Electrochemical methods in understanding the redox processes of drugs and biomolecules and their sensing

Progression of the biochemical information of drugs and its interaction with biological substances require efficient methodologies suitable for generating information without incurring any significant damage to the analytes. Electrochemical methods provide useful information and compatible to the biological environments, without any significant alterations in the analyte, the methods are capable in onsite applications. Present review discusses about the application of the electrochemical techniques in evaluating the mechanism of interaction of drugs with the biomaterials like proteins, lipids, and DNA. The redox process leads to the determination of the drugs and biomolecules through the development of modified electrodes. The modified ultra-microelectrodes (UMEs) or nano electrodes are useful in sensing at the extracellular level of single cells. The electrochemical collision using UMEs provides information about the single molecular level. Present article discusses a brief review of some of the drug and biomolecule interactions using macro and also UMEs.     

Miniaturized electrochemical sensors and their point-of-care applications

Most of the current analytical methods depend largely on laboratory-based analytical techniques that require expensive and bullky equipment,potentially incur costly testing,and involve lengthy detection processes.With increasing requirements for point-of-care testing(POCT),more attention has been paid to miniaturized analytical devices.Miniaturized electrochemical(MEC)sensors,including different material-based MEC sensors(such as DNA-,paper-,and screen electrode-based),have been in strong demand in analytical science due to their easy operation,portability,high sensitivity,as well as their short analysis time.They have been applied for the detection of trace amounts of target through measuring changes in electrochemical signal,such as current,voltage,potential,or impedance,due to the oxidation/reduction of chemical/biological molecules with the help of electrodes and electrochemical units.MEC sensors present great potential for the detection of targets including small organic molecules,metal ions,and biomolecules.In recent years,MEC sensors have been broadly applied to POCT in various fields,including health care,food safety,and environmental monitoring,owing to the excellent advantages of electrochemical(EC)technologies.This review summarized the state-of-the-art advancements on various types of MEC sensors and their applications in POCT.Furthermore,the future perspectives,opportunities,and challenges in this field are also discussed.     

Electrodes supported on ion-exchange membranes as sensors in gases and low-conductivity solvents

An electroanalytical sensor is proposed that is suitable for the detection of electroactive analytes present in gases or low-conductivity solvents where supporting electrolytes cannot be introduced. It consists of a porous working electrode supported on one surface of a cationic ion-exchange membrane (Nafion 417), the other surface of which is in contact with an electrolyte solution containing the counter and reference electrodes. Such an ion-exchange membrane replaces a conventional supporting electrolyte dissolved in the analyte sample and can be regarded as a solid polymer electrolyte (SPE) confined in the close neighbourhood of the working electrode. Alternative procedures followed for coating SPE membranes with various materials (Pt, Au, C or Hg) are described, together with the general properties displayed by the resulting composite electrodes in analyte-free gaseous or liquid media. These assemblies have been used as both voltammetric and amperometric sensors for electroactive analytes present in gases and in aqueous or organic solvents with no supporting electrolyte. The results indicate that their performance is similar to that expected on conventional electrodes, the only difference being a slightly lower degree of reversibility for the electrode processes investigated. Detection limits for some analytes were calculated and the use of SPE electrodes as sensors suitable for the continuous monitoring of electroactive analytes dispersed in gases or non-conductive liquids is reported. Preliminary attempts to use these assemblies for the determination of trace metals in low-conductivity solvents by anodic stripping voltammetry are discussed.     

无机物的光学和电化学传感器

本文讨论将溶胶凝胶作为一种基质来发展独特的传感策略．溶胶凝胶为传感基质的制备和发展提供了无限空间,这种空间得益于基质物理性质的多样性,可以通过改变一些传感器已知的制备条件和合成技术来实现．我们在对传感需求的认真考虑和研究的基础上,开发出了用于一些分析物的新的检测方法,同时发展了它们的应用．溶胶凝胶被用来监测浓强酸（[H^＋]=1～11M）,浓强碱（[OH^-]：1～10M）及采用双传感方法来测定混合溶剂／溶质系统．本文还讨论了使用配体嫁接的块状溶胶凝胶对金属离子进行光学测定．最后介绍了用电化学法和溶胶凝胶修饰的电极来测定六价铬的方法．     

毛细管电泳安培检测技术进展

对毛细管电泳离柱和柱端安培检测方式、不同形式电极在安培检测中的应用、安培检测在芯片毛细管电泳中的应用、安培检测池等内容进行了总结和讨论 ,并预测了安培检测技术未来发展方向     

