Glucose oxidase-polypyrrole electrodes synthesized in p-toluenesulfonic acid and sodium p-toluenesulfonate

Amperometric glucose biosensors have been developed based on entrapment on platinum (Pt) electrode using cyclic voltammetry technique in glucose oxidase (GOD) and pyrrole containing p-toluenesulfonic acid (pTSA) or sodium p-toluenesulfonate (NapTS) as supporting electrolyte solutions. Both of electrolyte solutions were suitable media for the formation and deposition of polypyrrole-GOD (PPy-GOD) layers on Pt substrate. Pt/PPy-GOD electrodes brought about in different morphological properties as well as different electrochemical and biochemical response. The highest responses obtained in pTSA and NapTS electrolytes were observed at pH of 4.5 and 7.0 for Pt/PPy-GOD electrodes, respectively. While linearity was observed between 0.0-1.0 mM glucose substrate for both electrodes, I(max) value of Pt/PPy-GOD(NapTS) electrode was approximately twice as high as that of Pt/PPy-GOD(pTSA) electrode as 25.4 and 14.2 microA, respectively. Five commercial drinks were tested with enzyme electrodes and compared with results obtained spectrophotometrically using glucose kit. Results revealed that Pt/PPy-GOD(NapTS) electrode exhibited better biosensor response.     

Tailoring Electrode/Electrolyte Interfacial Properties in Flexible Supercapacitors by Applying Pressure

Electrode/electrolyte interfacial properties of flexible supercapacitors assembled with nanostructured activated carbon fabric (ACF) electrodes can be tailored by applying a pressure and tuning electrolyte ion size relative to electrode pore size. Experimental results reveal that increasing pressure between the supercapacitor electrodes can significantly improve capacitive performance. The ratio of solvated ion size in the electrolyte to the pore size on the electrodes determines the minimum pressure necessary to achieve an optimum performance. For a specific electrode material, this minimum pressure for optimum performance is primarily governed by the size of the larger solvated ions (either the anions or cations), and is lower (～689 KPa) when the ratio of the solvated ion size to the pore size is higher than 0.6, and is higher (at least 1379 KPa) when the ratio is lower than 0.6. An analytical model capable of predicting the experimental performance data has been developed. These results together provide a fundamental understanding of pressure dependence of electrode/electrolyte interfacial properties and pave the way for practical applications of flexible supercapacitors.     

Electrochemiluminescent hybridization chip with electric field aided mismatch discrimination

This paper describes a heterogeneous DNA-hybridization assay based on electrochemiluminescence (ECL) detection on gold electrodes. Short, 15-mer oligonucleotides were conjugated with a synthesized electrochemiluminescent label, bis(2,2'-bipyridine)-5-isothiocyanato-1,10-phenanthroline ruthenium(II) at the amino-modified 5'-end. Gold electrodes were derivatized with 15-mer oligonucleotide probes via 1-(3-(dimethylamino)propyl)-3-ethylcarbodiimide hydrochloride (EDC)/N-hydroxysuccinimide (NHS) cross-linking reaction and hybridized with Ru-labeled strands. Two types of self-assembled-monolayers have been utilized for the immobilization reaction, 3-mercaptopropanoic acid (3-MHA) and 16-mercaptohexadecanoic acid (16-MHA). Longer thiols were more stable at high electrode potentials needed for the ECL generation. The system was sensitive down to 1 fmol of labeled complementary strand, detected in 30 microL of buffer. Mismatch discrimination was achieved both passively by washing and actively by application of negative electrode potential on electrodes prior to detection, but active denaturing lead to better results. Two base-pair mismatches were discriminated at room temperature.     

