Prussian Blue Modified Carbon Ionic Liquid Electrode: Electrochemical Characterization and Its Application for Hydrogen Peroxide and Glucose Measurements

Prussian blue modified carbon ionic liquid electrodes (PB‐CILEs) were fabricated using chemical and electrochemical procedures. Chemically fabricated PB‐CILE exhibited an excellent sensitivity (0.0866 μA μM^?1), low detection limit (0.01 μM) and two linear ranges (0.01–1 and 1–600 μM) toward hydrogen peroxide. Then, glucose oxidase (GOx) was immobilized on the surface of PB‐CILE to fabricate glucose biosensor using three different procedures involving cross linking with glutaraldehyde (GLU) and bovine serum albumin (BSA), entrapment into the Nafion matrix and covering with a sol‐gel layer. Glucose biosensor fabricated using cross linking procedure showed the best sensitivity (0.0019 μA μM^?1) and operational stability for glucose.     

High-Sensitive Glucose Biosensor Based on Ionic Liquid Doped Polyaniline/Prussian Blue Composite Film

The Prussian blue/ionic liquid-polyaniline/multiwall carbon nanotubes (PB/IL-PANI/MWNTs) composite film was fabricated by using cyclic voltammetry. The ion liquid acting as a lubricating agent, could enhance the electron delocalization degree and reduce the struc-tural defects of the polyaniline. The surface morphology of the composite film revealed that the PB nanoparticles have smaller size than that in pure PB film. Due to the introduction of ion liquid, the PB/IL-PANI/MWNTs composite film showed wonderful synergistic effect which can remarkably enhance sensitivity, expand linear range and broaden acidic adapt-ability for hydrogen peroxide detection. The composite film demonstrated good stability in neutral solution contrast to pure PB film, with a linear range from 2.5 μmol/L to 0.5 mmol/Land a high sensitivity of 736.8 μA·(mmol/L)^-1·cm^-2 for H₂O₂ detection. Based on the com-posite film, an amperometric glucose biosensor was then fabricated by immobilizing glucose oxidase. Under the optimal conditions, the biosensor also exhibits excellent response to glucose with the linear range from 12.5 μmol/L to 1.75 mmol/L and a high sensitivity of 94.79 μA (mmol/L)^-1·cm^-2 for H₂O₂. The detection limit was estimated 1.1 μmol/L. The resulting biosensor was applied to detect the blood sugar in human serum samples without any pretreatment, and the results were comparatively in agreement with the clinical assay.     

Prussian Blue‐Modified Titanate Nanotubes: A Novel Nanostructured Catalyst for Electrochemical Reduction of Hydrogen Peroxide

Prussian blue (PB) modified titanate nanotubes (PB‐TiNT) have been synthesized by the reaction of Fe²⁺‐modified TiNT with hexacyanoferrate(III) ions. The rate constant for heterogeneous catalytic reaction between PB‐TiNT and H₂O₂ was found to be k=2×10⁴ dm³ mol^?1 s^?1, which is an order of magnitude higher than the values of k reported for conventionally prepared, electrochemically deposited PB films. On the PB‐TiNT modified electrode with subnanomolar surface concentration of PB (Γ(PB)=2.8×10^?11 mol/cm²), a stable, reproducible and linear response towards H₂O₂ was obtained in the concentration range 0.02–4 mM, with the sensitivity of 0.10 AM^?1 cm^?2 at ?150 mV.     

普鲁士蓝修饰生物传感器的研究进展

文中叙述了普鲁士蓝(PB)结构特征和电化学特性,PB在过氧化氢传感器中的应用。综述了PB葡萄糖传感器及其他基于PB的生物氧化酶传感器的研究进展。引用文献52篇。     

Prussian Blue Nanoparticles Self Assembling on Electrochemically Reduced Graphene Oxide Modified GC Electrode for Sensitive Hydrogen Peroxide Detection

A facile, fast, and convenient route was suggested for the fabrication of Prussian blue nano particles (PBNPs) assembled on reduced graphene oxide (RGO) modified glassy carbon electrode (PBNPs|RGO|GCE). RGO was electrodeposited on the surface of GCE and the prepared RGO|GCE was immersed into a ferric‐hexacyanoferrate(III) solution and PBNPs were assembled on the RGO|GCE for a certain period of time. The PBNPs film thickness can be easily controlled by adjusting the assembling duration. The developed PBNPs|RGO|GCE was successfully used for determining hydrogen peroxide, with a linear response over the concentration range 0.5‐400 μM, a good accuracy and precision, detection limit 0.44 μM, and sensitivity 1168 mA M^?1 cm^?2.     

