Amperometric sensors based on tyrosinase-modified screen-printed arrays

This paper describes the design, development and characteristics of a tyrosinase (polyphenol oxidase) modified amperometric screen-printed biosensor array, with the enzyme cross-linked in a redox-hydrogel namely the PVI₁₃-dmeOs polymer. Two types of Au-screen-printed four-channel electrode arrays, differing in design and insulating layer, were compared and investigated. Au-, graphite-coated-Au- and Carbopack C-coated-Au-surfaces, serving as the basis for tyrosinase immobilisation, were investigated and the performances of the different arrays were evaluated and compared in terms of their electrocatalytic characteristics, as well as operational- and storage stability using catechol as model substrate. It was found that the Carbopack C-coated array was the best choice for tyrosinase immobilisation procedure mainly due to a higher mechanical stability of the deposited enzyme layer, combined with good sensitivity and stability for up to 6 months of use. In the batch mode the biosensors responded linearly to catechol up to 30 μM with limits of detection from 0.14 μM. Parameters from cyclic voltammograms indicated that the reversibility of the direct electrochemical reaction for catechol on the three types of electrode surfaces (no tyrosinase modification) was not the limiting factor for the construction and performance of tyrosinase biosensors.     

Amperometric acetylcholine and choline sensors with immobilized enzymes

Acetylcholine and choline sensors are prepared by immbilizing enzymes on nylon net attached to a hydrogen peroxide snsor. Choline oxidase is used for the choline sensor; acetylcholinesterase choline oxidase are used for acetylcholine. The platinum/silver electrode pair is polarized at +0.6 V. The assembly is protected with an acetate cellulose membrane to enhance selectivity. The ranges measured are 1–10 μmol l^?1 in 0.1–1 ml of sample. The response times are 1–2 min.     

Amperometric uric acid sensors based on polyelectrolyte multilayer films

Uricase (UOx) and polyelectrolyte were used for preparation of a permselective multilayer film and enzyme multilayer films on a platinum (Pt) electrode, allowing the detection of uric acid amperometrically. The polyelectrolyte multilayer (PEM) film composed of poly(allylamine) (PAA) and poly(vinyl sulfate) (PVS) were prepared via layer-by-layer assembly on the electrode, functioning as H₂O₂-selective film. After deposition of the permselective film (PAA/PVS)₂PAA, UOx and PAA were deposited via layer-by-layer sequential deposition up to 10 UOx layers to prepare amperometric sensors for uric acid. Current response to uric acid was recorded at +0.6 V vs. Ag/AgCl to detect H₂O₂ produced from the enzyme reaction. The response current increased with increasing the number of UOx layers. Even in the presence of ascorbic acid, uric acid can be detected over the concentration range 10⁻⁶-10⁻³ M. The response current and deposited amount of UOx were affected by deposition bath pH and the addition of salt. The deposition of PAA/UOx film prepared in 2 mg ml⁻¹ solution (pH 11) of PAA with NaCl (8 mg ml⁻¹) and 0.1 mg ml⁻¹ solution (pH 8.5) of UOx with borate (100 mM) resulted in an electrode which shows the largest response to uric acid. The response of the sensor to uric acid was decreased by 40% from the original activity after 30 days.     

Amperometric ion sensors based on laser-patterned composite polymer membranes

A polymer membrane for the selective amperometric transfer and sensing of molecular ions has been designed and characterised. The membrane was formed from two polymer layers, a supporting film of polyethylene terephthalate on which an electrolyte film containing polyvinylchloride is cast. The polyester layer has a laser-etched pattern of circular micro-holes in one region. These hole structures are arranged in a rectangular geometry and measure 22 μm in diameter with separation distances of 105 μm and 120 μm. The polyvinylchloride underlayer is a composite system comprised of a 2-nitrophenyl octyl ether plasticising solution containing an electrolytic salt of tetrabutylammonium tetrakts-(4-chlorophenyl)borate. In this way, an array of micro-interfaces between an analyte solution and a PVC gel electrolyte is formed and used as a liquid|liquid interface for the amperometric monitoring of ion transfer reactions. The membrane was characterised in terms of the voltammetric response to choline transfer. The study includes an examination of the fabrication methodology, materials composition and membrane structure.     