Glucose oxidase-polypyrrole electrodes synthesized in <Emphasis Type="Italic">p</Emphasis>-toluenesulfonic acid and sodium <Emphasis Type="Italic">p</Emphasis>-toluenesulfonate

Amperometric glucose biosensors have been developed based on entrapment on platinum (Pt) electrode using cyclic voltammetry technique in glucose oxidase (GOD) and pyrrole containing p-toluenesulfonic acid (pTSA) or sodium p-toluenesulfonate (NapTS) as supporting electrolyte solutions. Both of electrolyte solutions were suitable media for the formation and deposition of polypyrrole-GOD (PPy-GOD) layers on Pt substrate. Pt/PPy-GOD electrodes brought about in different morphological properties as well as different electrochemical and biochemical response. The highest responses obtained in pTSA and NapTS electrolytes were observed at pH of 4.5 and 7.0 for Pt/PPy-GOD electrodes, respectively. While linearity was observed between 0.0–1.0 mM glucose substrate for both electrodes, I _max value of Pt/PPy-GOD_NapTS electrode was approximately twice as high as that of Pt/PPy-GOD_pTSA electrode as 25.4 and 14.2 μA, respectively. Five commercial drinks were tested with enzyme electrodes and compared with results obtained spectropho-tometrically using glucose kit. Results revealed that Pt/PPy-GOD_NapTS electrode exhibited better biosensor response.     

A new format of electrodes for the electrochemical reduction of cytochromes P450

New approach to the electrochemical reduction of cytochromes P450 (P450s, CYPs) at electrodes chemically modified with appropriate substrates for P450s ("reverse" electrodes) was proposed. The method is based on the analysis of cyclic voltammograms, square-wave voltammograms and amperograms with subsequent determination of electrochemical characteristics such as catalytic current and redox potential. The sensitivity of proposed method is 0.2-1 nmol P450/electrode. The changes of maximal current and of redox potentials in square-wave voltammograms as well as the changes of catalytic current in amperometric experiments proved to be informative and reliable. Planar regime of screen-printed electrodes (strip-type sensors) enabled to utilise 20-60 microl of electrolyte volume. The enzyme-substrate pairs P450 2B4/benzphetamine and P450scc/cholesterol were investigated. Electrochemical parameters of electrodes with unspecific P450 substrates differed considerably from electrodes with appropriate substrates.     

Electrochemiluminescence of an electrocatalytic action of etimicin on Tris(2,2′‐bipyridyl)ruthenium(II) immobilized in Nafion modified carbon paste electrode

A sensitive electrochemiluminescence (ECL) detection of etimicin at Tris(2,2′‐bipyridyl)ruthenium(II) [Ru(bpy)₃²⁺]–Nafion modified carbon paste electrodes was developed. The immobilized Ru(bpy)₃²⁺ shows good electrochemical and photochemical activities. Electrochemical and electrochemiluminescence characterizations of the modified carbon electrodes were made by means of cyclic voltammetry and electrochemical impendence spectroscopy. The modified electrode showed an electrocatalytic response to the oxidation of etimicin, producing a sensitized ECL signal. The ECL sensor showed a linear response to etimicin in the range of 8.0–160.0 ng mL^?1 with a detection limit of 6.7 ng mL^?1. This method for etimicin determination possessed good sensitivity and reproducibility with a coefficient of variation of 5.1% (n = 7) at 100 ng mL^?1. The ECL sensor showed good selectivity and long‐term stability. Its surface could be renewed quickly and reproducibly by a simple polish step. Copyright © 2009 John Wiley & Sons, Ltd.     

Electrochemiluminescence of luminol at the titanate nanotubes modified glassy carbon electrode

A new strategy for the construction of a sensitive and stable electrochemiluminescent platform based on titanate nanotubes (TNTs) and Nafion composite modified electrode for luminol is described, TNTs contained composite modified electrodes that showed some photocatalytic activity toward luminol electrochemiluminescence emission, and thus could dramatically enhance luminol light emission. This extremely sensitive and stable platform allowed a decrease of the experiment electrochemiluminescence luminol reagent. In addition, in luminol solution at low concentrations, we compared the capabilities of a bare glassy carbon electrode with the TNT composite modified electrode for hydrogen peroxide detection. The results indicated that compared with glassy carbon electrode this platform was extraordinarily sensitive to hydrogen peroxide. Therefore, by combining with an appropriate enzymatic reaction, this platform would be a sensitive matrix for many biomolecules. Copyright © 2013 John Wiley & Sons, Ltd.     

