Recent development of non-faradaic potentiometry

Non-faradaic potentiometry has been plagued by a great many fundamental errors and a lack of conceptualization. Of greatest concern is the second Nernst equation hiatus. Potentiometry may be generally classified as faradaic and non-faradaic. The former deals with the redox reactions using the Nernst equation to explain the potential origin. The latter deals with the non-redox reactions using the Boltzmann and modified Boltzmann equations to explain the origin of electrode potential. Redox faradaic potentiometry has been well described in the textbooks. However, non-faradaic potentiometry has been almost completely neglected in the literature. Many well-known electrodes, such as the pH glass electrode, common reference electrodes, and ion selective electrodes (ISE) have been mistakenly interpreted as redox reactions or ion exchange reactions. New theories and experimental results show their mechanisms to be non-faradaic in nature. Furthermore, the reaction mechanisms for ISE have been confused in textbooks with redox reactions and the Nernst equation. The ISE potentials originating from adsorption of ions or charged particles based on surface charge density will be explained using the double and counterion triple layers concept. The new counterion triple layer concept may be applied to the potential development of sensors. The reason for a new concept, theory, or mechanism is to better explain the phenomena. Examples will be given of how our new concept explains the capacitor, counterion triple layer, surface adsorbed layers interactions, and the interface structure. We will also discuss the new sensor development based on the new adsorption concept. For the first time a new type of Ag/AgCl reference electrode for non-faradaic potentiometry will be presented, one without a liquid junction and with a Pt wire instead of a salt bridge. They will help open up a new horizon for electrochemical sensor research and may be used under unusual conditions, such as high temperature and high pressure, stirring, etc.     

Electroacoustic miniaturized DNA-biosensor

A micrometer-sized electroacoustic DNA-biosensor was developed. The device included a thin semi-crystalline polyethylene terephthalate (PET) dielectric layer with two Ag microband electrodes on one side and a DNA thiol-labeled monolayer adsorbed on a gold surface on the other. A resonance wave was observed at 29 MHz with a network analyzer, upon AC voltage application between the two Ag electrodes, corresponding to electromechanical coupling induced by molecular dipoles of the PET polymer chain in the dielectric layer. It was found that the device size and geometry were well adapted to detect DNA hybridization, by measuring the capacity of the resonance response evolution: hybridization induced polarization of the dielectric material that affected the electromechanical coupling established in the dielectric layer. The 0.2 mm(2) sensor sensitive area allows detection in small volumes and still has higher detection levels for bioanalytical applications, the non-contact configuration adopted avoids electric faradic reactions that may damage biosensor sensitive layers, and finally, PET is a costless raw material, easy to process and well adapted for large scale production. The well-balanced technological and economic advantages of this kind of device make it a good candidate for biochip integration.     

A study of the ionic conduction of mica surface by admittance spectroscopy

The ionic conduction on the surface of humid mica has been analyzed by admittance spectroscopy as a function of relative humidity for different surface treatments. Measurements at low frequency indicate that water adsorption proceeds first in the form of a strongly adsorbed uniform thin layer, then with the formation of highly inhomogeneous thick aggregates.     

Gly‐Gly‐His Immobilized On Monolayer Modified Back‐Side Contact Miniaturized Sensors for Complexation of Copper Ions

Miniaturized planar back‐side contact transducers (BSC) with chemically modified gold surface have been utilized as electrochemical sensors. The electrodes have been functionalized by sequential immobilization of aryl diazonium salts or alkanethiols and short peptide Gly‐Gly‐His. The applicability of gold substrates modified with aryl diazonium salts in voltammetric detection of copper(II) ions in aqueous solutions has been studied. The combination of two fundamental elements of the solid‐state electrode, i.e. back‐side contact (BSC) gold sensor and self‐assembled monolayers, allowed one to obtain reliable miniaturized copper(II) ion sensors. It can have important future applications in environmental sensing or in implantable biodevices.     

Application of thin film mercury electrodes and solid amalgam electrodes in electrochemical analysis of the nucleic acids components: detection of the two-dimensional phase transients of adenosine

The optical diffractive (DOE)-based sensor was used to the study of the optical roughness of different carbon/graphite electrodes modified by mercury film (MFEs) and solid amalgam-alloy electrodes (S-MeAEs). The electrode surfaces were visualised by an optical metallurgical microscope. The adsorption of adenosine at the MFEs and S-MeAEs has been investigated by capacitance measurement. Some kinetics aspects, such as the influence of the surface morphology, nature of the substrate and thickness of the mercury film and amalgam-alloy on the formation of two-dimensional (2D) physisorbed adenosine adlayer on the MFEs and S-MeAEs, were studied.     

