Redox cycling in nanofluidic channels using interdigitated electrodes

Amperometric detection is ideally suited for integration into micro- and nanofluidic systems as it directly yields an electrical signal and does not necessitate optical components. However, the range of systems to which it can be applied is constrained by the limited sensitivity and specificity of the method. These limitations can be partially alleviated through the use of redox cycling, in which multiple electrodes are employed to repeatedly reduce and oxidize analyte molecules and thereby amplify the detected signal. We have developed an interdigitated electrode device that is encased in a nanofluidic channel to provide a hundred-fold amplification of the amperometric signal from paracetamol. Due to the nanochannel design, the sensor is resistant to interference from molecules undergoing irreversible redox reactions. We demonstrate this selectivity by detecting paracetamol in the presence of excess ascorbic acid. Figure  

Prussian Blue-coated interdigitated array electrodes for possible analytical application

Thin films of iron(III) hexacyanoferrate(II) (Prussian Blue) were electrochemically deposited on interdigitated array (IDA) electrodes, yielding systems which can be considered as chemiresistors in sensing alkali metal ion concentrations in an adjacent electrolyte. This is due to the fact that the conductivity of the film being measured by a steady-state current on application of a voltage to the two-fingered electrodes of the IDA depends on both the redox stare of the film and the cation concentration in the electrolyte. From the dependence of the steady-state current on the electrode (bias) potential at variable cation concentrations for different alkali metal ions and for mixtures of alkali metal ions, the possibilities of analytical application were elucidated. In addition, by using the methods of staircase coulometry and scanning conductivity, the electron diffusion coefficient D_e was determined as a function of the redox state of Prussian Blue. It is concluded that Prussian Blue-coated IDA electrodes are, in principle, suitable as chemiresistors for the determination of alkali metal ion concentrations with increasing selectivity in the series Li < Na < K < Rb < Cs.     

Microfluidic cells with interdigitated array gold electrodes: Fabrication and electrochemical characterization

Microfluidic flow cells combined with an interdigitated array (IDA) electrode and/or individually driven interdigitated electrodes were fabricated and characterized for application as detectors for flow injection analysis. The gold electrodes were produced by a process involving heat transfer of a toner mask onto the gold surface of a CD-R and etching of the toner-free gold region by short exposure to iodine-iodide solution. The arrays of electrodes with individual area of 0.01 cm² (0.10 cm of length × 0.10 cm of width and separated by gaps of 0.05 or 0.03 cm) were assembled in microfluidic flow cells with 13 or 19 μm channel depth. The electrochemical characterization of the cells was made by voltammetry under stationary conditions and the influence of experimental parameters related to geometry of the channels and electrodes were studied by using K₄Fe(CN)₆ as model system. The obtained results for peaks currents (I_p) are in excellent agreement with the expected ones for a reversible redox system under stationary thin-layer conditions. Two different configurations of the working electrodes, E_i, auxiliary electrode, A, and reference electrode, R, on the chip were examined: E_i/R/A and R/E_i/A, with the first presenting certain uncompensated resistance. This is because the potentiostat actively compensates the iR drop occurring in the electrolyte thin layer between A and R, but not from R to each E_i. This is confirmed by the smaller difference between the cathodic and anodic peak potentials for the second configuration. Evaluation of the microfluidic flow cells combined with (individually driven) interdigitated array electrodes as biamperometric or amperometric detectors for FIA reveals stable and reproducible operation, with peak heights presenting relative standard deviations of less than 2.2%. For electrochemically reversible species, FIA peaks with enhanced current signal were obtained due to redox cycling under flow operation. The versatility of microfluidic flow cells, produced by simple and low-cost technique, associated with the rich information content of electrochemical techniques with arrays of electrodes, opens many future research and application opportunities.     