Immobilization of tyrosinase in polysiloxane/polypyrrole copolymer matrices

Immobilization of tyrosinase in conducting copolymer matrices of pyrrole functionalized polydimethylsiloxane/polypyrrole (PDMS/PPy) was achieved by electrochemical polymerization. The polysiloxane/polypyrrole/tyrosinase electrode was constructed by the entrapment of enzyme in conducting matrices during electrochemical copolymerization. Maximum reaction rate (V(max)) and Michaelis-Menten constant (K(m)) were investigated for immobilized enzyme. Enzyme electrodes were prepared in two different electrolyte/solvent systems. The effect of supporting electrolytes, p-toluene sulfonic acid and sodium dodecyl sulfate on the enzyme activity and film morphology were determined. Temperature and pH optimization, operational stability and shelf-life of enzyme electrodes were also examined. Phenolic contents of green and black tea were determined by using enzyme electrodes.     

Rapid non-equilibrium aluminium-ligand interactions: studies on the precipitation of aluminium by laser light scattering, ultrafiltration and centrifugation.

The study aimed to develop simple assays to study aluminium-ligand interactions in natural/biological systems where equilibrium is rarely reached and thus where the initial seconds or hours of interactions are important. The immediate and non-equilibrium precipitation of aluminium hydroxide, in aqueous solution at neutral pH, was therefore studied by laser light scattering (diffraction), ultrafiltration and centrifugation. The interaction of weak ligands, present in the gastrointestinal lumen, on the precipitation of aluminium hydroxide was also investigated. The initial kinetics and particle sizes of precipitated aluminium hydroxide were sensitive to a number of external factors, including the presence of weak ligand (bicarbonate), sheer force (stirring), electrolyte concentration and initial (i.e. added) aluminium concentration. However, after a few seconds (no weak ligand), or several hundred seconds (with weak ligand), the subsequent observed changes to the solid phase were of small magnitude and occurred slowly. Thus, a 25-min window, within 5 and 30 min of pH adjustment, can be used to study the interactions of aluminium-ligand. This may approximate better to most natural systems where unperturbed aluminium-ligand equilibrium must rarely exist.     

Activity coefficients of NaCl in trehalose-water and maltose-water mixtures at 298.15 K

The ionic mean activity coefficients of NaCl in trehalose-water and maltose-water mixtures have been experimentally determined at 298.15 K from emf measurements by electrochemical cell containing ion selective electrodes (ISE): Na-ISE/NaCl (m), sugar (Y%), H(2)O (100-Y%)/Cl-ISE. The electrolyte molality (m) ranged between 0.01 and 3 mol kg(-1), approximately, and the weight percent (Y%) of sugar in the mixture of solvents between 0, 10, 20, 30 and 40%. The system is considered as an electrolyte in a mixture of solvents and the data have been analysed by using the Debye-Hückel and Pitzer equations. The results obtained with both equations are in quite agreement with each other. The variation of the fit parameter from both equations were studied relative to the change in the dielectric properties of the mixture of solvents. Standard free energy of transference were comparatively discussed in terms of ion-solvent, ion-ion interactions and the hydration of both the electrolyte and the sugar.     

Multi-channel electrochemiluminescence of luminol at a copper electrode.

Multi-channel electrochemiluminescence (ECL) of luminol at a copper electrode has been studied under conventional cyclic voltammetric (CV) conditions. Compared with the ECL of luminol at other electrodes, three ECL peaks were observed at 0.30, -0.24 and -0.65 V (vs. SCE), respectively, which was also imaged by a CCD camera. The effects of potential scan direction, anodic reverse potential, the presence of N2 and O2 of the solution, the pH of the solution, the NaNO3 concentration and the potential scan rate were examined. The effect of n-alkanethiol self-assembled monolayers on copper electrodes and 20 L-amino acids, dopamine, adrenaline and noradrenaline on the ECL of luminol were also investigated. The emission spectra of various ECL peaks at different potentials demonstrated that all ECL peaks were related to the luminol reaction. The results show that the oxygen dissolved in solution and copper oxide covered on the surface of the electrode play an important role in the luminol ECL process at a copper electrode. It has been proposed that three ECL channels of luminol at a copper electrode resulted from the reactions of luminol or luminol radical electrooxidized by luminol with various electrogenerated oxygen-containing species, such as O2, OOH- and copper oxides at different potentials.     