Disposable Gold Electrode Array for Simultaneous Electrochemical Studies

An efficient and inexpensive eight gold electrode array has been manufactured by a combination of screen printing and gold electrodeposition techniques. Gold electrodeposition was performed in potentiostatic and galvanostatic conditions. Different treatments, involving temperature and polishing control, led to electrodes with different roughness. The electrochemical behavior of the generated gold surface was studied by cyclic voltammetry showing the characteristic response of polycrystalline gold, in contrast with disposable gold electrodes fabricated by screen printing from gold inks. The electrodes were chemically modified through the adsorption of alkanethiols self‐assembled monolayers and the coupling of a model protein. Both reactions were followed by cyclic voltammetry and Electrochemical Impedance Spectroscopy (EIS). The electrodes have shown high reproducibility in their electrochemical behavior as well as in their modifications.     

Biophysical measurement of red blood cells by laboratory on print circuit board chip

Microfluidic impedance pulse sensor has emerged as an easily handled and low‐cost platform in the electrical analysis of biological cells. In the conventional method, impedance sensor demanded expensive patterning metal electrodes on the substrate, which are directly in touch with electrolytes in order to measure the microfluidic channel impedance change. In this article, a cost‐effective microfluidic impedance sensor built upon a dielectric film coated printed circuit board is introduced. Impedance electrodes are protected by a dielectric film layer from electrochemical erosion between electrodes and electrolyte. Human red blood cells from adult and neonatal were utilized to demonstrate the feasibility of the proposed device in the electroanalysis of biological cells.     

Electrocatalysis at chemically modified electrodes : Detection/determination of redox gaseous species in continuous-flow systems

The electrocatalytic response of chemically modified carbon paste and glassy carbon electrodes with anchored Fe(II)/Fe(III) centers is presented for gaseous species such as NO₂, SO₂, H₂S, and Cl₂. Carbon paste electrodes are modified by direct admixing of tris[4,7-diphenyl-1,10-phenanthroline]iron(II) perchlorate, and glassy carbon electrodes are modified by oxidative electropolymerisation of tris[5-amino-1,10-phenanthroline]iron(II) perchlorate. The electrocatalytic cycle operating in the integrated reaction/pre-electrode layer of chemically modified electrodes results in significant signal enhancement. Chemical modification of the conducting surfaces protects the electrode surface from poisoning. evaluation was done in a continuous-flow system using gravitational flow fo supporting electrolyte carrier propulsion, direct injection of air containing parts per billion or parts per million (v/v) of the gaseous species, and amperometric detection with the chemically modified electrodes as part of a thin-layer cell.     

溶菌酶在裸金电极和疏基乙酸或正十二疏烷基醇修饰电极上的吸附

电化学石英晶体阻抗系统;疏基乙酸;溶菌酶在裸金电极和疏基乙酸或正十二疏烷基醇修饰电极上的吸附     

In situ radiotracer study of thiourea adsorption on n-Si (100) and p-Si (100) electrodes

The application of a radiotracer method to in situ studies of the adsorption of thiourea labelled with either C-14 or S-35 nuclides on smooth n-type and p-type Si (100) electrodes and on rough p-Si electrodes is described. The adsorption takes place over the whole potential range studied, i.e. −0.5 to 1.2 V. It was found that during the interaction of thiourea with the silicon surface, two different products are formed. The dependence of the surface concentration of the adsorbates on the electrode potential and on the bulk concentration of thiourea was determined. Two different species are proposed to be present on the electrode surface as a result of surface processes: physically adsorbed thiourea molecules and sulphur atoms which are chemically bonded to the surface. Different activities of smooth and rough silicon electrodes towards the adsorption of thiourea were demonstrated.     

巯基—聚吡咯薄膜修饰电极的制备及其电化学性能

通过将巯基乙酸作为一种支持电解质,将巯基固定在导电聚吡咯薄膜电极上,从而制得巯基—聚吡咯薄膜修饰电极,该修饰电极保持了巯基的螯合性能,并具有良好的稳定性。对水溶液中的重金属离子具有很好的吸附作用,其灵敏度与未修饰的玻碳电极相比,测汞离子时电沉积提高了3倍,化学吸附时提高了近5倍。并对其吸附机理进行了初步的探讨,证明了其对汞离子的吸附为不可逆的产物弱吸附。     

Recent advances in NADH electrochemical sensing design

NADH electrochemical sensor development has been one of the most studied areas of bioelectroanalysis because of the ubiquity of NAD(P)H based enzymatic reactions in nature. The different solutions proposed are still far from the realisation of the “ideal” NADH sensor and the research area is still challenging. The principles and the recent approaches in NADH electrochemical sensing design are reported in this review. An overview of selected examples and novel sensor materials for the electrocatalysis of NADH is given with emphasis on the appropriate design to obtain improved performances. The literature data taken in consideration has been grouped depending on the strategy used in: surface modified electrodes for NADH sensing, surface redox mediated NADH probes, and bulk modified electrodes for the electrocatalytic oxidation of NADH. A list of already reported dehydrogenase-based biosensors is also given.     

