DNA‐Modified Screen‐Printed Electrodes with Nanostructured Films of Multiwall Carbon Nanotubes,Hydroxyapatite and Montmorillonite

Nanostructured films were deposited at the surface of working electrode of the screen‐printed assembly and utilized for the surface modification with double‐stranded DNA. The basic electrochemical properties of the sensors were investigated using voltammetric methods. Modified electrodes were also characterized by scanning electron microscopy and electrochemical impedance measurements. It was found that the electrode modification with DNA and nanomodifier leads to an enhanced sensitivity of the DNA voltammetric detection. New potentialities of the utilization of the K₃[Fe(CN)₆] cyclic voltammetric signal and electrochemical impedance spectroscopy were found. The DNA‐based biosensors showed good repeability and necessary stability within several days.     

Recent electroanalytical applications of boron-doped diamond electrodes

This review overviews recent reports on the electroanalytical applications of boron-doped diamond (BDD) electrodes. Because BDD electrodes have excellent features for electroanalysis, such as wide potential window, low background current, electrochemical stability, and fouling resistance, they can be useful for sensitive and stable detection of various substances, including drugs, bio-related substances, metal ions, and organic pollutants. Many articles have reported high-sensitivity detection of real samples, demonstrating that this electrode material is practically applicable. Surface modification of the BDD electrodes using metal nanoparticles, nanocarbons, and polymers can increase the sensitivity of the electrochemical detection. Furthermore, research on the electroanalytical device equipped with BDD electrodes will be expanded by combining peripheral technologies related to the device fabrication.     

Template‐Free Galvanic Nanostructuring of Gold Electrodes for Sensitive Electrochemical Biosensors

Gold nanostructuring of smooth gold disk‐electrodes has been performed by electrodeposition. FE‐SEM images indicate a strongly enlarged electrochemically active surface of the modified electrodes. This could be approved by the gold oxide reduction peak in cyclic voltammetry. The electrodes were also applied for sequence‐specific DNA detection. For this, complementary single stranded capture probes were immobilized on the electrodes and consecutively hybridized with complementary and noncomplementary [OsO₄(bipy)]‐labeled DNA targets. We found that intermediate dehybridization steps did not decrease the sensitivity for the specific target. Moreover, the surface modification increased the voltammetric signal by an approx. factor of 9. Further, an enhanced linear calibration range was observed. The presented simple nanostructuring process holds great promise for many electrochemical sensor applications.     

A Review on the Effects of Introducing CNTs in the Modification Process of Electrochemical Sensors

This review summarizes some developments in the fabrication of modified sensors and biosensors through the incorporating the carbon nanotubes (CNTs) in their modification ingredients. A large number of papers have paid attention towards the application of carbon nanotubes (CNTs) as electrode constituents and studied its electrochemical behavior. Here, we survey the achievements in the detection of various substances with high selectivity and sensitivity provided using CNTs based electrodes. Moreover, modified electrodes by CNTs have demonstrated the electrocatalytic features and higher sensitivity in detection of analytes. The improved characteristics arises from the large surface area and good conductivity of CNTs. However, it should be considered that the use of single walled carbon nanotubes (SWCNTs) or multi‐walled carbon nanotubes (MWCNTs), the presence of impurities, and the chemical procedures adopted are effective on the performance of the modified sensors.     

Functional groups modulate the sensitivity and electron transfer kinetics of neurochemicals at carbon nanotube modified microelectrodes

The surface properties of carbon-based electrodes are critically important for the detection of biomolecules and can modulate electrostatic interactions, adsorption and electrocatalysis. Carbon nanotube (CNT) modified electrodes have previously been shown to have increased oxidative sensitivity and reduced overpotential for catecholamine neurotransmitters, but the effect of surface functionalities on these properties has not been characterized. In this study, we modified carbon-fiber microelectrodes (CFMEs) with three differently functionalized single-wall carbon nanotubes and measured their response to serotonin, dopamine, and ascorbic acid using fast-scan cyclic voltammetry. Both carboxylic acid functionalized and amide functionalized CNTs increased the oxidative current of CFMEs by approximately 2-6 fold for the cationic neurotransmitters serotonin and dopamine, but octadecylamine functionalized CNTs resulted in no significant signal change. Similarly, electron transfer was faster for both amide and carboxylic acid functionalized CNT modified electrodes but slower for octadecylamine CNT modified electrodes. Oxidation of ascorbic acid was only increased with carboxylic acid functionalized CNTs although all CNT-modified electrodes showed a trend towards increased reversibility for ascorbic acid. Carboxylic acid-CNT modified disk electrodes were then tested for detection of serotonin in the ventral nerve cord of a Drosophila melanogaster larva, and the increase in sensitivity was maintained in biological tissue. The functional groups of CNTs therefore modulate the electrochemical properties, and the increase in sensitivity from CNT modification facilitates measurements in biological samples.     

