Recent advances in nanomaterial-based electrochemical sensing of nitric oxide and nitrite for biomedical and food research

Nitric oxide (NO) and nitrite are of significant importance in clinical/biomedical research and in quality control applications for the food industry. Electrochemical sensing of NO and nitrite has been extensively pursued over the last two years. Efficient interfaces based on functional nanomaterials and bioactive molecules (e.g. metals, metal oxides, carbon-based nanomaterials, conducting polymers, and heme proteins) have been widely explored toward sensor development. Herein, we review the most recent advances in the electrochemical sensing of NO and nitrite, while the critical roles of nanomaterials in the design of advanced electrochemical sensors are highlighted.     

Carbon Nanotubes Heavy Metal Detection with Stripping Voltammetry: A Review Paper

The challenge of heavy metal detection for environmental, industrial and medical purposes has led to the development of many analytical techniques. Stripping voltammetry is a very sensitive electrochemical method and has been widely used for heavy metal detection. Carbon nanotubes, a well‐studied carbon material with physical and chemical properties suited for electrode material is commonly employed for sensitive and selective metal detection in electrochemistry. This article reviews the recent (2011–2016) applications of carbon nanotubes as an electrode or electrode surface modifier for heavy metals detection with stripping voltammetry.     

二氧化锆/石墨烯复合材料对亚硝酸盐的电化学传感研究

制备了一种二氧化锆/还原氧化石墨烯(ZrO2NPs/rGO)复合材料修饰电极的亚硝酸盐电化学传感器,并成功用于亚硝酸盐的检测.采用循环伏安法和电流-时间曲线考察了修饰电极的电化学行为.实验结果表明,ZrO2NPs/rGO复合材料修饰电极对亚硝酸盐具有良好的电流响应.在最优实验条件下,电流-时间曲线中的电流响应信号与亚硝酸盐浓度在3.0×10Symbolm@@_7～1.0×10Symbolm@@_6 mol/L和1.0×10Symbolm@@_6～6.0×10Symbolm@@_6 mol/L的范围内呈良好的线性关系,检测限为1.0×10Symbolm@@_7 mol/L(S/N 3).该传感器灵敏性高、稳定性和重现性好.使用此传感器检测实际样品香肠中的亚硝酸盐的回收率为93.7％～110.4％,相对标准偏差为1.6％～2.1％.     

A Novel Cerium Tungstate Nanosheets Modified Electrode for the Effective Electrochemical Detection of Carcinogenic Nitrite Ions

In this present scenario, for the first time, we propose a facile and simple wet chemical approach for the fabrication of two‐dimensional (2D) cerium tungstate (CeW₂O₉;CeW) nanosheets and evaluated as an electrochemical sensor for the detection of nitrite ions. The successful formation of CeW₂O₉ nanosheets was confirmed by various physicochemical techniques such as X‐ray diffraction, Fourier transform infrared spectroscopy, Raman, Scanning electron microscope, Transmission electron microscope and Energy dispersive X‐ray studies. The electrochemical properties of the CeW nanosheets were studied by using cyclic voltammograms (CV) and chronoamperometric techniques. As an electrochemical sensor, the CeW nanosheets modified glassy carbon electrode (GCE) showed superior electrocatalytic activity in the oxidation of nitrite in terms of higher anodic peak current and lower oxidation potential when compared with unmodified GCE. CeW nanosheets based electrochemical sensor has been fabricated which detect nitrite in wide linear response range, good sensitivity and very low detection limit of 0.02–986 μM, 2.85 μA μM⁻¹ cm⁻² and 8 nM, respectively. Moreover, the CeW nanosheets modified GCE exhibited excellent selectivity even in the presence of common metal ions and biologically co‐interfering compounds. For the practical viability of the prepared amperometric sensor has been utilized in various water samples such as tap, lake and drinking water and the obtained recoveries are appreciable.     