Amperometric tape ion sensors for cadmium(II) ion analysis

This paper describes a novel tape platform ion sensing methodology specific to the detection of cadmium(II) ions in aqueous solution based on assisted ion transfer reactions across a polarized water | organic gel micro-interface. The tape ion sensors were constructed to incorporate the micro-water | polyvinylchloride-2-nitrophenylethyl ether (PVC-NPOE) gel interfaces referred to as ionodes. The sensors have overall thicknesses less than 300 μm, allowing their packaging in a disposable tape format. The detection methodology is based on the selective assisted transfer of the cadmium ion in aqueous phase by ETH 1062 present in the PVC-NPOE gel layer and was first investigated using cyclic voltammetry. Quantitative analysis of cadmium(II) ions in aqueous solution using the tape sensors was then conducted under stop-flow conditions. Detection limits as low as 20 ppb (178 nM) for Cd(II) ions in very small volumes as low as a single 20 μl droplet without any sample preconcentration was achieved in an analysis time of approximately 20 s, which could be easily employed for the direct measurement of Cd(II) ion levels in various field applications. The tape ion sensor can also be used in a flow-cell geometry to preconcentrate Cd(II) ions from aqueous samples and further improve the detection limit.     

Amperometric glycolate sensors based on glycolate oxidase and polymeric electron transfer mediators

Using experiments involving cyclic voltammetry and stationary potential measurements, it was shown that siloxane polymers with covalently attached ferrocene and 1,1'-dimethylferrocene relays efficiently mediate electron transfer from reduced glycolate oxidase to a conventional carbon-paste electrode. Sensors containing these polymeric relay systems and glycolate oxidase respond rapidly to low (< 0.1 mM) glycolate concentrations, with steady-state current responses achieved in less than 1 min. The dependence of the sensor response on the nature of the siloxane polymer backbone, the type of polymer-bound redox mediator used and the amount of redox mediator present is discussed. From these considerations, sensors have been designed which can operate efficiently at low applied potential and can avoid decreased current response due to dissolved oxygen.     

Carbon nanotube gas and vapor sensors

Carbon nanotubes have aroused great interest since their discovery in 1991. Because of the vast potential of these materials, researchers from diverse disciplines have come together to further develop our understanding of the fundamental properties governing their electronic structure and susceptibility towards chemical reaction. Carbon nanotubes show extreme sensitivity towards changes in their local chemical environment that stems from the susceptibility of their electronic structure to interacting molecules. This chemical sensitivity has made them ideal candidates for incorporation into the design of chemical sensors. Towards this end, carbon nanotubes have made impressive strides in sensitivity and chemical selectivity to a diverse array of chemical species. Despite the lengthy list of accomplishments, several key challenges must be addressed before carbon nanotubes are capable of competing with state-of-the-art solid-state sensor materials. The development of carbon nanotube based sensors is still in its infancy, but continued progress may lead to their integration into commercially viable sensors of unrivalled sensitivity and vanishingly small dimensions.     

Mass transfer in amperometric gas sensors

The mass transfer in amperometric gas sensors intended for atmosphere monitoring is studied theoretically and experimentally. External and internal constituents of the diffusion resistance (DR) of the sensors are determined. The external constituent is defined by conditions of convective diffusion of air under analysis relative to the sensor. The internal constituents are defined by parameters of construction of sensor elements, and electrolyte film, as well as the structure of the indicator electrode, and solubility of the gas under analysis in the electrolyte. Testing a chlorine sensor shows that the DR of the internal constituents is independent of the conditions of convective diffusion of the environment under analysis near the sensor. The similarity criterion of sensors of different types is shown to be the relative share of DRs of individual constituents in the overall DR of the sensor. The results obtained can be used for the development and design of sensors with required range and resolution.     