Manganese dioxide graphite composite electrodes: application to the electroanalysis of hydrogen peroxide, ascorbic acid and nitrite.

The modification of carbon powder with manganese dioxide using a wet impregnation procedure with electrochemical characterisation of the modified powder is described. The process involves saturation of the carbon powder with manganese(II) nitrate followed by thermal treatment at ca. 773 K leading to formation of manganese(IV) oxide on the surface of the carbon powder. The construction of composite electrodes based on manganese dioxide modified carbon powder and epoxy resin is also described, including optimisation of the percentage of the modified carbon powder. Composite electrodes showed attractive performances for electroanalytical applications, proving to be suitable for the electrochemical detection of hydrogen peroxide, ascorbic acid and nitrite ions with limits of detection comparable to the detection limits achieved by other analytical techniques. The results obtained for detection of these analytes, together with composite electrodes flexible design and low cost offers potential application of composite electrodes in biosensors.     

In-channel modification of electrochemical detector for the detection of bio-targets on microchip

The coulometric efficiency (C_eff) of an amperometric detector integrated on PDMS/glass capillary electrophoresis microfluidic device (microchip) has been enhanced by in-channel electrochemical modification. In-channel electrochemical deposition of gold particles was performed in order to vertically increase the surface area of the Au sensing microelectrode. The roughness of the electrodes was characterized using scanning electron microscopy and profilometric analysis. The degree of electrode modification was also characterized by roughness factor determination. Separation processes including detection potential was optimized and the analytical performance of the microchip was tested using a mixture of dopamine (DA) and catechol (CA). The modified electrochemical detector provided well-resolved separation of DA and CA in less than 60 s with enhanced sensitivity; no peak broadening was observed. The limit of detection using in-channel modification of working electrode for DA and CA are 60 and 110 nM, respectively. Thus, in-channel electrochemical deposition of metallic particles should be used to enhance the C_eff of integrated amperometric detection of analytes with good redox properties in order to obtain lower LODs.     

An indium tin oxide electrode modified with gold nanorods for use in potential-controlled surface plasmon resonance studies

The modification of electrodes with gold nanoparticles results in an increased electrode surface area, enhanced mass transport, and improved catalytic properties. We have extended this approach to indium tin oxide (ITO) electrodes to obtain optically transparent gold nanorod-modified electrodes which display enhanced electrochemical capabilities and have the additional advantage of showing a tunable surface plasmon resonance. The procedures for attaining high surface coverage (15 gold nanorods per square µm) of such electrodes were optimized, and the potential-dependent surface plasmon resonance was studied under controlled electrical potential. In an exemplary sensor application, we demonstrate the detection of mercury via potential-dependent formation of an Au-Hg amalgam.

还原氧化石墨烯/金纳米修饰电极在新冠病毒检测中的应用

研究使用电化学沉积法在丝网印刷碳电极表面制备了还原氧化石墨烯和金纳米颗粒,构建了一种用于新冠病毒检测的石墨烯电化学传感器。通过扫描电子显微镜(SEM)和相应的电化学方法对纳米复合材料在电极表面的成功修饰进行了表征分析。并采用差分脉冲伏安法对传感器的性能进行检测,实验构建的电化学传感器具有良好的灵敏度,该传感器检线性范围为10_-10^-10_-6^mol/L,具有良好的重复性和特异性。     

Electrochemical Nano-Roughening of Gold Microstructured Electrodes for Enhanced Sensing in Biofluids**

A key challenge for sensor miniaturization is to create electrodes with smaller footprints, while maintaining or increasing sensitivity. In this work, the electroactive surface of gold electrodes was enhanced 30-fold by wrinkling followed by chronoamperometric (CA) pulsing. Electron microscopy showed increased surface roughness in response to an increased number of CA pulses. The nanoroughened electrodes also showed excellent fouling resistance when submerged in solutions containing bovine serum albumin. The nanoroughened electrodes were used for electrochemical detection of Cu²⁺ in tap water and of glucose in human blood plasma. In the latter case, the nanoroughened electrodes allowed highly sensitive enzyme-free sensing of glucose, with responses comparable to those of two commercial enzyme-based sensors. We anticipate that this methodology to fabricate nanostructured electrodes can accelerate the development of simple, cost-effective, and high sensitivity electrochemical platforms.     