Theory of the steady-state current of a redox couple at interdigitated array electrodes of which pairs are insulated electrically by steps

The possibility of constructing an interdigitated array electrode (IDA) with a submicrometre gap is proposed in which adjacent microband electrodes are separated from each other by an insulated step. Then the IDA is an assembly of protrusive and hollow microband electrodes. The unit model of the IDA consisted of half of the lower (hollow) microband electrode, an insulated step and half of the upper (protrusive) microband electrode with a finite thickness on the step. The boundary value problem involving the two-dimensional Laplace equation is presented for redox cycling at the IDA under diffusion control and is solved numerically by a boundary element method. The steady-state current was computed as a function of the height of the step and the thickness of the upper electrode. It was larger than the current at the ordinary IDA, partly because the true electrode area was larger than the area of the ordinary IDA. The current varied linearly with the logarithm of the step height. It was expressed by a simple approximate equation in order to facilitate prediction of its numerical value.     

Characterisation of the interdigitated electrode array with tantalum silicide electrodes separated by insulating barriers

A novel design of an interdigitated electrode array impedimetric sensor is proposed with electrode digits separated by an insulating barrier. This configuration results in that the major part of the electric current between electrodes follows close to the surface of the barrier and not through the solution thus permitting to enhance the sensitivity to possible chemical reactions on its surface. As a model system the effect of electrostatically assembled polyelectrolyte layers deposited using layer-by-layer method on the sensor impedance was studied. The sensitivity of the devices depends on the barrier height and is considerably enhanced comparing to conventional flat sensor structures. Devices may be used as a transducer for direct label-free biosensor development.     

Addressable electrode array device with IDA electrodes for high-throughput detection

An electrochemical device is proposed for high-throughput electrochemical detection that consists of 32 row and 32 column electrodes on a single glass substrate. The row and column electrodes are connected to interdigitated array (IDA) electrodes to form 1024 (32 × 32) addressable sensor points in the device. Electrochemical responses from each of the 1024 sensors were successfully acquired on the device within 1 min using redox cycling at individual IDA electrodes, which ensures application of the device to comprehensive, high-throughput electrochemical detection for enzyme-linked immunosorbent assay (ELISA), reporter gene assay for monitoring gene expressions, and DNA analysis.     

Specific detection of oxytetracycline using DNA aptamer-immobilized interdigitated array electrode chip

An electrochemical sensing system for oxytetracycline (OTC) detection was developed using ssDNA aptamer immobilized on gold interdigitated array (IDA) electrode chip. A highly specific ssDNA aptamer that bind to OTC with high affinity was employed to discriminate other tetracyclines (TCs), such as doxycycline (DOX) and tetracycline (TET). The immobilized thiol-modified aptamer on gold electrode chip served as a biorecognition element for the target molecules and the electrochemical signals generated from interactions between the aptamers and the target molecules was evaluated by cyclic voltammetry (CV) and square wave voltammetry (SWV). The current decrease due to the interference of bound OTC, DOX or TET was analyzed with the electron flow produced by a redox reaction between ferro- and ferricyanide. The specificity of developed EC-biosensor for OTC was highly distinguishable from the structurally similar antibiotics (DOX and TET). The dynamic range was determined to be 1-100 nM of OTC concentration in semi-logarithmic coordinates.     

Indirect voltammetric detection of fluoride ions in toothpaste on a comb-shaped interdigitated microelectrode array

A novel technique based on dynamic electrochemistry for the detection of fluoride ions was developed. It is based on its strong complexation with ferric ion. Formed fluoroferric complex is cathodically inactive at the potential of the reduction of free ferric aquo ion. The voltammetric and amperometric response of platinum comb-shaped interdigitated microelectrode array is decreased after fluoride addition. This decrease serves for the quantification of fluoride ions added to the solution. The detection limit of 4.5 × 10⁻⁵ mol dm⁻³ was achieved when one of the segments of interdigitated microelectrode array (IDA) was used as an indicating electrode. The detection limit is about one order of magnitude lower than in the case of conventional platinum macroelectrode. In comparison with ISE electrodes this method is faster and also avoiding large error resulting from the antilogarithmization of ISE Nerstian response. The method was applied to the analysis of toothpaste.     

An interesting route using electron-beam lithography and photolithography to pattern submicron interdigitated electrodes array for sensing applications

Journal of the Iranian Chemical Society - Increasing the interest in the silicon-based devices resulted in developing new methods and techniques to achieve advanced and more reliable designs and...     

