Development of chemical sensors based on redox-dependent receptors. Preparation and characterization of phenanthrenequinone-modified electrodes

The study of phenanthrenequinone(PQ)-modified electrodes, prepared by electropolymerization of a phenanthrenequinone-pyrrole derivative, is described. The surface-confined PQ is shown to behave similarly to PQ in solution, acting as a redox-dependent receptor toward aromatic ureas in aprotic solvents. Large, positive shifts in the E1/2 of the PQ0/- redox couple are observed in the presence of these ureas, due to a strong hydrogen bonding interaction between the PQ radical anion and urea. The effect is fully reversible. Of the substrates examined, only aromatic ureas produce a significant shift. Nonaromatic ureas or other HN and HO containing compounds have little effect on the E1/2. The magnitude of the shift is also independent of electrode coverage, allowing reproducible measurements to be made despite significant loss in material from the surface.     

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.     

Antioxidant sensors based on DNA-modified electrodes

TiO2/ITO modified electrodes were developed to quantitatively photooxidize adsorbed ds-DNA and to study the effect of antioxidants as ds-DNA protecting agents. TiO2 films are used for efficient ds-DNA immobilization, for ds-DNA oxidation through photogenerated hydroxyl radicals, and as electrodes for amperometric sensing. The films, prepared by a sol-gel process, are deposited on ITO glass electrodes. Damages occurring after ds-DNA oxidation by ROS are detected by adding MB as an intercalant probe and by monitoring the electrochemical reduction current of the intercalated redox probe. The MB electrochemical signal is found to be sensitive enough to monitor ds-DNA structure changes, and the electrochemical sensor has been applied to the evaluation of the antioxidant properties of glutathione and gallic acid.     

Antioxidant redox sensors based on DNA modified carbon screen-printed electrodes

Antioxidant redox sensors based on DNA modified carbon screen-printed electrodes were developed. The carbon ink was doped with TiO2 nanoparticles, onto which double-strand DNA was adsorbed. A redox mediator, namely, tris-2,2'-bipyridine ruthenium(II) [Ru(bpy)3(2+)] was electrooxidized on the electrode surface to subsequently oxidize both the adsorbed ds-DNA and the antioxidants in solution. The resulting oxidation damage of the adsorbed ds-DNA was then detected by square wave voltammetry in a second solution containing only Ru(bpy)3Cl2 at a low concentration (microM). A kinetic model was developed to study the protecting role of antioxidants in aqueous solutions. The electrochemical sensor has been applied to evaluate the redox antioxidant capacity of different molecules.     

Scalable arrays of chemical vapor sensors based on DNA-decorated graphene

Arrays of chemical vapor sensors based on graphene field effect transistors functionalized with single-stranded DNA have been demonstrated. Standard photolithographic processing was adapted for use on large-area graphene by including a metal protection layer, which protected the graphene from contamination and enabled fabrication of high quality field-effect transistors （GFETs）. Processed graphene devices had hole mobilities of 1,640 ± 250 cm2.V-1.s-1 and Dirac voltages of 15 ± 10 V under ambient conditions. Atomic force microscopy was used to verify that the graphene surface remained uncontaminated and therefore suitable for controlled chemical functionalization. Single-stranded DNA was chosen as the functionalization layer due to its affinity to a wide range of target molecules and π-π stacking interaction with graphene, which led to minimal degradation of device characteristics. The resulting sensor arrays showed analyte- and DNA sequence-dependent responses down to parts-per-billion concentrations. DNA/GFET sensors were able to differentiate among chemically similar analytes, including a series of carboxylic acids, and structural isomers of carboxylic acids and pinene. Evidence for the important role of electrostatic chemical gating was provided by the observation of understandable differences in the sensor response to two compounds that differed only by the replacement of a （deprotonating） hydroxyl group by a neutral methyl group. Finally, target analytes were detected without loss of sensitivity in a large background of a chemically similar, volatile compound. These results motivate further development of the DNA/graphene sensor family for use in an electronic olfaction system.     

Reversible potentiometric oxygen sensors based on polymeric and metallic film electrodes.

