Electrochemical utilisation of chemical vapour deposition grown carbon nanotubes as sensors

We overview recent developments in the fabrication of the world’s smallest electrode, the carbon nanotube via chemical vapour deposition (CVD) and demonstrate how these electrodes are beneficially utilised and tailored towards the electrochemical sensing of target analytes. The use of carbon nanotubes arrays grown via CVD to beneficially tailor the arrays to their intended electro-analytical application is also highlighted.     

Electrochemical and optical sugar sensors based on phenylboronic acid and its derivatives

Recent progress in electrochemical and optical sugar sensors based on phenylboronic acid (PBA) and its derivatives as recognition components is reviewed. PBAs are known to bind diol compounds including sugars to form cyclic boronate esters that are negatively charged as a result of the addition of OH^? ions from solution. Based on the formation of PBA charged species, sugars and their derivatives can be detected by means of electrochemical and optical techniques. For the development of PBA-based electrochemical sensing systems or sensors, PBA is modified with a redox-active marker, because PBA itself is electrochemically inactive, and ferrocene derivatives are often employed for this purpose. Ferrocene-modified PBAs have been used as redox-active additives in solution for the electrochemical detection of sugars and derivatives. PBA-modified electrodes have also been constructed as reagentless electrochemical sensors, where PBAs are immobilized on the surface of metal and carbon electrodes through mainly two routes: as a self-assembled monolayer film and as a polymer thin film. PBA-modified electrodes can be successfully used to detect sugars and derivatives through potentiometric and voltammetric responses. In addition, PBA-modified electrodes can be used for the immobilization of glycoenzymes on an electrode surface by the formation of boronate esters with carbohydrate chains in the glycoenzymes, thus resulting in enzyme biosensors. For the development of PBA-based optical sensors, a variety of chromophores and fluorophores have been coupled with PBA. Azobenzene dyes have been most frequently used for the preparation of colorimetric sugar sensors, in which the absorption wavelength and intensity of the dye are dependent on the type and concentration of added sugars. The sensitivity of the sensors is significantly improved based on multi-component systems in which alizalin red S, pyrocatechol violet, starch–iodine complex, and cyclodextrin are employed as indicators. Anthracene, pyranine, fluorescein, and rhodamine dyes have been used as fluorophores for fluorescence sensors. These dyes have been used in solution or immobilized in films, hydrogels, nanospheres, and quantum dots (QDs) to enhance the sensitivity. QDs-based sensors have been successfully applied for continuous monitoring of glucose in cells. Holographic glucose sensors have also been developed by combining PBA-immobilized hydrogels and photonic crystal colloidal arrays.     

Electrochemical DNA sensors based on enzyme dendritic architectures: an approach for enhanced sensitivity

The modification of enzymes with multiple single-stranded oligonucleotides opens up a new concept for the development of DNA sensors with enhanced sensitivity. This work describes the generation of reporter sequences labeled with an enzyme for the demonstration of their ability to specifically hybridize and to permit signal amplification by successive hybridization steps. The synthetic pathway for the labeling of GOx with oligonucleotide sequences is based on the oxidation of the glycosidic residues of the enzyme and their covalent binding with 5'-end amine-modified oligonucleotides. Spectrophotometric characterization of these functionalized sequences results in an average number of three linked oligonucleotides per enzyme molecule. Their specificity is demonstrated in both a direct and a sandwich-type hybridization assay. The transduction of the enzyme-linked DNA sensors is based on self-assembled multilayers, including a chemically modified anionic horseradish peroxidase electrochemically connected to a water-soluble cationic poly[(vinylpyridine)Os(bpy)(2)Cl] redox polymer in an electrostatic ordered assembly. The sensing layer is constructed by the covalent binding of the DNA probe over the redox polymer through the 3'-phosphate group, enabling the capture of the target sequence. Upon addition of glucose, hybridization results in the production of H(2)O(2), which readily diffuses to the electrocatalytic assembly, giving rise to a cathodic current at 100 mV vs Ag/AgCl. Hybridization is always performed at room temperature, and after 30 min of incubation, an amperometric response is obtained that is proportional to DNA concentration. The simultaneous sandwich assay enables the quantification of a free-label 44-mer oligonucleotide at 1 nM concentration. Signal amplification is realized by a new hybridization step over the free sequences, giving rise to a dendritic architecture that accumulates enzyme molecules per hybridization event.     

Electrochemical performance, biocompatibility, and adhesion of new polymer matrices for solid-state ion sensors.