Galvanic Corrosion of Lithium‐Powder‐Based Electrodes

Lithium metal is considered to be the most promising anode for the next generation of batteries if the issues related to safety and low coulombic efficiency can be overcome. It is known that the initial morphology of the lithium metal anode has a great influence on the cycling characteristics of a lithium metal battery (LMB). Lithium‐powder‐based electrodes (Li_p‐electrodes) are reported to diminish the occurrence of high surface area lithium deposits. Usually, ultra‐thin lithium foils (<50 µm) and Li_p‐electrodes are prepared on a copper substrate, thus a metal–metal contact area is generated. The combination of these two metals in the presence of an electrolyte, however, can lead to galvanic corrosion. Herein, the corrosion behavior of Li_p‐electrodes is studied. The porosity of such electrodes leads to a high amount of accessible Cu surface in contact with electrolyte. As a consequence, Li_p‐electrodes aged for 1 week in the electrolyte show spontaneous lithium dissolution near the junction to copper and void formation on the lithium‐powder particles. This corrosion process affects the delivered capacity of Li_p‐electrodes and increases the overvoltage of the lithium electrodissolution process. The occurrence of corrosion at the Cu|Li_p interface raises concerns about the practicality of multi‐metallic component systems for LMBs.     

Fast and Sensitive Detection of Bacillus anthracis Spores by Immunoassay

Bacillus anthracis is one of the most dangerous potential biological weapons, and it is essential to develop a rapid and simple method to detect B. anthracis spores in environmental samples. The immunoassay is a rapid and easy-to-use method for the detection of B. anthracis by means of antibodies directed against surface spore antigens. With this objective in view, we have produced a panel of monoclonal antibodies against B. anthracis and developed colorimetric and electrochemiluminescence (ECL) immunoassays. Using Meso Scale Discovery ECL technology, which is based on electrochemiluminescence (ECL) detection utilizing a sulfo-Tag label that emits light upon electrochemical stimulation (using a dedicated ECL plate reader, an electrical current is placed across the microplate with electrodes integrated into the bottom of the plate, resulting in a series of electrically induced reactions leading to a luminescent signal), a detection limit ranging between 0.3 × 10(3) and 10(3) CFU/ml (i.e., 30 to 100 spores per test), depending on the B. anthracis strain assayed, was achieved. In complex matrices (5 mg/ml of soil or simulated powder), the detection level (without any sample purification or concentration) was never altered more than 3-fold compared with the results obtained in phosphate-buffered saline.     

Quantitative electrochemiluminescence detection of proteins: Avidin-based sensor and tris(2,2'-bipyridine) ruthenium(II) label

Quantitative electrochemiluminescence (ECL) detection of a model protein, bovine serum albumin (BSA) was achieved via biotin–avidin interaction using an avidin-based sensor and a well-developed ECL system of tris(2,2′-bipyridine) ruthenium(II) derivative as label and tri-n-propylamine (TPA) as coreactant. To detect the protein, avidin was linked to the glassy carbon electrode through passive adsorptions and covalent interaction with carboxylate-terminated carbon nanotubes that was used as binder to immobilize avidin onto the electrode. Then, biotinylated BSA tagged with tris(2,2′-bipyridine) ruthenium(II) label was attached to the prepared avidin surface. After binding of BSA labeled with tris(2,2′-bipyridine) ruthenium(II) derivative to the surface-immobilized avidin through biotin, ECL response was generated when the self-assembled modified electrode was immersed in a TPA-containing electrolyte solution. Such double protein labeling protocol with a biotin label for biorecognition and ruthenium label for ECL detection facilitated the detection of protein compared to the classical double antibody sandwich format. The ECL intensity was linearly proportional to the feed concentration of BSA over two orders of magnitude in the range of 15 nM to 7.5 μM. The detection limit was estimated to be 1.5 nM. Further application to the lysozyme analysis was carried out to validate the present approach for an effective and favorable protocol for the quantitative detection of proteins. The dynamic range of lysozyme was from 0.001 g L⁻¹ to 0.1 g L⁻¹ and the detection limit was 0.1 mg L⁻¹. Electrochemical impedance and cyclic voltammetric measurements along with some necessary control experiments were conducted to characterize the successful formation of self-assembled modified electrodes and to grant the whole detection process.     