Electrochemical sensors for environmental gas analysis

The application of electrochemical sensors for measurement of concentration of pollutant gases in air in the part-per-billion (10⁹) range is reviewed. Performance-limiting factors, particularly the effects of extremes and of relatively rapid changes in ambient temperature and humidity, are noted. Variations in composition of the electrolyte in the meniscus at the electrode–gas interface and instability of the solid–liquid–gas contact line, causing important variations in current due to background electrode reactions, are deduced and suggested as the reason for the performance limitations. Suggestions are made for mitigation through instrument design.     

Semiconductor gas sensors in bioreactor control

A simple semiconductor gas sensor (TGS 812) is used for the on-line measurement and control of indole during the production of l-tryptophan from indole and l-serine with immobilized E. coli cells. Indole is estimated in the reactor gas space. In combination with an automatic indole supply system, a feed-batch process became possible. The indole concentration was monitored and kept within the optimal range (300–600 mg l^?1). A simple gas-sensing electrode dipped in the reaction medium provides direct measurement of organic solvents and gases in the liquid. Such a system is suitable for on-line determination of ethanol (10–70 g l^?1) during continuous production of ethanol with immobilized yeast cells.     

Ionic liquid high temperature gas sensors

An ionic liquid piezoelectric gas sensor was demonstrated for detection of polar and nonpolar organic vapors at high temperature with fast linear and reversible response.     

Phthalocyanine-based field-effect transistors as gas sensors

In this review molecular field-effect transistors are described and compared with their gate-modified inorganic counterparts. The different processes involved in gas sensing are summarized. The advantages of transistors on resistors are demonstrated. The sensitivity of molecular field-effect transistors to strong oxidizing species, for example ozone, is detailed and compared with their sensitivity to humidity and volatile organic compounds. Application to ozone monitoring in urban atmospheres is also described.     

Organic semiconductors in potentiometric gas sensors

Solid-state potentiometric sensors based on the chemical modulation of the work function of organic semiconductors are discussed. The theory of the chemical work function modulation is briefly reviewed. There are several sensor configurations, in which this transduction principle can be employed. First is the Kelvin probe, second is the chemically sensitive field-effect transistor in which the conventional metal gate of the silicon-based transistor has been replaced by an organic semiconductor. Chemical modulation of work function enters also into the operation of the third type of sensor discussed in this review, on “organic field-effect transistor”. It is shown that in reality such sensors are “field-modulated chemiresistors”, rather than potentiometric sensors.     

Porous metal oxides as gas sensors

Semiconducting metal oxides are frequently used as gas-sensing materials. Apart from large surface-to-volume ratios, well-defined and uniform pore structures are particularly desired for improved sensing performance. This article addresses the role of some key structural aspects in porous gas sensors, such as grain size and agglomeration, pore size or crack-free film morphology. New synthesis concepts, for example, the utilisation of rigid matrices for structure replication, allow to control these parameters independently, providing the opportunity to create self-diagnostic sensors with enhanced sensitivity and reproducible selectivity.     

Chlorine gas sensors using one-dimensional tellurium nanostructures

Tellurium nanotubes have been grown by physical vapor deposition under inert environment at atmospheric pressure as well as under vacuum conditions. Different techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and optical absorption have been utilized for characterization of grown structures. Films prepared using both types of tellurium nanotubes were characterized for sensitivity to oxidizing and reducing gases and it was found that the relative response to gases depends on the microstructure. Nanotubes prepared at atmospheric pressure (of argon) showed high sensitivity and better selectivity to chlorine gas. Impedance spectroscopy studies showed that the response to chlorine is mainly contributed by grain boundaries and is therefore enhanced for nanotubes prepared under argon atmosphere.     