Ammonium and potassium ion-selective membranes formulated with PVC/hydroxylated PVC, polyurethane/hydroxylated PVC, and moisture-curable silicone rubber matrices are studied in an effort to extend the lifetime of solid-state ion sensors through improved membrane adhesion. The PVC/membranes exhibit electrochemical performance equivalent to that of conventional PVC membranes in terms of slope, detection limit, and selectivity. The polyurethane- and silicone-rubber-based membranes have better adhesion to silicon nitride than do PVC or hydroxylated PVC matrices. Incorporating a silanizing reagent (silicon tetrachloride) significantly improves the adhesion of the polyurethane matrix. The use of silicon tetrachloride in membrane matrices also enhances the electrochemical stability of the interfacial potential between ion-selective polymer-matrix membranes and silver epoxy inner reference electrodes of solid-state sensors. The biocompatibility of the polymer matrices is examined via radiotracer protein adsorption studies and whole blood clotting time measurements. The polyurethane- and silicone-rubber-based membranes exhibit less overall nonspecific protein adsorption than the PVC or hydroxylated PVC matrices.     

Configurable electrodes for capacitive-type sensors and chemical sensors

This paper describes a novel design for capacitive sensors or chemical sensors, which features configurable interdigitated electrodes: The electrode spacing can be varied by means of switches on the CMOS chip. This new design allows for performing two capacitive measurements with one single-sensor capacitor so that the number of sensors required to acquire a certain amount of information can be significantly reduced. The use of the same sensor and the same polymer layer for two measurements at a different electrode periodicity provides a better signal quality for the difference signal since detrimental influences, such as humidity and sensor drift, are similar for both electrode configurations and are strongly correlated. Such high signal quality is required for, e.g., the successful recognition of n-octane in the presence of tenfold larger background signals of humidity or, in general, for the determination of low analyte concentrations in humid air. The baseline drift in the concentration predictions based on the differential signal from the two electrode configurations was an order of magnitude lower than that for uncorrelated signals produced by two separate interdigitated capacitors on the same chip. Since the number of required sensors is reduced and, owing to the differential readout of two electrode configurations, reference capacitors are no longer necessary, the overall chip size and/or the number of sensor chips and, consequently, costs can be considerably reduced.     

Two-channel phototurbidity sensors

Translated from Izmeritel'naya Tekhnika, No. 5, pp. 21–23, May, 1992.     

Semiconductor gas sensors

Abstract

The technology associated with the use of semiconductors in monitoring the composition of the atmosphere has been advancing rapidly in recent years. The twin demands of remote process control and concern for the environment have produced requirements for sensing different gases in a wide range of applications. In this paper the authors review the state of the art of semiconductor gas sensor development and anticipate the directions in which future progress is likely to be made.

MST/221     

Amplitude fiber-optic sensors

Translated from Izmeritel'naya Tekhnika, No. 1, pp. 34, 39–40, January, 1992.     

Frequency-coded chemical sensors

We have developed a new method to intelligently sample analytes and introduce the analytes to sensors. The method automatically adjusts sampling duration according to the sensors' response to the analytes and converts the amplitude of the sensor output to a frequency output, giving us another opportunity to reduce noise in the signal. It also addresses some of the common sensor issues such as response time, saturation, chemical dynamic range, and sensor protection, saving precious detection time, protecting sensors, and enabling sensitive sensors built for low-concentration detection to be used for high-concentration detection as well. We have put together a system using a tuning fork chemical sensor as a sample sensor to demonstrate the feasibility and benefits of the new sensing technique.     

pH-sensitive holographic sensors

Holographic sensors for monitoring H+ (pH) have been fabricated from ionizable monomers incorporated into thin, polymeric, hydrogel films which were transformed into volume holograms using a diffusion method coupled with holographic recording, using a frequency doubled Nd:YAG laser (532 nm). Unlike other optical pH sensors, it is possible to tailor the operational replay wavelength of the holographic sensor by careful control of the exposure conditions. The holographic diffraction wavelength (color) of the holograms was used to characterize their shrinkage and swelling behavior as a function of pH in various media. The effects of hydrogel composition, ionic strength, temperature, and factors influencing reversibility and response time are evaluated. Optimized holographic pH sensors show milli-pH resolution. The pH-sensing range of the holograms can be controlled through variation of the nature of the ionizable co-monomer used in polymer film construction; a series of holographic sensors displaying visually perceptible, fully reversible color changes over different pH ranges are demonstrated. A poly(hydroxyethyl methacrylate-co-methacrylic acid) holographic sensor was shown to be able to quantify the change in H+ concentrations in real time in a sample of milk undergoing homolactic fermentation in the presence of Lactobacillus casei.