The diamond/aqueous electrolyte interface: an impedance investigation

We have investigated the electrochemical interface between diamond electrodes and aqueous electrolytes using electrochemical techniques such as cyclic voltammetry and ac impedance spectroscopy. High-quality CVD-grown boron-doped polycrystalline diamond electrodes and IIa single crystalline natural diamond electrodes have been used in this study. In the case of hydrogen-terminated diamond electrodes, the electrochemical interface is dominated by the electrochemical double layer. Frequency-dependent impedance spectroscopy reveals a potential regime in which the contribution of ion adsorption becomes relevant. We have conducted experiments to evaluate the effect of pH and ionic strength on the double layer. Our results suggest that only ions resulting from water auto-dissociation, i.e., hydroxide and hydronium ions, are responsible for ion adsorption and, thus, able to modify the charge at the double layer. In contrast, no effect of the adsorption of several dissolved ions (such as Na+, K+, Cl-) has been observed On the basis of the electrochemical characterization of H-terminated diamond surfaces, we also discuss the phenomenon of the surface conductivity in diamond, as well as the pH sensitivity of the diamond surface. The influence of the O2/OH- and H2/H3O+ redox couples on the origin of the surface conductivity is discussed.     

A novel Surface Plasmon Resonance enhanced Total Internal Reflection Ellipsometric application: electrochemically grafted isophthalic acid nanofilm on gold surface

The scope of this study is to modify a Surface Plasmon Resonance (SPR) sensor slide with isophthalic acid to evaluate the possible application on the detection of copper(II) ions in aqueous media by total internal reflection ellipsometry. A gold sensor surface was modified by an electrochemical diazonium reduction modification method. The modified surfaces are characterized with cyclic voltammetry (CV) and ellipsometry. Isophthalic acid monolayer modified gold slides were used for in situ detection of aqueous Cu(2+) solution with the SPR enhanced total internal reflection ellipsometry (SPRe-TIRE) technique. Layer formation, pH dependency of adsorption, sensor response of the SPRe-TIRE and isothermal kinetic parameters were examined. A high dependency on the number of CV cycles in the monolayer-multiple layer transition was observed. The suggested sensor gave a linear response over a wide range of Cu(2+) concentrations. It was also reported that adsorption on the SPRe-TIRE sensor gave Langmuir adsorption model behavior.     

Cholinesterase immobilisation on the surface of screen-printed electrodes based on concanavalin A affinity

This paper reports a new method for the immobilisation of acetylcholine esterase (AChE) on the surface of screen-printed electrodes (SPEs) based on the affinity between the glycoprotein enzyme and concavalin A (Con A). The surface of the working electrode has been modified with a Nafion layer that contains graphite, the mediator 7,7,8,8-tetracyanoquinodimethane (TCNQ) and heptylamine. The enzyme-free SPEs were characterised by cyclic voltammetry in buffer solutions and amperometry using cysteamine as analyte. The AChE immobilisation process leads to the sandwich structure: electrode-carbohydrate-Con A-enzyme. The first step of the immobilisation is the covalent activation of an amino group bound in a Nafion layer. The following steps are based on the affinity. The non-specific adsorption has been totally eliminated using BSA solutions at two different pHs. Various amounts of enzyme, from 0.1 to more than 2 mIU AChE, have been loaded on the electrode surface. The method offers the advantage of a free diffusion, which allows obtaining a response time of less than 2 min. An operational stability of more than 10 measurements was registered, while the active surface of the electrode was successfully reloaded for three consecutive times without any important change of the analytical performances.     

Electrochemical and surface characterization of 4-aminothiophenol adsorption at polycrystalline platinum electrodes

The formation of a self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) on polycrystalline platinum electrodes has been characterized by surface analysis and electrochemistry techniques. The 4-ATP monolayer was characterized by cyclic voltammetry (CV), linear sweep voltammetry, Raman spectroscopy, reflection-absorption infrared (RAIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). CV was used to study the dependence of the adsorption time and 4-ATP solution concentration on the relative degree of coverage of 4-ATP monolayers on polycrystalline Pt electrodes. The adsorption time range probed was 24-72 h. The optimal concentration of 4-ATP needed to obtain the highest surface at the lowest adsorption time was 10 mM. RAIR and Raman spectroscopy for 4-ATP-modified platinum electrodes showed the characteristic adsorption bands for 4-ATP, such as nuNH, nuCH(arom), and nuCS(arom), indicating the adsorption on the platinum surface. The XPS spectra for the modified Pt surface presented the binding energy peaks of sulfur and nitrogen. High energy resolution XPS studies, RAIR, and Raman spectrum for platinum electrodes modified with 4-ATP indicate that the molecules are sulfur-bonded to the platinum surface. The formation of a S-Pt bond suggests that ATP adsorption leads to an amino-terminated electrode surface. The thickness of the monolayer was evaluated via angle-resolved XPS (AR-XPS) analyses, giving a value of 8 A. As evidence of the terminal amino group on the electrode surface, the chemical derivatization of the 4-ATP SAM was done with 16-Br hexadecanoic acid. This surface reaction was followed by RAIR spectroscopy.     