Development of Pen-type Portable Electrochemical Sensor Based on Au-W Bimetallic Nanoparticles Decorated Graphene-chitosan Nanocomposite Film for the Detection of Nitrite in Water,Milk and Fruit Juices

The development and fabrication of a simple, portable, and sensitive detection tool to precisely monitor nitrite level is of growing importance in electrochemistry research, given the strong interest in the protection of drinking water quality, treatment of wastewater, food production, and control of remediation processes. This work describes the fabrication of a simple, cost-effective, pen-type electrochemical sensor based on bimetallic gold and tungsten nanoparticles electrochemically decorated on graphene-chitosan modified pencil graphite electrode (PGE) for the trace detection of nitrite in real samples. The prepared nanocomposite was characterized using XRD, SEM, and EDS. The electrochemical behavior of the sensor was evaluated by cyclic voltammetry (CV) and impedance electrochemical spectroscopy (EIS). Results revealed that the proposed sensor displayed excellent electrocatalytic activity towards electro-oxidation of nitrite with an irreversible redox reaction. The AuNPs-WNPs@Gr-Chi/PGE sensor exhibited excellent analytical performance with a wide linear range from 10 to 250 μM towards nitrite. The LOD and LOQ were calculated to be 0.12 μM and 0.44 μM, respectively. The designed electrochemical sensor was successfully applied for the detection of nitrite in water, milk, and natural fruit juice samples.     

Simultaneous electrochemical determination of nitrate and nitrite in aqueous solution using Ag-doped zeolite-expanded graphite-epoxy electrode

In this work a new electrochemical sensor based on an Ag-doped zeolite-expanded graphite-epoxy composite electrode (AgZEGE) was evaluated as a novel alternative for the simultaneous quantitative determination of nitrate and nitrite in aqueous solutions. Cyclic voltammetry was used to characterize the electrochemical behavior of the electrode in the presence of individual or mixtures of nitrate and nitrite anions in 0.1 M Na₂SO₄ supporting electrolyte. Linear dependences of current versus nitrate and nitrite concentrations were obtained for the concentration ranges of 1-10 mM for nitrate and 0.1-1 mM for nitrite using cyclic voltammetry (CV), chronoamperometry (CA), and multiple-pulsed amperometry (MPA) procedures. The comparative assessment of the electrochemical behavior of the individual anions and mixtures of anions on this modified electrode allowed determining the working conditions for the simultaneous detection of the nitrite and nitrate anions. Applying MPA allowed enhancement of the sensitivity for direct and indirect nitrate detection and also for nitrite detection. The proposed sensor was applied in tap water samples spiked with known nitrate and nitrite concentrations and the results were in agreement with those obtained by a comparative spectrophotometric method. This work demonstrates that using multiple-pulse amperometry with the Ag-doped zeolite-expanded graphite-epoxy composite electrode provides a real opportunity for the simultaneous detection of nitrite and nitrate in aqueous solutions.     

A novel nitrite sensor based on poly-1-naphthylamine doped by a ferrocenesulfonic-acid-modified electrode

A novel sensor for detecting nitrite based on poly-1-naphthylamine doped by a ferrocenesulfonic acid (PNAFc) modified electrode has been proposed. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) have confirmed that ferrocene-sulfonic acid (Fc) can be doped in poly-1-naphthylamine (PNA) and enhances its electrochemical activity. In a nitrite solution, the PNAFc electrode shows an excellent electrocatalytic activity for the oxidation of nitrite. Based on differential pulse voltammetry (DPV), the response was evaluated with respect to pH, scan rate, temperature, and other variables. The optimum analytical conditions for the determination of nitrite were established. Under optimum conditions, the linear range for nitrite determination was from 0.5 to 100 μM with a detection limit of 0.5 μM. The stability and anti-interference ability of the PNAFc electrode were also evaluated. The results indicate that this sensor is feasible for the determination of nitrite in real water samples. The text was submitted by the authors in English.     