A selective metabolite array for the detection of phosphometabolites

Immobilised metal ion affinity (IMA) has been traditionally used specifically for the separation of phosphorylated proteins and nucleic acids, in proteomics and genomics, respectively. This report describes the novel application of IMA in metabolomics for the development of metabolite arrays to detect phosphometabolites using a plasma polymer-modified surface. Immobilisation of gallium, zirconium, cobalt, copper, zinc, nickel, iron, and chromium to acrylic acid plasma polymer followed by subsequent exposure to metabolites (phospho- and non-phosphometabolites) was investigated. Results analysed using ToF-SIMS suggests that gallium and zirconium exhibit higher phosphometabolite affinity and specificity compared to other metals, and can be used to develop metabolite arrays for the detection of phosphometabolites.     

The in situ investigation of the polyaniline-derived N-doped carbon with the interdigitated array electrodes towards the oxygen reduction reaction

Journal of Solid State Electrochemistry - Nowadays, tremendous effort has been made in searching clean, high-efficient and sustainable energy, and related energy conversion methods. Oxygen...     

Calibrationless determination of electroactive species using chronoamperograms at collector segment of interdigitated microelectrode array

The possibility of calibrationless chronoamperometric determination is described using a pair of individually addressable and diffusion layers interacting segments of interdigitated microelectrode array (IDA). It utilizes dual voltammetric mode where the first segment is polarized with potential corresponding to the limiting current of determined species electrode reaction and the second segment is polarized with potential corresponding to the opposite electrode reaction limiting current. Time at which the current of the collector segment reaches one half of the steady state is hyperbolically dependent on the diffusion coefficient of analyte. The determination of diffusion coefficient allows direct calculation of bulk concentration avoiding calibration with a standard solution. The equipment for measuring of fast response of IDA arrays in dual mode has been developed using a bipotentiostat connected with A/D transducer. It allows less than 1 ms sampling period for ultrafast registration of chronoamperogram. The method was tested and validated with [Fe(CN)₆]⁴⁻, [Ru(NH₃)₆]Cl₃, and ferrocene model samples using various types of IDA arrays.     

The detection of formaldehyde in textiles using interdigitated microelectrode array diffusion layer titration with electrogenerated hypobromite

An interdigitated microelectrode array (IDA) was applied to the determination of formaldehyde released from textiles produced in industry. The proposed method is based on formaldehyde reaction with hypobromite which is formed in weakly basic media by control current electrooxidation of bromide on the generator segment of the IDA array. The unreacted hypobromite diffuses through the gap between individually polarisable IDA segments and it is amperometrically detected on the collector segment of the IDA. The efficiency of this nonconvective transfer process in the absence of formaldehyde was substantially higher (78%) in comparison with that when using the rotating ring disc electrode. The influence of the added formaldehyde on the transfer process can be utilised to develop a simple and sensitive analytical procedure for formaldehyde detection with a detection limit of 4×10⁻⁶ mol dm⁻³.     

Sensitive electrochemical detection of the hydroxyl radical using enzyme-catalyzed redox cycling

Enzyme-catalyzed signal amplification was introduced to the electrochemical detection of the OH radical. In the presence of phenol as a trapping agent, glucose as a substrate, and pyrroloquinoline quinone-containing glucose dehydrogenase (PQQ-GDH) as a catalyst, the current signal for the trapping adducts (catechol and hydroquinone) produced by the hydroxylation of phenol could be amplified and detected sensitively. The limit of detection (S/N = 3) for catechol was 8 nM. The trapping efficiency of phenol was also estimated.     

An electrochemical immunosensor using p-aminophenol redox cycling by NADH on a self-assembled monolayer and ferrocene-modified Au electrodes