Prussian Blue/Reduced Graphene Oxide Composite for the Amperometric Determination of Dopamine and Hydrogen Peroxide

Prussian blue has significant application for the construction of electrochemical biosensors. In this work, Prussian blue-reduced graphene oxide modified glass carbon electrodes were successfully fabricated using electrochemical deposition. The high surface area of graphene oxide enhanced the deposition of Prussian blue and the resulting electrocatalytic activity. Infrared spectroscopy and scanning electron microscopy showed that the relatively porous Prussian blue was on the surface of reduced graphene oxide. Cyclic voltammetry showed that Prussian blue-coated reduced graphene oxide composite films improved electron transfer compared to Prussian blue films. The Prussian blue-reduced graphene oxide composite film provided higher response for the reduction of hydrogen peroxide and the oxidation of dopamine compared with the Prussian blue film due to synergistic effects between the reduced graphene oxide and Prussian blue particles. The sensitivity of the electrode was 0.1617 µA µM^?1 cm^?2. The linear dynamic range extended from 0.5 µM to 0.7 mM dopamine with a limit of detection equal to 125 nM. This work provided a versatile strategy for the design and construction of sensitive amperometric sensors with robust electrocatalytic behavior.     

Stability Improvement of Prussian Blue by a Protective Cellulose Acetate Membrane for Hydrogen Peroxide Sensing in Neutral Media

The cellulose acetate covered Prussian blue modified glassy carbon electrode (GCE/PB/CA) was fabricated as a novel hydrogen peroxide sensor. It was shown by scanning electron microscope (SEM) and atomic force microscope (AFM) that Prussian blue was covered and protected by cellulose acetate perfectly. The modified electrode showed a good electrocatalytic activity for H₂O₂ reduction in neutral aqueous solution. H₂O₂ was detected amperometrically in 0.05 mol/L phosphate buffer solutions (pH 7.0, containing 0.1 mol/L KCl as supporting electrolyte) at an applied potential of ?0.2 V (vs. SCE). The response current was proportional to the concentration of H₂O₂ in the range of 1.0×10^?5 mol/L to 2.5×10^?4 mol/L with the detection limit of 2.2×10^?6 mol/L at a signal to noise ratio 3.     

以新亚甲蓝为介体的过氧化氢传感器的电化学行为研究

利用共价键合法,将新亚甲蓝(NMB)与辣根过氧化酶(HRP)修饰于玻碳电极表面,制成一种新型的电流型H2O2传感器。探讨了该传感器在0·1mol/L磷酸缓冲溶液(pH=7·0)中的电化学性质。结果表明,NMB作为介体能够有效地在辣根过氧化酶和电极之间传递电子。测得电子转移系数为0·861,表观反应速率常数为1·27s-1。研究了传感器对H2O2的响应及动力学性质,米氏常数为8·27μmol/L,线性响应范围为2·5~100μmol/L。同时研究了pH、缓冲容量及温度等因素对H2O2传感器的影响。     

基于普鲁士蓝/二氧化锰复合材料修饰电极上的无酶过氧化氢传感器

合成了一种普鲁士蓝/二氧化锰(PB/MnO2)复合材料。表征结果显示两者成功地复合在一起。电化学测试结果表明复合材料比单独的PB具有更好的电化学活性。由修饰玻碳电极(GCE)构建的传感器对过氧化氢(H2O2)的还原具有良好的稳定性、重现性和选择性。     

Investigation of the Effect of Different Glassy Carbon Materials on the Performance of Prussian Blue Based Sensors for Hydrogen Peroxide

Three different kinds of glassy carbon (GC‐R, GC‐K, GC‐G) were equally pretreated, further modified with electrochemically deposited Prussian Blue and used as sensors for hydrogen peroxide at an applied potential of ?50 mV (vs. Ag|AgCl). Their performance was evaluated with respect to the following parameters: the coverage and electrochemistry of the electrodeposited Prussian Blue, the sensitivity and the lower limit of detection for hydrogen peroxide, and the operational stability of the sensors. GC‐R showed the best behavior concerning the surface coverage and the operational stability of the electrodeposited Prussian Blue. For this electrode the sensitivity for hydrogen peroxide (10 μM) was 0.25 A/M cm² and the detection limit was 0.1 μM. Scanning electron microscopy was used to study the surfaces of the three electrodes before and after the electrodeposition of Prussian Blue and to search for the reason for the three different behaviors between the different glassy carbon materials. The Prussian Blue modified GC‐R was also used for the construction of a glucose biosensor based on immobilizing glucose oxidase in Nafion membranes on top of electrodeposited Prussian Blue layer. The operational stability of the glucose biosensors was studied in the flow injection mode at an applied potential of ?50 mV (vs. Ag|AgCl) and alternatively injecting standard solutions of hydrogen peroxide (10 μM) and glucose (1 mM) for 3 h. For the GC‐R based biosensor a 2.8% decrease of the initial glucose response was observed.     