A simple and sensitive portable system for a rapid evaluation of bisphenol A contamination in potable and environmental waters using a mesoporous silica-modified carbon paste electrode

In this work, two ordered mesoporous silicas (HMS and SBA-15) were prepared and incorporated into carbon paste electrodes (CPEs) to obtain mesostructured sensors for a rapid determination of bisphenol A (BPA) in waters by voltammetric techniques. The materials were characterised by nitrogen adsorption-desorption measurements, transmission electron microscopy and scanning electron microscopy. The electrochemical properties of the modified carbon paste electrodes were studied by differential pulse voltammetry (DPV) and cyclic voltammetry (CV). Results showed that the sensor modified with HMS (HMS-CPE) exhibited strong adsorption activity toward the oxidation of BPA, with a well-defined voltammetric peak at +0.6 V. Moreover, the HMS-CPE exhibited a wider linearity range, from 0.44 to 3.5 μM BPA, with a detection limit of 61 nM (S/N = 3) and good reproducibility by DPV. The enhanced performance of the HMS-CPE could be attributed to its high surface area, with a 3 D wormhole-like channel structure that favoured an excellent accessibility, high adsorption capacity and faster adsorption rate of BPA. This novel sensor was coupled to a portable system and successfully applied for a rapid determination of BPA in tap, mineral, well and river water samples with good recovery, ranging from 98 ± 12 to 103 ± 7%.     

Nanostructured metal particlemodified electrodes for electrocatalytic and sensor applications

Nanotechnology has become one of the most exciting frontier fields in analytical chemistry. The huge interest in nanomaterials, for example in chemical sensors and catalysis, is driven by their many desirable properties. Although metal is a poor catalyst in bulk form, nanometre-sized particles can exhibit excellent catalytic activity due to their relative high surface area-to-volume ratio and their interface-dominated properties, which significantly differ from those of the bulk material. The integration of metal nanoparticles into thin film of permselective membrane is particularly important for various applications, for example in biological sensing and in electrocatalysis. We have already established different techniques to design permselective membrane-coated chemically modified electrodes with incorporated redox molecules for electrocatalytic, electrochromic and sensor applications. Recently, we have prepared nanostructured platinum and copper (represented M_nano, M = Pt and Cu) modified GC/Nafion electrodes (GC/Nf/M_nano) and characterized by using AFM, XPS, XRD and electrochemical techniques. The nanostructured M_nano modified electrodes were utilized for efficient electrocatalytic selective oxidation of neurotransmitter molecules in the presence of interfering species such as ascorbic acid (AA) and uric acid (UA). It has been also shown that the modified electrodes could be used as sensors for the detection of submicromolar concentrations of biomolecules with practical applications to real samples such as blood plasma and dopamine hydrochloride injection solution. The GC/Cu_nano electrode has been used for catalytic reduction of oxygen.     

Chemically modified teflon capillary columns for gas chromatography II. Solid surface effects in direct coated columns

Summary The preparation of teflon capillary columns employing direct coating of the stationary phase to the chemically modified teflon surface and the role of the chemically modified teflon in the separation mechanism are described. Two types of contributions from the modified teflon have been observed: nonspecific adsorption of the carbon surface and specific interactions of polar groups in the carbon skeleton. The use of polar liquid phases can eliminate adsorption due to the presence of polar groups in the modified teflon.     

Adsorbed Layers of Ferritin at Solid and Fluid Interfaces Studied by Atomic Force Microscopy

The adsorption of the iron storage protein ferritin was studied by liquid tapping mode atomic force microscopy in order to obtain molecular resolution in the adsorbed layer within the aqueous environment in which the adsorption was carried out. The surface coverage and the structure of the adsorbed layer were investigated as functions of ionic strength and pH on two different charged surfaces, namely chemically modified glass slides and mixed surfactant films at the air-water interface, which were transferred to graphite substrates after adsorption. Surface coverage trends with both ionic strength and pH indicate the dominance of electrostatic effects, with the balance shifting between intermolecular repulsion and protein-surface attraction. The resulting behavior is more complex than that seen for larger colloidal particles, which appear to follow a modified random sequential adsorption model monotonically. The structure of the adsorbed layers at the solid surfaces is random, but some indication of long-range order is apparent at fluid interfaces, presumably due to the higher protein mobility at the fluid interface. Copyright 2000 Academic Press.