Optical and electrochemical sol-gel sensors for inorganic species

The use of sol-gels as a sensing matrix for the development of unique sensing strategies is discussed. Sol-gels offer almost limitless possibilities for sensing substrates due to the variety of physical properties that can be obtained by altering a number of discussed fabrication conditions and techniques. By careful consideration of the sensing requirements, novel detection methods have been developed for a variety of analytes and applications. Here, sol-gels have been used to monitor pH at the extreme ends of the scale ([H⁺] = 1–11 M and [OH⁻] = 1–10 M) and in mixed solvent/solute systems using dual sensing approaches. The use of ligand-grafted sol-gel monoliths for optical determination of metal ion species is also discussed. The electrochemical determination of Cr(VI) by electrodeposited sol-gel modified electrodes is also presented.     

Pencil‐Drawn Dual Electrode Detectors to Discriminate Between Analytes Comigrating on Paper‐Based Fluidic Devices but Undergoing Electrochemical Processes with Different Reversibility

A simple method is described to discriminate between analytes comigrating under on‐plate separation conditions, whose electrochemical behavior displays different reversible characters. It is based on the use of dual electrode detectors pencil‐drawn at the end of paper‐based fluidic channels defined by hydrophobic barriers. Simultaneous detection of comigrating species is achieved by applying to the upstream pencil‐drawn working electrode a potential for the oxidation (or reduction) of both analytes, while to the downstream pencil‐drawn working electrode a potential is imposed for the reverse process involving the product of the sole analyte undergoing a reversible enough electrochemical process. The performance of these inexpensive devices was preliminarily optimized by adopting hexacyanoferrate(II) as prototype species undergoing a reversible anodic process at carbon electrodes. They were then used as dual electrode detectors for thin‐layer chromatographic runs conducted on paper‐based microfluidic devices. Two types of synthetic solutions, one containing different contents of dopamine (DA) and ascorbic acid (AA) and the other of paracetamol (PA) and AA, were chosen as model samples. This choice was prompted us by the fact that in both cases these analytes comigrated under the adopted experimental conditions and required similar enough oxidation potentials. Nevertheless, DA and PA underwent reversible enough anodic processes while an irreversible electrochemical reaction is involved in the AA oxidation. Satisfactory results were found for both couples of target analytes, whose simultaneous detection was achieved within 230 s and was characterized by good enough repeatability and sensitivity. In particular, this approach appears to be well suited for the rapid and inexpensive assembling of electrochemical detectors for flow analysis systems.     

Recent developments on the modification of graphite electrodes with nanoparticles

The surface structure of common graphite electrodes are suitable for electrochemical detection of various analytes due to their favorable properties such as good conductivity and resistance to environmental and chemical hazards. Also this material is cheap and available. Modifying the surface of electrode improves their ability for various determinations. Modifying graphite electrodes with nanoparticles has attracted lots of attention due to their unique characteristics. In this article we review applications of modified graphite electrodes with nanomaterials.     

Nanoelectrodes, nanoelectrode arrays and their applications

This review deals with the topic of ultrasmall electrodes, namely nanoelectrodes, arrays of these and discusses possible applications, including to analytical science. It deals exclusively with the use of nanoelectrodes in an electrochemical context. Benefits that accrue from use of very small working electrodes within electrochemical cells are discussed, followed by a review of methods for the preparation of such electrodes. Individual nanoelectrodes and arrays or ensembles of these are addressed, as are nanopore systems which seek to emulate biological transmembrane ion transport processes. Applications within physical electrochemistry, imaging science and analytical science are summarised.     

Electrochemical Sample Preparation for the Voltammetric Determination of Heavy-Metal Ions in Wine

An original, simple, and rapid method consuming little labor and eliminating the contamination of a sample and the loss of analytes is proposed for the electrochemical preparation of wine samples. The time of electrochemical sample preparation (ECSP) is no longer than 10 min. A four-electrode single-compartment electrolyzer allows all stages of voltammetric analysis (electrochemical sample preparation, electrochemical preconcentration and determination) to be carried out continuously. The processes occurring at electrodes at different stages of analysis are described. The concentrations of heavy metals determined in wines by stripping voltammetry (SVA) and atomic absorption spectroscopy (AAS) are compared.     