A Novel Electrochemical Method for the Analysis of Hydrogen Peroxide with the Use of a Glassy Carbon Electrode Modified by a Prussian Blue/Copper‐Gold Bimetallic Nanoparticles Hybrid Film

A novel Prussian blue/copper‐gold bimetallic nanoparticles hybrid film modified electrode was prepared by electrochemical deposition on a glassy carbon electrode (PB/Cu‐AuNPs/GCE). Morphology and electrochemistry of this electrode were studied by UV‐vis spectroscopy, scanning electron microscopy, X‐ray diffraction, cyclic voltammetry and electrochemical impedance spectroscopy. The sensor showed significantly better electrocatalytic activity for the reduction of hydrogen peroxide in comparison with the single PB/GCE and PB/AuNPs/GCE. This was attributed to the synergistic effect of PB and Cu‐Au bimetallic nanoparticles. Also, the sensor demonstrated an overall high level of performance for the analysis of H₂O₂ in the concentration range from 0.002 to 0.84 mM.     

Self‐Assembled Prussian Blue Nanoparticles Based Electrochemical Sensor for High Sensitive Determination of H2O2 in Acidic Media

In this paper, self‐assembled Prussian blue nanoparticles (PBNPs) on carbon ceramic electrode (CCE) were developed as a high sensitive hydrogen peroxide (H₂O₂) electrochemical sensor. The PBNPs film was prepared by a simple dipping method. The morphology of the PBNPs‐modified CCE was characterized by scanning electron microscopy (SEM). The self‐assembled PB film exhibited sufficient mechanical, electrochemical stability and high sensitivity in compare with other PB based H₂O₂ sensors. The sensor showed a good linear response for H₂O₂ over the concentration range 1 μM–0.26 mM with a detection limit of ca. 0.7 μM (S/N=3), and sensitivity of 754.6 mA M^?1 cm^?2. This work demonstrates the feasibility of self‐assembled PBNPs‐modified CCE for practical sensing applications.     

层层自组装法制备普鲁士蓝修饰电极及对过氧化氢的测定

Fe3+可与电沉积在玻碳电极表面的对氨基苯磺酸发生静电吸附作用并与[Fe(CN)6]4-形成普鲁士蓝(PB),进一步交替重复吸附Fe3+和[Fe(CN)6]4-反应,形成PB晶体.该晶体对还原过氧化氢(H2O2)具有很高的电化学活性.通过循环伏安法、交流阻抗法和计时电流法对传感器进行了电化学表征.研究了该传感器对H2O2的电催化作用,探讨了工作电位,PH值及干扰物质对响应电流的影响.结果表明,在磷酸盐缓冲溶液中(pH =5.4,0.1 mol/L),响应电流与H2O2的浓度在0.97 ～ 32.33 mmol/L范围内具有良好的线性关系,相关系数为0.9993,传感器的响应时间小于5 s,检测限为0.48 mmol/L( S/N为3).     

普鲁士蓝-多壁碳纳米管复合材料修饰电极测定过氧化氢

利用电化学方法在多壁碳纳米管(MWCNT)修饰的玻碳电极表面聚合一层普鲁士蓝(PB)(PB/MWCNT/GCE),制备了一种新型的过氧化氢(H2O2)传感器。研究了该传感器对H2O2的电催化作用。讨论了支持电解质种类、酸度、修饰层厚度、电位和扫速等对H2O2响应的影响。研究表明,该传感器在以1.0mol/L KCl为支持电解质的磷酸盐溶液(pH=2.0)中,对H2O2具有明显的催化效应,测定的线性范围变宽,在2.9×10-6~8.8×10-2mol/L范围内还原峰电流与H2O2的浓度呈良好的线性关系,相关系数为0.9949;检出限为1.4×10-6mol/L。该电极用于医用消毒水中H2O2的测定,结果令人满意。     