Electrochemical Biosensing for Cancer Cells Based on TiO2/CNT Nanocomposites Modified Electrodes

Both TiO₂ nanoparticles and carbon nanotubes have been usually utilized to modify the electrodes to enhance the detection sensitivity of biomolecular recognition. In this research, novel TiO₂/CNT nanocomposites have been prepared and doped on the carbon paper as the modified electrodes. Subsequently, the redox behavior of the ferricyanide probe and the surface properties of the cancer cells coated on the modified electrodes have been investigated by using electrochemical and contact angle measurements. Compared with electrochemical signals on bare carbon paper and nanocomposite modified substrates, the significantly enhanced electrochemical signals on the modified electrodes covered with cancer cells have been observed. Meanwhile, different leukemia cells (i.e., K562/ADM cells and K562/B.W. cells) could be also recognized because of their different electrochemical behavior and hydrophilic/hydrophobic features on the modified electrodes due to the specific components on the plasma membranes of the target cells. This new strategy may have potential application in the development of the biocompatible and multi‐signal responsive biosensors for the early diagnosis of cancers.     

农药残留的安培检测法*

建立灵敏高效的农药分析方法对于有效解决由农残超标引起的食品卫生安全和环境污染等问题具有重要意义。安培检测法作为一种简便、快速、灵敏、准确的电化学方法,最近几年来被越来越多地应用于农药分析研究,其研究热点主要集中于通过对电化学体系中工作电极的选择和优化来改善检测的性能,提高灵敏度,降低检测限。本文根据检测体系中工作电极的分类从常规电极、修饰电极以及微电极等3方面对农药残留安培检测体系的研究进展作了综述,并认为集成便携化是农残电化学检测方法的研究发展趋势。     

Catalytically active platinum blacks prepared by magnetron sputtering in vacuum and their using in fuel cells with solid polymer electrolyte

Highly disperse platinum film were vacuum-plasma-deposited onto titanium foil and gas-diffusion layers. The platinum deposits have complicated structure. By measuring hydrogen desorption peaks, the catalysts’ active specific surface area was determined and the roughness factor calculated. The electrochemical activity of the electrodes on gas-diffusion layers in the oxygen reduction and hydrogen oxidation reactions was determined. It was shown that the catalysts’ specific activity depends on the platinum content and the Nafion-ionomer additive. The high-activity electrodes were tested in Membrane Electrode Assemblies of low-temperature fuel cells.     

Nanostructured DNA Microarrays for Dual SERS and Electrochemical Read‐out

We present a strategy to fabricate nanostructured microarrays ready to perform a dual read‐out, namely electrochemical (EC) as well as surface‐enhanced Raman spectroscopy (SERS) based detection of DNA hydridization. A polystyrene nanobeads monolayer assembly, obtained by means of a Langmuir Blodgett type technique, followed by electrochemical Au deposition, was employed to construct homogeneous nanostructures in the form of inverse‐opal nanovoids on a 32‐electrode Au microarray chip. Characterization of the obtained nanostructured electrodes of the array by means of cyclic voltammetry demonstrated high reproducibility of the surface modification process. The performance of the obtained array platform was investigated by modifying the microarray electrodes with three different oligonucleotide capture probes using a previously developed potential‐assisted surface modification protocol. Two ferrocene‐labeled target DNA sequences and one target RNA sequence with a Texas red label were detected electrochemically and via SERS, respectively.     

Selective Electrochemical Detection of Explosives with Nanomaterial Based Electrodes

Explosive detection technologies play a critical role in maintaining national security, remain an active research field with many devices and analytical/electroanalytical techniques. Analytical chemistry needs for homeland defense against terrorism make it clear that real-time and on-site detection of explosives and chemical warfare agents (CWAs) are in urgent demand. Thus, current detection techniques for explosives have to be improved in terms of sensitivity and selectivity, opening the way to electrochemical devices suitable to obtain the targeted analytical information in a simpler, cheaper and faster way. For the electrochemical determination of energetic substances, a large number of sensor electrodes have been presented in literature using different modification materials, especially displaying higher selectivity with molecularly imprinted polymers (MIPs). MIPs have already been utilized for the detection of hazardous materials due to their mechanical strength, flexibility, long-time storage and low cost. The sensitivity of MIP-based electrosensors can be enhanced by coupling with nanomaterials such as graphene oxide (GOx), carbon nanotubes (CNTs), or nanoparticles (NPs). Specific characteristics of involved nanomaterials, their modification, detection mechanism, and other analytical aspects are discussed in detail. Non-MIP electrosensors are generally functionalized with materials capable of charge transfer, H-bonding or electrostatic interactions with analytes for pre-concentration and electrocatalysis on their surface, whereas nanobio-electrosensors use analyte-selective aptamers having specific sequences of DNA, peptides or proteins to change the potential or current. This review intends to provide a combination of information related to MIPs and nanomaterial-based electrochemical sensors, limited to the most significant and illustrative work recently published.     

Electrochemical Detection of Phenylurea Herbicides in Liquid Chromatography

Abstract

This paper describes the electrochemical detection of ten phenylurea herbicides after on-line trace enrichment on a small C18 precolumn and liquid chromatography on a C18 analytical column. The method presented shows sub-ppb sensitivity in surface water samples without extensive sample pretreatment. Electrode contamination occurs but does not seriously interfere in the routine analysis of such samples. Selective determination (at 1. 0 V) of metoxuron in the presence of other phenylureas allows the detection of 30 ppt of the herbicide in surface water.     