Cysteine combined with carbon black as support for electrodeposition of poly (1,8-Diaminonaphthalene): Application as sensing material for efficient determination of nitrite ions

Poly 1,8-Diaminonaphtahlene/cysteine (poly 1,8-DAN/Cys) combined with carbon black (CB) nanoparticles are proposed as an excellent sensor for the detection of nitrite ions. To design the electrocatalyst, a simple approach consisting on drop-casting method was applied to disperse carbon black on the surface of glassy carbon electrode, followed by the immobilization of cysteine on the surface of CB nanoparticles. The electrochemical polymerization of 1,8-Diaminonaphthalene was conducted in acidic medium by using cyclic voltammetry. The prepared hybrid material was denoted poly 1,8-DAN /Cys/CB. Several methods were used to characterize the structural and electrochemical behavior of the reported hybrid material including Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), amperometry and differential pulse voltammetry (DPV). The prepared electrode displayed an outstanding electroactivity towards nitrite ions reflected by an enhancement in the intensity of the current and a decrease of the charge transfer resistance. Poly 1,8-DAN/Cys/CB displayed an excellent sensing performance towards the detection of nitrite with a very low detection limit of 0.25 µM. Two linear ranges of 1–40 µM and 20–210 µM when using amperometry and differential pulse voltammetry (DPV) were obtained respectively. This work highlights the simple preparation of a polymeric film rich in amine and thiol groups for nitrite detection.     

A Novel Nitrite Amperometric Sensor and Its Application in Food Analysis

Brilliant cresyl blue (BCB), one of the phenoxazine dyes, was electropolymerized on the glassy carbon (GC) electrode. The resulting electroactive polymer film could provide more active sites for anodic oxidation of nitrite, based on which a novel nitrite sensor was developed. The optimized fabrication and sensing conditions were investigated. This sensor exhibited high sensitivity, low detection limit and simple operation toward the electrochemical oxidation of nitrite. It was successfully applied to the determination of nitrite in some food samples and the results were consistent with those obtained with the standard spectrophotometric procedure.     

Electrochemical study and flow-injection amperometric detection of trace NO(2)(-) at CuPtCl(6) chemically modified electrode

A thin film of mixed-valent CuPtCl₆ is deposited on a glassy carbon electrode by continuous cyclic scanning in a solution containing 3×10⁻³ M CuCl₂+3×10⁻³ M K₂PtCl₆+1 M KCl in the potential range from 700 to −800 mV. The cyclic voltammetry is used to study the electrochemical behaviors of nitrite on CuPtCl₆/GC modified electrode and the electrode displays a good catalytic activity toward the oxidation of nitrite. The effects of the film thickness, pH, the electrode stability and precision have been evaluated. Experiments in flow-injection analysis are performed to characterize the electrode as an amperometric sensor for the detection of nitrite. The modified electrode shows a wide dynamic range, quite a low detection limit and short response time. The linear relationship between the flow-injection peak currents and the concentrations of nitrite is at a range of 1×10⁻⁷–2×10⁻³ M with a detection limit of 5×10⁻⁸ M.     

Electrochemical determination of nitrite and iodate based on Pt nanoparticles self-assembled on a chitosan modified glassy carbon electrode

A promising electrochemical sensor was fabricated by the self-assembling of Pt nanoparticles (nano-Pts) on a chitosan (CS) modified glassy carbon electrode (GCE). A field-emission scanning electron microscope (FE-SEM), transmission electron microscopy (TEM) and electrochemical techniques were used for characterization of these composites. It has been found that nano-Pts are inserted into the CS layer uniformly, and have a larger surface area compared to the chitosan modified glassy carbon electrode. Electrocatalytic experiments for the oxidation of nitrite and the reduction of iodate have shown that nano-Pts/CS/GCE can decrease the over-potential and increase the faradic current, which can be used for the sensitive determination of nitrite and iodate. Moreover, the prepared modified electrode exhibits good reproducibility and stability, and it is possible that this novel electrochemical sensor can be applied in the sensing and/or biosensing field.     

