nanoporous Pt particles‐modified Ti (nanoPt/Ti) electrode was prepared through a simple hydrothermal method using aqueous H2PtCl6 as a precursor and formaldehyde as a reduction agent. The nanoPt/Ti electrode was then modified with limited amounts of tin particles generated by cyclic potential scans in the range of ?0.20 to 0.50 V in a 0.01 mol·L?1 SnCl2 solution, to synthesize a Sn‐modified nanoporous Pt catalyst (Sn/nanoPt/Ti). Electroactivity of the nanoPt/Ti and Sn/nanoPt/Ti electrodes towards formaldehyde oxidation in a 0.5 mol·L?1 H2SO4 solution was evaluated by cyclic voltammetry and chronoamperometry. Electrooxidation of formaldehyde on the nanoPt/Ti electrode takes place at a potential of 0.45 V and then presents high anodic current densities due to the large real surface area of the nanoPt/Ti electrode. The formaldehyde oxidation rate is dramatically increased on the Sn/nanoPt/Ti electrode at the most negative potentials, where anodic formaldehyde oxidation is completely suppressed on the nanoPt/Ti electrode. Chronoamperogramms (CA) of the Sn/nanoPt/Ti electrode display stable and large quasi‐steady state current densities at more negative potential steps. Amperometric data obtained at a potential step of 100 mV show a linear dependence of the current density for formaldehyde oxidation upon formaldehyde concentration in the range of 0.003 to 0.1 mol·L?1 with a sensitivity of 59.29 mA·cm?2 (mol·L?1)?1. A detection limit of 0.506 mmol·L?1 formaldehyde was found. The superior electroactivity of the Sn/nanoPt/Ti electrode for formaldehyde oxidation can be illustrated by a so‐called bifunctional mechanism which is involved in the oxidation of poisoning adsorbed CO species via the surface reaction with OH adsorbed on neighboring Sn sites.  相似文献   

14.
A voltammetric sensor was fabricated by applying a Nafion and multi-walled carbon nanotubes (MWCNTs) composite film on the surface of a carbon ionic liquid electrode (CILE), which was prepared by mixing 1-butyl-3-methylimidazolium hexafluorophosphate with graphite powder. The electrochemical behavior of adenine on the Nafion-MWCNTs/CILE was investigated in pH 5.5 buffer solution. Adenine showed an irreversible adsorption-controlled oxidation reaction with enhanced electrochemical response, which was due to the presence of high conductive MWCNTs on the CILE surface. The electrochemical parameters of adenine electro-oxidation were determined, and the experimental conditions were optimized. Under the optimal conditions, the oxidation peak current was linear to the adenine concentration over the range of 1.0?×?10?7 to 7.0?×?10?5 mol L?1 with a detection limit of 3.3?×?10?8 mol L?1 (signal/noise?=?3). The electrode showed good stability and selectivity, and was further applied to milk powder samples with satisfactory results.  相似文献   

15.
In this paper a room temperature ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF6) was used as binder for the construction of carbon ionic liquid electrode (CILE) and a new electrochemical biosensor was developed for determination of H2O2 by immobilization of hemoglobin (Hb) in the composite film of Nafion/nano‐CaCO3 on the surface of CILE. The Hb modified electrode showed a pair of well‐defined, quasi‐reversible redox peaks with Epa and Epc as ?0.265 V and ?0.470 V (vs. SCE). The formal potential (E°′) was got by the midpoint of Epa and Epc as ?0.368 V, which was the characteristic of Hb Fe(III)/Fe(II) redox couples. The peak to peak separation was 205 mV in pH 7.0 Britton–Robinson (B–R) buffer solution at the scan rate of 100 mV/s. The direct electrochemistry of Hb in the film was carefully investigated and the electrochemical parameters of Hb on the modified electrode were calculated as α=0.487 and ks=0.128 s?1. The Nafion/nano‐CaCO3/Hb film electrode showed good electrocatalysis to the reduction of H2O2 in the linear range from 8.0 to 240.0 μmol/L and the detection limit as 5.0 μmol/L (3σ). The apparent Michaelis–Menten constant (KMapp) was estimated to be 65.7 μmol/L. UV‐vis absorption spectroscopy and FT‐IR spectroscopy showed that Hb in the Nafion/nano‐CaCO3 composite film could retain its native structure.  相似文献   