Various materials and sensor configurations that exhibit reversible potentiometric responses to the partial pressure of oxygen at room temperature in neutral pH solution are examined. In one arrangement, platinum electrodes are coated with plasticized poly(vinyl chloride) films doped with a cobalt(II) tetraethylene pentamine complex. For such sensors, potentiometric oxygen response is attributed to a mixed potential originating from the underlying platinum electrode surface as well as a change in redox potential of the Co(II)-tetren-doped film as the complex binds oxygen reversibly. The response due to the platinum surface is prolonged by the presence of the Co(II)-tetren/PVC film. Alternately, thin films of metallic copper, electrochemically deposited on platinum and/or sputtered or vapor deposited on a single crystal silicon substrate, may be used for reversible oxygen sensing. The long-term reversibility and potentiometric stability of such copper film-based sensors is enhanced (up to 1 month) by preventing the formation of cuprous oxide on the surfaces via the application of an external nonpolarizing cathodic current through the working electrode or by specifically using sputtered copper films that have [100] preferred crystal structures as determined by X-ray diffraction. The implications of these findings in relation to fabricating analytically useful potentiometric oxygen sensors are discussed.     

An approach to fabricating chemical sensors based on ZnO nanorod arrays

Vertically and laterally aligned ZnO nanorod arrays were synthesized on Pt-coated Si substrates by catalyst-free metal organic chemical vapor deposition. An approach to fabricating chemical sensors based on the nanorod arrays using a coating-and-etching process with a photo-resist is reported. Tests of the devices as oxygen gas sensors have been performed. Our results demonstrate that the approach holds promise for the realization of sensitive and reliable nanorod array chemical sensors.     

Smart optical sensors for chemical substances based on porous silicon technology

A simple geometry optical sensor based on porous silicon technology is theoretically and experimentally studied. We expose some porous silicon optical microcavities with different porous structures to several substances of environmental interest: Very large red shifts in the single transmission peak in the reflectivity spectrum due to changes in the average refractive index are observed. The phenomenon can be ascribed to capillary condensation of vapor phases in the silicon pores. We numerically compute the peak shifts as a function of the liquid volume fraction condensed into the stack by using the Bruggeman theory. The results presented are promising for vapor and liquid detection and identification.     

Peroxidase model electrodes: heme peptide modified electrodes as reagentless sensors for hydrogen peroxide

A peroxidase model electrode was devised for reagentless sensing of hydrogen peroxide (H2O2). A small model molecule, which mimics the vicinity of the reaction center of a redox enzyme, can communicate electrochemically with an electrode. Heme nonapeptide (MW congruent to 1600) having peroxidase activity was adopted as a peroxidase model compound and was covalently immobilized on a tin oxide (SnO2) electrode as a roughly monomolecular layer. The modified electrode thus obtained responded to H2O2 at concentrations down to 10(-6) M without electron mediator or promoter, at a mild potential of +150 or +300 mV vs Ag/AgCl. In a batch system, the response reached a steady state in a few seconds. Measurements were possible also in a flow system with an assay time of 0.5-1.0 min/sample. The steady-state response of the electrode was kinetically analyzed.     

Thin film chemical sensors based on p-CuO/n-ZnO heterocontacts

Previous work on bulk ceramic heterocontacts (n-ZnO/p-CuO) has indicated significant sensitivity to the presence of specific adsorbed chemical species. Here, these results are extended to thin film heterostructures fabricated via chemical solution methods. It is expected that thin film sensor architectures will possess significant advantages over their bulk counterparts. In this study, the desired properties of porosity and crystallinity have been optimized with respect to pyrolysis temperature for each ZnO and CuO sol-gel process. The results of microscopy and X-ray diffraction (XRD) indicated that an optimal balance of these two properties is achieved at a pyrolysis temperature of 250 °C. The CuO films were seen to possess a level of porosity significantly higher than that seen in the ZnO films, making them an ideal candidate for the top layer in a planar thin film heterostructure. Results of current-voltage measurements conducted in 4000 ppm hydrogen have confirmed that the inherent porosity of the CuO films led to an enhanced sensor response in CuO on ZnO heterostructures. Lastly, the fabrication and structural characterization of a mixed solution type heterostructure has been detailed. Atomic force microscopy and XRD data indicated the presence of ZnO pillars dispersed among a matrix of CuO.     