Electrochemical methods for the determination of heparin

A review of studies on the determination of heparin in various samples (pharmaceuticals, biological fluids) by electrochemical methods of analysis in 1976–2014 is presented. Heparin is most often determined in pharmaceuticals by polarography using cationic dyes, and in biological samples, by differential pulse methods on non-stationary mercury electrodes. Works on the creation of heparin-selective electrodes coated with a polyvinylchloride membrane with quarternary ammonium salts are most promising; they can, probably, be used for the creation of portable devices for the determination of heparin.     

New approaches in the development of DNA sensors: hybridization and electrochemical detection of DNA and RNA at two different surfaces

Up to now, the development of the electrochemical DNA hybridization sensors relied on solid electrodes, on which both the hybridization and detection steps have been performed. Here we propose a new method in which the DNA hybridization is performed at commercially available magnetic beads and electrochemical detection on detection electrodes (DE). Due to minimum nonspecific DNA adsorption at the magnetic beads, very high specificity of the DNA hybridization is achieved. Optimum DE can be chosen only with respect to the given electrode process. It is shown that high sensitivity and specificity in the detection of relatively long target DNAs can be obtained (a) by using cathodic stripping voltammetry at mercury or solid mercury amalgam DEs for the determination of purine bases, released from DNA by acid treatment, and (b) by enzyme-linked immunoassay of target DNA modified by osmium tetroxide,2,2'-bipyridine (Os,bipy) at carbon DEs. Direct determination of Os,bipy at mercury and carbon electrodes is also possible.     

Modification of electrodes with catalytic, size-exclusion films

The application of electroanalytical methodology to the study of liquid-phase samples can be complicated by the adsorption of sample components on the electrode surface. Macromolecules are particularly problematic in this regard. An early means of addressing this problem was to use a membrane permeable to the analyte as a barrier between the sample phase and the electrochemical cell. Amperometric determination of oxygen in biological fluids is a historically important example. This approach was refined by modifying electrodes with semi-permeable, conducting films applied directly to the surface of the working electrode. Cellulose acetate is an example of a conductive material that blocked adsorption of compounds in biological samples but was permeable to analytes such as hydrogen peroxide. Modification of electrodes with ion-exchange films and, more recently, porous sol?Cgel films was an expansion of this methodology. A complicating factor was that oxidation or reduction of most analytes requires a catalyst. The development of films that are size-exclusion barriers to interferents and incorporate an electron-transfer catalyst is described.     

Surfactant templated sulfonic acid functionalized silica microspheres as new efficient ion exchangers and electrode modifiers

Porous sulfonic acid functionalized silica spheres have been prepared by oxidation ofthiol-functionalized mesoporous silica samples obtained by co-condensation of (mercaptopropyl)trimethoxysilane and tetraethoxysilane in the presence ofcetyltrimethylammonium as a template. The physicochemical characteristics of the resulting ion exchangers have been analyzed by various techniques and discussed with respect to the amount of functional groups in the materials. Their ion exchange behavior was then studied from batch experiments (determination of cation exchange capacities) and by electrochemistry at carbon paste electrodes modified with these solids. In particular, ion exchange voltammetry applied to two model electroactive cations, Cu2+ and Ru(NH3)6(3+), has pointed out the key role played by the content of organofunctional groups in the materials (which strongly affects their structure and porosity) on their performance as electrode modifiers for preconcentration of target analytes prior to electrochemical detection.     

LC with Electrochemical Detection. Recent Application to Pharmaceuticals and Biological Fluids

Many pharmaceutical compounds have electroactive groups and are readily measurable and detectable by liquid chromatography with electrochemical detection (LC–EC). LC–EC techniques have many advantages as measurement systems and new materials have been developed for working electrodes. Use of modern electroanalytical techniques for detection in LC of pharmaceutical compounds is discussed in this review. EC detection in LC often results in improved selectivity and detection limits for electroactive pharmaceutical compounds. Selected literature on the determination of pharmaceutical compounds in their dosage forms and in biological samples are reported.     

Reduced Graphene Sheets Modified Electrodes for Electrochemical Detection of Sulfide

This paper describes a new electrochemical sensor based on reduced graphene sheets (RGSs) modified glassy carbon electrodes for rapid detection of sulfide. The morphology and electrochemical properties of the RGSs are characterized by atomic force microscopy and cyclic voltammetry. The effects of the scan rates and pH are investigated to evaluate the oxidation processes. Analytical performances of RGSs modified electrodes for direct determination of sulfide in phosphate buffer solutions (PBSs) are also assessed. The RGSs are shown to be viable potential material for sulfide detection as shown by their electrochemical performance.     