基于不同工作电极的亚硝酸盐电化学传感器

亚硝酸盐是环境和生物循环中不可或缺的一部分,但其浓度超标不仅会污染环境,还会致癌。因此对亚硝酸盐实现高效、快速精密检测具有重要的科学和实际意义。基于电化学传感技术的污染物分析与检测已成为研究热点,尤其工作电极的选用和设计对提升响应速度、灵敏度、检测限及降低成本、简化操作等至关重要而备受研究者广泛关注。本文将以玻碳电极、碳糊电极、金属薄膜、聚合物薄膜及碳布电极为分类,针对亚硝酸盐的检测,详细综述基于不同电极的电化学传感器的研究进展。以期通过构建方法和电催化性能的对比为构建新型传感器提供理论与实际指导。     

A Sensitive and Selective Nitrite Detection in Water Using Graphene/Platinum Nanocomposite

A glassy carbon electrode modified with reduced graphene oxide and platinum nanocomposite film was developed simply by electrochemical method for the sensitive and selective detection of nitrite in water. The electrochemical reduction of graphene oxide (GO) efficiently eliminates oxygen‐containing functional groups. Pt nanoparticles were electrochemically and homogeneously deposited on the ErGO surface. Field emission scanning electron microscopy (FE‐SEM), Raman spectroscopy, attenuated total reflectance‐fourier transform infrared spectroscopy (ATR‐FTIR), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) were used to examine the surface morphology and electrocatalytic properties of the Pt‐ErGO nanocomposite film‐modified electrode surface. The fabricated nitrite sensor showed good electrochemical performance with two linear ranges; one from 5 to 100 µM (R²=0.9995) and the other from 100 to 1000 µM (R²=0.9972) and a detection limit of 0.22 µM. The proposed sensor was successfully applied for the detection of nitrite in tap water samples which proves performance of the Pt‐ErGO nanocomposite films.     

导电高分子在神经界面电极中的应用

神经界面电极作为人体和外部器件间信息融合的媒介, 为人们进一步探究神经系统高级功能的机制提供了有效工具. 传统的神经电极多以金属和半导体材料为主, 这两类材料因具有惰性材料的特性及优越的 导电性能而成为早期神经电极的主要制备材料, 但由于其刚性过大和光滑表面导致的机械失配及与生物组织间过高的电化学阻抗限制了神经电极的进一步发展. 导电高分子作为一种有机导电材料, 同时具备柔软性 (杨氏模量约在0.01~10 GPa)和导电性(高掺杂度的导电高分子的电导率在金属范围, 10⁰~10⁵ S/cm)的特征, 是制备神经电极的有效材料. 近年来, 人们利用导电高分子材料对传统电极材料进行改性甚至替代, 以提高电极比表面积、 减小界面阻抗, 并提高电极检测的灵敏性; 同时减小电极与组织间的应变失配, 减少炎症反应, 并进一步在导电高分子中引入功能性生物大分子, 减少生物组织对电极的排异反应, 增加电极在体内长期植入的稳定性. 本文讨论和总结了导电高分子材料在神经电极中的应用, 分别对导电高分子作为涂层修饰神经电极、 全导电高分子材料神经电极及导电高分子复合材料神经电极等展开讨论, 分析了导电高分子在神经界面电极中的应用前景及存在的问题, 以期对神经界面电极在脑科学和生物电子医疗等前沿领域的进一步发展提供参考.     

A novel nitrite sensor based on graphene/polypyrrole/chitosan nanocomposite modified glassy carbon electrode

A novel nitrite sensor was fabricated based on a graphene/polypyrrole/chitosan nanocomposite film modified glassy carbon electrode. The nanocomposite film was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy and Raman spectroscopy. The electron transfer behaviour of the modified electrodes was investigated in [Fe(CN)(6)](3-)/(4-) redox probe using cyclic voltammetry and electrochemical impedance spectroscopy. Differential pulse voltammetry and amperometry were used to study the electrochemical properties of the proposed sensor. Under optimum conditions, the sensor exhibited good reproducibility and stability for nitrite determination. Linear response was obtained in the range of 0.5-722 μM with a detection limit of 0.1 μM (S/N = 3) for nitrite determination.     