A Hybrid Electrolytes Design for Capacity‐Equivalent Dual‐Graphite Battery with Superior Long‐Term Cycle Life

Based on cation/anion graphite intercalation chemistry (GIC) processes, dual‐graphite batteries promise to be an energy storage device of high safety and low cost. However, few single electrolyte systems can simultaneously meet the requirements of both high oxidative stability during high voltage anion‐GIC on cathode and high reversibility upon cation‐GIC on anode. Thus, in order to rigidly remedy the irreversible capacity loss, excessive electrode materials need to be fabricated within full cell, resulting in an imbalance toward capacity‐dependent mass loading proportion between both electrodes. This work introduces a hybrid (dual‐organic) electrolytes design strategy into this promising technology. Segregated by a Nafion‐based separator, an ionic liquid electrolyte within the cathodic side can endure high operation potentials, while high Li‐GIC reversibility can be achieved in a superconcentrated ether‐based electrolyte on the anode side. On a mechanistic level, various cation‐GIC processes conducted in different electrolyte systems are clearly revealed and are summarized based on systematical characterizations. More importantly, after synergistically tuning the advantage and drawback of each electrolyte in this hybrid system, the dual‐graphite full cell assembled with capacity‐equivalent graphite‐based electrodes (1:1 mass loading) demonstrates superior long‐term cycling stability with ultrahigh capacity retention for over 3000 cycles.     

Flexible and Highly Scalable V2O5‐rGO Electrodes in an Organic Electrolyte for Supercapacitor Devices

Vanadium pentoxide–reduced graphene oxide (rGO) free‐standing electrodes are used as electrodes for supercapacitor applications, eliminating the need for current collectors or additives and reducing resistance (sheet resistance 29.1 Ω □^?1). The effective exfoliation of rGO allows improved electrolyte ions interaction, achieving high areal capacitance (511.7 mF cm^?2) coupled with high mass loadings. A fabricated asymmetric flexible device based on rGO/V₂O₅‐rGO (VGO) consists of approximately 20 mg of active mass and still delivers a low equivalent series resistance (ESR) of 3.36 Ω with excellent cycling stability. A prototype unit of the assembled device with organic electrolyte is shown to light up eight commercial light‐emitting diode bulbs.     

Stimulating the anaerobic degradation of aromatic hydrocarbons in contaminated sediments by providing an electrode as the electron acceptor

The possibility that electrodes might serve as an electron acceptor to simulate the degradation of aromatic hydrocarbons in anaerobic contaminated sediments was investigated. Initial studies with Geobacter metallireducens demonstrated that although toluene was rapidly adsorbed onto the graphite electrodes it was rapidly oxidized to carbon dioxide with the electrode serving as the sole electron acceptor. Providing graphite electrodes as an electron acceptor in hydrocarbon‐contaminated sediments significantly stimulated the removal of added toluene and benzene. Rates of toluene and benzene removal accelerated with continued additions of toluene and benzene. [¹⁴C]‐Toluene and [¹⁴C]‐benzene were quantitatively recovered as [¹⁴C]‐CO₂, demonstrating that even though the graphite adsorbed toluene and benzene they were degraded. Introducing an electrode as an electron acceptor also accelerated the loss of added naphthalene and [¹⁴C]‐naphthalene was converted to [¹⁴C]‐CO₂. The results suggest that graphite electrodes can serve as an electron acceptor for the degradation of aromatic hydrocarbon contaminants in sediments, co‐localizing the contaminants, the degradative organisms and the electron acceptor. Once in position, they provide a permanent, low‐maintenance source of electron acceptor. Thus, graphite electrodes may offer an attractive alternative for enhancing contaminant degradation in anoxic environments.     