16.
A nanostructured manganese dioxide electrode material was prepared using a solid‐reaction route starting with MnCl2·4H2O and NH4HCO3, and its electrochemical performance as a positive electrode for MnO2/activated carbon hybrid supercapacitor with 1 mol·L?1 LiOH electrolyte was reported. The material was proved to be a mixture of nanostructured γ‐MnO2 and α‐MnO2 containing some bound water in the structure, which was characterized by X‐ray diffraction analysis, infrared spectrum analysis, and transmission electron microscope observation. Electrochemical properties of the MnO2 electrode and the MnO2/AC capacitor were investigated by cyclic voltammetry, ac impedance and galvanostatic charge/discharge methods. Experimental results showed that the MnO2 electrode exhibited faradaic pseudocapacitance behavior and higher specific capacitance in 1 mol·L?1 LiOH electrolyte. The MnO2/AC hybrid capacitor with 1 mol·L?1 LiOH electrolyte presented excellent rate charge/discharge ability and cyclic stability.  相似文献   

17.
Alternate adsorption of positively charged colloid-Au nanoparticles (nano-Au⊕) and negatively charged hemoglobin (Hb) on L-cysteine (L-cys) modified gold electrode resulted in the assembly of {Hb/nano-Au⊕}n layer-by-layer films/L-cys modified gold electrode. The nano-Au⊕ was characterized by transmission electron micrograph (TEM) and microelectrophoresis. The modified electrode interface morphology was characterized by electrochemical impedance spectroscopy (EIS), atomic force mi- croscopy (AFM), cyclic voltammograms (CV) and chronoamperometry. Direct electron transfer between hemoglobin and gold electrodes was studied, and the apparent Michaelis-Menten constant ( km app) of the modified electrode was evaluated to be 0.10 mmol·L?1. Moreover, the higher activity of proteins in the nano-Au⊕ films could be retained compared with the electropolymerization membrane, since the pro- teins in nano-Au⊕ films retained their near-native structure. Direct electron transfer between hemoglo- bin and electrode and electrochemically catalyzed reduction of hydrogen peroxide on a modified elec- trode was studied, and the linear range was from 2.1×10-8 to 1.2 ×10?3 mol·L-1 (r = 0.994) with a detection limit of 1.1×10-8 mol·L-1 H2O2.  相似文献   

18.
利用ITO基底上层层组装构建的多层内嵌银纳米粒子的磷酸钛薄膜固定了血红蛋白并且用于生物传感研究。由于银纳米粒子与磷酸钛膜的协同作用,实验中可以观察到Hb的直接电子传递。研究表明所制备的Hb-Ag-TiP/PDDA/ITO电极对H2O2响应迅速、稳定,检测限达3.3×10-6 mol·L-1。  相似文献   

19.
A new electrochemical biosensor was constructed by immobilization of hemoglobin (Hb) on a DNA modified carbon ionic liquid electrode (CILE), which was prepared by using 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIMBF4) as the modifier. UV‐vis absorption spectroscopic result indicated that Hb remained its native conformation in the composite film. The fabricated Nafion/Hb/DNA/CILE was characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). A pair of well‐defined redox peaks was obtained on the modified electrode, indicated that the Nafion and DNA composite film provided an excellent biocompatible microenvironment for keeping the native structure of Hb and promoting the direct electron transfer rate of Hb with the basal electrode. The electrochemical parameters of Hb in the composite film were further calculated with the results of the charge transfer coefficient (α) and the apparent heterogeneous electron transfer rate constant (ks) as 0.41 and 0.31 s?1. The proposed electrochemical biosensor showed good electrocatalytic response to the reduction of trichloroacetic acid (TCA), H2O2, NO and the apparent Michaelis–Menten constant (KMapp) for the electrocatalytic reaction was calculated, respectively.  相似文献   

20.
Mesoporous silica KIT-6 has novel three-dimensional gyroidal channel structure, space group of 1a-3d, and ordered tunable pores up to 10 nm. In this paper, such mesostructured silica was employed as hard template to prepare semicrystalline gyroidal mesoporous MnO2. The structure was investigated by XRD, TEM and HRTEM, and found to be of high quality 1a-3d symmetry, in good accordance with the template structure. The material has a BET surface of 118 m2·g^-1 and pore volume of 0.35 cm3·g^- 1 after eliminating template. Mesoporous MnO2 has shown good electrochemical property as supercapacitor material in 1 mol·L^-1 Na2SO4 and 1 mol·L^-1 LiClO4 solutions, but interesting pseudocapacitance behavior was observed in the case of 6 mol·L^-1 KOH. It was found that mesoporous MnO2 performed stable reversible electrochemical behavior with capacitance of 220 F·g^-1 in a potential range of -0.1-0.55 V vs. Hg/HgO in alkaline solution, demonstrating that it is a promising novel electrode material for the fabrication of electrochemical capacitors.  相似文献   

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