Overview of significant examples of electrochemical sensor arrays designed for detection of nitric oxide and relevant species in a biological environment

Ultramicroelectrode sensor arrays in which each electrode, or groups of electrodes, are individually addressable are of particular interest for detection of several species concomitantly, by using specific sensing chemistry for each analyte, or for mapping of one analyte to achieve spatio–temporal analysis. Microfabrication technology, for example photolitography, is usually used for fabrication of these arrays. The most widespread geometries produced by photolithography are thin-film microdisc electrode arrays with different electrode distributions (square, hexagonal, or random). In this paper we review different electrochemical sensor arrays developed to monitor, in vivo, NO levels produced by cultured cells or sliced tissues. Simultaneous detection of NO and analytes interacting with or released at the same time as NO is also discussed.     

Enhanced Electrocatalytic Detection of Choline Based on CNTs and Metal Oxide Nanomaterials

Choline is an officially established essential nutrient and precursor of the neurotransmitter acetylcholine. It is employed as a cholinergic activity marker in the early diagnosis of brain disorders such as Alzheimer’s and Parkinson’s disease. Low levels of choline in diets and biological fluids, such as blood plasma, urine, cerebrospinal and amniotic fluid, could be an indication of neurological disorder, fatty liver disease, neural tube defects and hemorrhagic kidney necrosis. Meanwhile, it is known that choline metabolism involves oxidation, which frees its methyl groups for entrance into single-C metabolism occurring in three phases: choline oxidase, betaine synthesis and transfer of methyl groups to homocysteine. Electrocatalytic detection of choline is of physiological and pathological significance because choline is involved in the physiological processes in the mammalian central and peripheral nervous systems and thus requires a more reliable assay for its determination in biological, food and pharmaceutical samples. Despite the use of several methods for choline determination, the superior sensitivity, high selectivity and fast analysis response time of bioanalytical-based sensors invariably have a comparative advantage over conventional analytical techniques. This review focuses on the electrocatalytic activity of nanomaterials, specifically carbon nanotubes (CNTs), CNT nanocomposites and metal/metal oxide-modified electrodes, towards choline detection using electrochemical sensors (enzyme and non-enzyme based), and various electrochemical techniques. From the survey, the electrochemical performance of the choline sensors investigated, in terms of sensitivity, selectivity and stability, is ascribed to the presence of these nanomaterials.     

Peroxidase-modified electrodes: Fundamentals and application

Peroxidase-modified amperometric electrodes have been widely studied and developed, not only because of hydrogen- and organic peroxides are important analytes but also because of the key role of hydrogen peroxide detection in coupled enzyme systems, in which hydrogen peroxide is formed as the product of the enzymatic reaction. Many important analytes, such as, aromatic amines, phenolic compounds, glucose, lactate, neurotransmitters, etc. could be monitored by using bi- or multi-enzyme electrodes. In this review the heterogeneous electron transfer properties of peroxidases are discussed as a basis for the analytical application of the peroxidase-modified amperometric electrodes, and examples are given for various peroxidase electrode designs and their application.     

Paper‐based Electrochemical Devices Coupled to External Graphene‐Cu Nanoparticles Modified Solid Electrode through Meniscus Configuration and their Use in Biological Analysis

This paper demonstrates, for the first time, the use of paper‐based electrochemical devices coupled to external solid working electrodes. The paper‐based electrochemical cells were fabricated using inexpensive and largely available office paper, according to a simple protocol that consists on the creation of hydrophobic barriers using paraffinized paper and preheated metal stamp. The counter and reference electrodes were integrated to the paper platform through the deposition of carbon and silver inks, respectively. The electrochemical paper analytical device (ePAD) was coupled to external glassy carbon rod electrode modified with reduced graphene oxide doped with Cu nanoparticles through meniscus configuration. The analytical usefulness of this electrochemical approach was demonstrated through the simultaneous determination of paracetamol and caffeine in biological samples. The analytes were successfully quantified in real urine samples and limits of detection of 24.6 nM (paracetamol) and 36.1 nM (caffeine) were obtained. The paper platform showed good stability (RSD of 1.07 % for the peak currents and 1.43 % for the peak potentials) and satisfactory performance. The use of solid electrodes coupled to paper electrochemical devices, firstly demonstrated here, opens new possibilities for the utilization of ePADs in electrochemistry and electroanalytical chemistry and offers advantages such as the extremely reduced consumption of reagents and the minimal generation of wastes.