Comparison of colloidal gold electrode fabrication methods: the preparation of a horseradish peroxidase enzyme electrode.

In order to prepare biosensing electrodes which respond to hydrogen peroxide, horseradish peroxidase has been adsorbed to colloidal gold sols and electrodes prepared by deposition of these enzyme-gold sols onto glassy carbon using three methods: evaporation, electrodeposition and electrolyte deposition. In the latter method the enzyme-gold sol is applied to the surface of a glassy carbon disk electrode followed by an equal volume of 2 mM CaCl2. The electrolyte causes the sol to precipitate on the electrode surface, producing an immobilized enzyme electrode. Satisfactory electrodes which gave an electrochemical response to hydrogen peroxide in the presence of the electron transfer mediator ferrocenecarboxylic acid were produced by all three methods. Evaporation of horseradish peroxidase-gold sols produced electrodes with the best reproducibility and the widest linear amperometric response range. These electrodes can also easily be stored in a dry state. Although not as good as evaporation, electrodeposition also produced satisfactory electrodes. Electro-deposition provides the added advantage that it lends itself to the preparation of multi-enzyme/multi-analyte electrodes by the adsorption of different enzymes to separate gold sols, followed by sequential electrodeposition onto discrete areas of a multichannel electrode.     

A Versatile Capacity Balancer for Asymmetric Supercapacitors

Asymmetric supercapacitors (ASCs) with high theoretical energy density have attracted extensive attention during the past years. However, the huge capacity gap between the two electrodes greatly limits high energy density. Regulating electrode mass can make the capacity balanced, while sacrificing weight and volume. Herein, a soluble bipolar molecule, 4‐hydroxy‐2,2,6,6‐tetramethylpiperidinyloxyl (4‐OH‐TEMPO), is proposed as a versatile mediator in the electrolyte to balance the capacity gap in different types of ASCs. 4‐OH‐TEMPO is able to quickly obtain or lose electrons at different potentials regardless of the pH values, thus can contribute large redox capacity at the interface of capacitive electrode in ASCs in both positive or negative electrodes, acidic or alkaline systems. A case study of two typical ACSs is presented, Zn//activated carbon (AC) system with 4‐OH‐TEMPO for positive electrode enhancement in a mildly acidic electrolyte and AC//Ni(OH)₂ system with 4‐OH‐TEMPO for negative electrode enhancement in an alkaline electrolyte. Both demonstrate that the addition of 4‐OH‐TEMPO can effectively balance the capacity mismatching between two electrodes, and its capacity contribution can be adjusted by concentration. The energy density of the two ACSs with 4‐OH‐TEMPO can be greatly promoted without significant sacrifice of the device's volume or mass.     

Mechanical Property Evolution of Silicon Composite Electrodes Studied by Environmental Nanoindentation

Mechanical degradation is largely responsible for the short cycle life of silicon (Si)‐based electrodes for future lithium‐ion batteries. An improved fundamental understanding of the mechanical behavior of Si electrodes, which evolves, as demonstrated in this paper, with the state of charge (SOC) and the cycle number, is a prerequisite for overcoming mechanical degradation and designing high capacity and durable Si‐based electrodes. In this study, Young's modulus (E) and hardness (H) of Si composite electrodes at different SOCs and after different cycle numbers are measured by nanoindentation under both dry and wet (liquid electrolyte) conditions. Unlike electrodes made of Si alone, E and H values of Si composite electrodes increase with increasing Li concentration. The composite electrodes under wet conditions are softer than that under dry conditions. Both E and H decrease with the cycle number. These findings highlight the effects of porosity, liquid environment, and degradation on the mechanical behavior of composite electrodes. The methods and results of this study on the mechanical property evolution of Si/polyvinylidene fluoride electrodes form a basis for exploring more effective binders for Si‐based electrodes. Furthermore, the evolving nature of the mechanical behavior of composite electrodes should be taken into consideration in future modeling efforts of porous composite electrodes.