Poly(dimethylsiloxane) cross-linked carbon paste electrodes for microfluidic electrochemical sensing

Recently, the development of electrochemical biosensors as part of microfluidic devices has garnered a great deal of attention because of the small instrument size and portability afforded by the integration of electrochemistry in microfluidic systems. Electrode fabrication, however, has proven to be a major obstacle in the field. Here, an alternative method to create integrated, low cost, robust, patternable carbon paste electrodes (CPEs) for microfluidic devices is presented. The new CPEs are composed of graphite powder and a binder consisting of a mixture of poly(dimethylsiloxane) (PDMS) and mineral oil. The electrodes are made by filling channels molded in previously cross-linked PDMS using a method analogous to screen printing. The optimal binder composition was investigated to obtain electrodes that were physically robust and performed well electrochemically. After studying the basic electrochemistry, the PDMS-oil CPEs were modified with multi-walled carbon nanotubes (MWCNT) and cobalt phthalocyanine (CoPC) for the detection of catecholamines and thiols, respectively, to demonstrate the ease of electrode chemical modification. Significant improvement of analyte signal detection was observed from both types of modified CPEs. A nearly 2-fold improvement in the electrochemical signal for 100 μM dithiothreitol (DTT) was observed when using a CoPC modified electrode (4.0 ± 0.2 nA (n = 3) versus 2.5 ± 0.2 nA (n = 3)). The improvement in signal was even more pronounced when looking at catecholamines, namely dopamine, using MWCNT modified CPEs. In this case, an order of magnitude improvement in limit of detection was observed for dopamine when using the MWCNT modified CPEs (50 nM versus 500 nM). CoPC modified CPEs were successfully used to detect thiols in red blood cell lysate while MWCNT modified CPEs were used to monitor temporal changes in catecholamine release from PC12 cells following stimulation with potassium.     

Electrochemical urea biosensor based on Proteus mirabilis urease immobilized over polyaniline PANi-Glassy carbon electrode

In this study, a novel, sensitive electrochemical enzyme-based biosensor for urea detection was presented. This biosensor combines a three-electrode system consisting of a classic Glassy Carbon Electrode (GCE) as the working electrode, a platinum counter electrode, and Ag/AgCl as the reference electrode. To construct this urea platform, a GCE was modified with a polyaniline (PANi) film. Then, bacterial urease from Proteus mirabilis was immobilized on the modified GCE (P_m-Urease-PANi-GCE). For the characterization of surface modification, Cyclic Voltammetry (CV) and Scanning Electron Microscope (SEM) were applied, while the Square Wave Voltammetry (SWV) technique was performed for urea detection. The main analytical characteristics of the P_m-Urease-PANi-GCE biosensor showed a good linear range from 0.1 to 10 mM of urea, a limit of detection (LOD) of 0.1 mM, a Michaelis-Menten K_m of 0.23 mM, and a sensitivity value 46 μA/mM/cm². This biosensor allows the detection of urea in solutions, and it could be improved for further medical, environmental, or engineering applications.     

A Thick-Film Carbon-Containing Electrode Modified with Formazan for Determining Copper, Lead, Cadmium, and Zinc

The electrochemical behavior of some hetarylated formazans introduced into the bulk of carbon-containing inks of thick-film screen-printed electrodes was studied. The compositions of complexes formed at the electrode surface were found, and their stability constants were estimated. It was shown that the modification of a carbon-containing thick-film electrode with 1-(o-chlorophenyl)-3-phenyl-5-(6-methyl-4-oxo-pyrimidinyl-2)formazan improves its sensitivity, lowers detection limits for Pb(II), Cu(II), Cd(II), and Zn(II), and ensures high precision of the results of analysis.     

Inkjet printed Prussian blue films for hydrogen peroxide detection

An inkjet printing method is described to fabricate hydrogen peroxide (H(2)O(2)) sensors. Insoluble Prussian blue (PB) nanoparticles were dispersed in aqueous solvent, and were printed on screen printed carbon electrodes with a piezoelectric inkjet printer for H(2)O(2) detection. The electrochemical behavior of the printed sensors was studied by using cyclic voltammetry and chronoamperometry. The printed sensors showed great electrocatalytic activity toward H(2)O(2) and can be used for amperometric detection of H(2)O(2). The calibration curves for H(2)O(2) determination showed a linear range from 0.02 to 0.7 mM with a sensitivity of 164.82 μA M(-1) cm(-2) for the printed PB film. The results showed the feasibility of applying inkjet printing technology on surface modification; the results also provide an alternative way for manufacturing electrochemical sensors.