Design of platinum hot wire gas sensors

The design characteristics of lower-power platinum gas sensors are studied. These sensors work by the detection of the positive ions produced during the catalytic oxidation of organic vapours on hot platinum wires and ribbons. These sensors are selective to long-chain hydrocarbons. A prototype sensor design is presented, which uses a small piece of platinum ribbon welded to a ceramic header with a wire mesh cathode to collect the positive ions. The ionic current is measured with a battery-run picoammeter circuit biased to float at −120 V. The ribbon is heated resistively with a standad power supply. At the operating temperature of 800 °C, the power consumption is about 2 W. The prototype is capable of detecting iso-octane vapour down to a concentration of 2 ppm. Platinum ribbon was used rather than wire as the wire had a greater tendency to melt due to thermal runaway in the resistive heating process. It was observed that the number of positive ions produced by the catalytic process decreased during long-term measurements. Scanning electron micrographs showed this to be due to facetting of the platinum surface. A few seconds' exposure at 1300 °C restored the surface and the ionic response. Thus periodic thermal cycling is necessary for the prototype sensor.     

Highly sensitive WO3 hollow-sphere gas sensors

In this paper, we describe how WO(3) hollow spheres have been synthesized in solution phase by the controlled hydrolysis of WCl(6) using novel carbon microspheres as the templates. All of the products were characterized by X-ray powder diffraction (XRD), scanning electronic microscopy (SEM), and transmission electron microscopy (TEM). The as-synthesized spheres had large diameters of about 400 nm and thin shells of about 30 nm composed of numerous small nanocrystals. Prompted by the porous structure and small crystal size of the shell wall, we constructed WO(3) hollow-sphere gas sensors and found that these sensors had good sensitivity to alcohol, acetone, CS(2), and other organic gases.     

Configuration and optimization of semiconductor gas sensors as gas chromatographic detectors

A tin oxide, gas-sensitive semiconductor sensor was configured as a gas chromatographic detector and its performance was optimized. Two sensor housings were compared but little difference was found in performance. The flow rate and temperature of the column and the internal heater voltage of the sensor affected both the sensitivity and peak shape. The temperature of the sensor surface was the most critical parameter. Optimal conditions for the gas chromatographic detection of a mixture of alkanes (C₁–C₅) and hydrogen were identified by using the simplex technique. The detection limit for hydrogen was improved by a factor of five to 20 ppb (v/v), illustrating the value of optimization and the excellent sensitivity of the detector. It is concluded that semiconductor gas sensors offer significant advantages as gas chromatographic detectors for the determination of reducing gases.     

Amperometric proton selective sensors utilizing ion transfer reactions across a microhole liquid/gel interface

A new cost-effective amperometric proton selective sensor utilizing a single microhole interface between two immiscible electrolyte solutions (ITIES) is developed. The sensing methodology is based on measuring currents associated with proton transfer across the interface assisted by a proton selective ionophore. The ellipse shaped micro-interface was first fabricated by simple mechanical punching with a sharp needle on a thin PVC film (12 μm thick) commercially available as a food wrapping material. The microhole was then filled up with a gellified polyvinylchloride (PVC)-2-nitrophenyloctylether (NPOE) to create a single microhole liquid/liquid interface. Direct ion transfer reactions across the polarized interface serving as ion sensing platforms were studied using cyclic voltammetry. In order to enhance the selectivity of proton sensing, a proton selective ionophore, octadecyl isonicotinate (ETH1778), was incorporated into the organic gel layer and their electrochemical sensing characteristics were investigated using cyclic voltammetry and differential pulse stripping voltammetry. As an example, we employed the proton selective sensor for the determination of glucose concentrations. The detection scheme involves two steps: (i) protons are first generated by the oxidation of glucose with glucose oxidase in the aqueous phase; and (ii) the current associated with the proton transfer across the interface is then measured for correlating the concentration of glucose.     

Metal-oxide based nanocomposites as materials for gas sensors

Correlations between the composition, structure, and sensor properties of SnO₂-M^IIO (M^IIO = Fe₂O₃, MoO₃, V₂O₅) nanocomposites prepared by wet chemistry synthesis were elucidated. The elemental and phase compositions of the materials, distribution of components between the bulk and surface, particle size, and specific surface area were examined. Surface modification of semiconductor oxides allows controlling the type and density of surface acid centers and redox properties of materials. The result is an increase in the sensor selectivity.