单缺位Dawson型磷钨杂多酸掺杂聚吡咯的过氧化氢传感器研究

在金电极上，用电化学方法将单缺位Ｄａｗｓｏｎ型磷钨杂多酸盐ａ２－Ｋ１０Ｐ２Ｗ１７Ｏ６１１５Ｈ２Ｏ的阴离子（Ｐ２Ｗ１７）掺杂到聚吡咯（ＰＰｙ）薄膜中，制成ＰＰｙ／Ｐ２Ｗ１７／Ａｕ的Ｈ２Ｏ２传感器。研究了它对 Ｈ２Ｏ２电还原过程的催化机理．其 ｉｐｅ与 ＣＨ２Ｏ２在 ６．０× １０－５～８． ８×１０－４ ｍｏｌ／Ｌ和８．８×１０－４～６．０×１０－３ｍｏｌ／Ｌ范围内呈良好的线性关系，检测下限为４．０×１０－５ｍｏｌ／Ｌ。用于模拟水样中Ｈ２Ｏ２的测定，结果较满意．     

A MgO Nanoparticles Composite Matrix‐Based Electrochemical Biosensor for Hydrogen Peroxide with High Sensitivity

A novel horseradish peroxidase (HRP) electrochemical biosensor based on a MgO nanoparticles (nano‐MgO)‐chitosan (chit) composite matrix was developed. The morphology of nano‐MgO‐chit nanocomposite was examined by scanning electron microscopy (SEM). The interaction between nano‐MgO‐chit nanocomposite matrix and enzyme was characterized with UV‐vis spectra. This proposed composite material combined the advantages of inorganic nanoparticles and organic polymer chit. The HRP immobilized in the nanocomposite matrix displayed excellent electrocatalytic activity to the reduction of H₂O₂ in the presence of hydroquinone as a mediator. The effects of the experimental variables such as solution pH and the working potential were investigated using steady‐state amperometry. The present biosensor (HRP‐modified electrode) had a fast response towards H₂O₂ (less than 10 s), and excellent linear relationships were obtained in the concentration range of 0.1–1300 μM, with a detection limit of 0.05 μM (S/N=3). Moreover, the stability and reproducibility of this biosensor were evaluated with satisfactory results.     

Nafion膜固定的麦尔多拉蓝为介体的过氧化氢、葡萄糖和乳糖生物传感器

以Nafion膜修饰玻碳电极固定的麦尔多拉蓝为辣根过氧化物酶和电极间的电子传递介体，成功地制成了性能优良的电流型单酶过氧化氢生物传感器；在此基础上通过固定双酶（辣根过氧化物酶－葡萄糖氧化酶）和三酶（辣根过氧化物酶－葡萄糖氧化酶－半乳糖苷酶）分别制成了葡萄糖和乳糖生物传感器；探讨了工作电位、pH、温度和干扰物质等对这3种生物传感器的影响。     

基于等离子体聚合膜固定酶的H2O2生物传感器

以玻碳电极为基础电极,用微波等离子体技术聚合沉积聚乙二胺等离子体膜,使之形成带氨基功能团的表面,再通过戊二醛交联共价固定辣根过氧化物酶,制得H2O2生物传感器.探讨了等离子体聚合膜的形成条件(如放电功率、单体流速、单体气压和聚合时间),讨论了工作电位、介体浓度和pH值对传感器响应的影响.此外,用红外光谱对等离子体聚合膜进行了表征.该传感器在5×10-7～1.1×10-3mol/LH2O2浓度范围内有线性响应,最低检测限为0.3μmol/L.将此传感器用于实际试样回收率的测定,结果良好.     

Carbon Electrodes Modified by Nanoscopic Iron(III) Oxides to Assemble Chemical Sensors for the Hydrogen Peroxide Amperometric Detection

In this study we show that nanoparticles of various ferric oxides (hematite, maghemite, amorphous Fe₂O₃, β‐Fe₂O₃ and ferrihydrite) incorporated into carbon paste exhibit electro‐catalytic properties towards hydrogen peroxide reduction. The modified paste electrode performances were evaluated and compared with those obtained with Prussian Blue‐modified carbon paste electrode, which represents an excellent chemical mediator towards the H₂O₂ redox reaction (as widely described in literature). The best catalytic activity was found for carbon paste modified by amorphous ferric oxide with 2–4 nm particle size, which was further tested for possible application as hydrogen peroxide sensor. At pH 7, the limit of detection was 2×10^?5 M H₂O₂ (S/N=3), the calibration curves were linear upto 8.5 mM H₂O₂ (R²=0.998), the measurement reproducibility (RSD=97%, n=4), the interelectrode reproducibility (RSD=16%, n_electrodes=5) and <3 s response time.