Redox cycling of enzymatically amplified electroactive species has been widely employed for high signal amplification in electrochemical biosensors. However, gold (Au) electrodes are not generally suitable for redox cycling using a reducing (or oxidizing) agent because of the high background current caused by the redox reaction of the agent at highly electrocatalytic Au electrodes. Here we report a new redox cycling scheme, using nicotinamide adenine dinucleotide (NADH), which can be applied to Au electrodes. Importantly, p-aminophenol (AP) redox cycling by NADH is achieved in the absence of diaphorase enzyme. The Au electrodes are modified with a mixed self-assembled monolayer of mercaptododecanoic acid and mercaptoundecanol, and a partially ferrocenyl-tethered dendrimer layer. The self-assembled monolayer of long thiol molecules significantly decreases the background current of the modified Au electrodes, and the ferrocene modification facilitates easy oxidation of AP. The low amount of ferrocene on the Au electrodes minimizes ferrocene-mediated oxidation of NADH. In sandwich-type electrochemical immunosensors for mouse immunoglobulin G (IgG), an alkaline phosphatase label converts p-aminophenylphosphate (APP) into electroactive AP. The amplified AP is oxidized to p-quinoneimine (QI) by electrochemically generated ferrocenium ion. NADH reduces QI back to AP, which can be re-oxidized. This redox cycling enables a low detection limit for mouse IgG (1 pg mL(-1)) to be obtained.     

Detection of chlorinated quinones using interdigitated electrodes coupled with capillary electrophoresis

An array of eight interdigitated microband gold electrodes (IDEs) has been developed together with electrophoretic separation for analysis of chlorinated hydroquinones (ClHQs) and benzoquinones (ClBQs). The IDE chip positioned very close to the separation capillary outlet served as an amplification/detection system without the requirement for frequent "capillary-electrode" alignment. ClHQs, electrophoretically migrating to the IDE surface, were oxidized at +1.1 V by seven electrodes of the array and then detected by the remaining electrode, poised at -0.1 V. Conversely, ClBQs were detected at +1.1 V by the detecting electrode after having been reduced at the 7 adjacent electrodes poised at -0.1 V. There was an amplification effect on both the detecting electrode as well as the adjacent electrodes because of the recycle between ClHQs and ClBQs. The detecting "amplification" current response was dependent on the potentials applied, the position of the detecting electrode on the array, the number of adjacent electrodes being used for recycling and the distance between the oxidative and reductive electrodes. Micellar electrokinetic chromatography (MEKC) separation of the analytes was achieved using 30 mM sodium dodecyl sulfate (SDS) with a detection limit in the range of 2-20 micro M. In addition to a facile "capillary-electrode" alignment, the important aspect described here was the capability of detecting through recycling a reduced compound (in the case of ClHQs) at a negative potential to circumvent fouling and electroactive interferences. An appealing feature was also the concurrent oxidation/reduction detection for each compound to ascertain peak assignment, as interfering compounds are less likely to exhibit the same oxidative/reductive characteristics and electrophoretic mobilities as the target analytes.     

LuIII bisphthalocyanines as mediators for redox reactions at thin-organic-film modified electrodes

Lutetium bisphthalocyanines, dissolved in a thin-film of nitrobenzene covering a graphite electrode, have already been used for ion transfer studies across the liquid∣liquid interface. These sandwich complexes are also good candidates for the electron exchange with species in water, across the interface. Their one-electron oxidation and reduction are fully reversible, the oxidized and reduced forms being chemically stable. Compared with ferrocene derivatives and porphyrins that have been extensively used previously, these compounds offer very interesting properties for the mediation of electron exchanges with redox species in aqueous solutions.     

Synchronous-scan fluorescence as a selective detection method for sodium dodecylbenzene-sulfonate and pyrene in environmental samples

Synchronous-scan fluorescence spectra of dodecylbenzene sulfonic acid sodium salt (SDBS) and pyrene in aqueous solution were studied. The concentration ranges of SDBS and pyrene in aqueous solutions were 0.01-10.00 and 0.001-0.050 mg L⁻¹, respectively. The optimized wavelength differences (Δλ) of 46-55 and 38 nm were maintained between excitation and emission wavelengths for SDBS and pyrene, respectively, and they were found to be suitable for effective determination of SDBS and pyrene without mutual interferences; the peaks were observed at λ_ex 229-232 nm (SDBS) and λ_ex 335 nm (pyrene). Linear relationships between synchronous-scan fluorescence spectroscopy (SFS) intensity and concentration of SDBS or pyrene in aqueous solution (Milli-Q water, river water, and mucus of fish gills) were established. It was demonstrated that SFS method was effective for simultaneous analyses of SDBS and pyrene in mixed solution.