基于Au/rGO/FeOOH的新型电化学传感器一步检测亚硝酸盐

亚硝酸盐是一种广泛存在的原料,长期食用会对人体健康不利甚至致癌。因此,简单、灵敏的亚硝酸盐检测方法的开发具有非常重要的意义。本文合成了金/还原氧化石墨烯/羟基氧化铁(Au/rGO/FeOOH)复合材料,并通过SEM、 XRD和EDX等测试进行了材料表征。将合成的复合材料滴涂在氧化氟锡(FTO)电极表面,利用它们的协同催化氧化性能,成功构建了一步检测亚硝酸盐(NO₂^-)的新型电化学传感器。在最佳优化实验条件下, 通过差分脉冲伏安法实现NO₂^-的定量检测, 其线性范围为0.001 ~ 5 mmol·L^-1, 检出限为0.8 μmol·L^-1(S/N = 3), 且响应时间小于2 s。同时, 所制备的传感器表现出良好的选择性和重现性, 也能用于实际样品的测定。     

Electrochemical sensors for monitoring environmental pollutants

Stricter environmental controls on the emission and discharge of chemical pollutants are creating an increased demand for the development of improved chemical sensor devices. Although electrochemical sensors show great promise for this task, their utility has been constrained by a number of practical problems, the most serious being the effect of surface adsorption of impurities leading to non-reproducible response. This review presents a survey of recent advances in electrochemical sensor technology which have attempted to improve the performance of these devices. Three main areas of development have been addressed; advances in sensor design and measurement techniques, novel approaches to conferring electrode selectivity and the use of microminiaturization and microelectronics fabrication techniques. Recent applications and future prospects for the measurement of toxic metals, organics and gases including volatile organic compounds are surveyed.     

Electrochemical non-enzymatic glucose sensors

The electrochemical determination of glucose concentration without using enzyme is one of the dreams that many researchers have been trying to make come true. As new materials have been reported and more knowledge on detailed mechanism of glucose oxidation has been unveiled, the non-enzymatic glucose sensor keeps coming closer to practical applications. Recent reports strongly imply that this progress will be accelerated in ‘nanoera’. This article reviews the history of unraveling the mechanism of direct electrochemical oxidation of glucose and making attempts to develop successful electrochemical glucose sensors. The electrochemical oxidation of glucose molecules involves complex processes of adsorption, electron transfer, and subsequent chemical rearrangement, which are combined with the surface reactions on the metal surfaces. The information about the direct oxidation of glucose on solid-state surfaces as well as new electrode materials will lead us to possible breakthroughs in designing the enzymeless glucose sensing devices that realize innovative and powerful detection. An example of those is to introduce nanoporous platinum as an electrode, on which glucose is oxidized electrochemically with remarkable sensitivity and selectivity. Better model of such glucose sensors is sought by summarizing and revisiting the previous reports on the electrochemistry of glucose itself and new electrode materials.     

Rapid bioanalysis with chemical sensors: novel strategies for devices and artificial recognition membranes

The increasing importance of biological analytes in chemistry has triggered the development of a vast number of techniques for rapidly assessing them. Aside from microbiological test methods, a wide range of analytical sensor and detection methods are being developed. Within this article, we review the literature on this topic from the last five years, stressing two main aspects of method development. The first aspect is the design of novel analytical strategies and transducers to generate signals more sensitively, more rapidly and more efficiently. Most of the progress in this field has focused on electrochemical detection, although novel approaches to optical and mass-sensitive measurements have been reported. Second, we provide an overview of two main approaches to creating artificial interaction layers for sensors based on tailored interaction sites in polymeric or biomimetic systems. The most prominent of these approaches is (molecular) imprinting, where selectivity is achieved by directly templating a polymer material with the target analyte or a model compound, thus achieving biomimetic interaction sites within both thin films and particles.