Ultrasensitive chemical sensors based on whispering gallery modes in a microsphere coated with zeolite

We propose a highly sensitive chemical sensor by functionally coating a zeolite film on the external surface of an optical microsphere. Using the perturbation theory, a model is developed to calculate sensor sensitivity and analyze the impact of the zeolite film thickness. The quality factor and detection limit are also investigated by using an approximate model. Simulations show that a zeolite coating can effectively increase sensitivity. The results provide physical insights for the design and optimization of various parameters for desired sensor performance.     

Development and application of mass sensors based on flexuralresonances in alumina beams

New mass sensors are described, which are based on the change in the flexural resonant frequencies of ceramic cantilever beams subject to piezoelectric excitation. The devices have been fabricated by screen-printing and firing a PZT-based paste on 96% alumina substrates with the methods of thick film technology and are, therefore, low cost and easy to manufacture. Inserted in an electronic feedback loop sustaining and tracking oscillations at one of the resonant frequencies, the sensors work as resonant microbalances with frequency output and can be employed for gravimetric chemical measurements. The beams have been implemented in two different sizes and, as a consequence, operated at different frequencies (about 82 and 149 kHz), in order to vary the mass sensitivity. The sensors' manufacturing and theory of operation are illustrated, and experimental results on their characterization are reported. For the two sensor sizes, mass sensitivities of about -280 and -1200 Hz/mg have been measured, in agreement with theoretical predictions. The influence of temperature has been investigated showing that, for slow thermal drifts, a satisfying degree of compensation can be achieved with a differential configuration. The devices have been successfully applied as sorption sensors for the measurement of air relative humidity (RH) by sensitizing the beams' surface with hydrophilic polymeric coatings. On the basis of past investigations, poly(N-vinylpyrrolidinone) and poly(ethyleneglycol) have been adopted as coating materials, obtaining respective frequency shifts of about 500 and 1400 Hz for RH ranging from 12 to 85%     

O(2)-responsive chemical sensors based on hybrid xerogels that contain fluorinated precursors

We report the development and analytical figures of merit associated with several new O(2)-responsive sensor materials. These new sensing materials are formed by sequestering the luminophore tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) ([Ru(dpp)(3)](2+)) within hybrid xerogels that are composed of two of the following methoxysilanes: tetramethoxysilane, n-propyl-trimethoxysilane, 3,3,3-trifluoropropyl-trimethoxysilane, phenethyl-trimethoxysilane, and pentafluorophenylpropyl-trimethoxysilane. Steady-state and time-resolved luminescence measurements are used to investigate these hybrid xerogel-based sensor materials and elucidate the underlying reasons for the observed performance. The results show that many of the [Ru(dpp)(3)](2+)-doped composites form visually uniform, crack-free xerogel films that can be used to construct O(2) sensors that have linear calibration curves and excellent long-term stability. To the best of our knowledge, the [Ru(dpp)(3)](2+)-doped fluorinated hybrid xerogels also exhibit the highest O(2) sensitivity of any reported [Ru(dpp)(3)](2+)-based sensor platform.     

MIS gas sensors based on porous silicon with Pd and WO3/Pd electrodes

Pd and WO₃/Pd gate metal-oxide-semiconductor (MIS) gas sensitive structures based on porous silicon layers are studied by the high frequency C(V) method. The chemical compositions of composite WO₃/Pd electrodes are characterized by secondary-ion mass spectrometry (SIMS). The atomic force microscopy (AFM) was used for morphologic studies of WO₃/Pd films. As shown in the experiments, WO₃/Pd structures are more sensitive and selective to the adsorption of hydrogen sulphide compared to Pd gate. The analyses of kinetic characteristics allow us to determine the response and characteristic times for these structures. The response time of MIS-structures with thin composite WO₃/Pd electrodes (the thickness of Pd is about 50 nm with WO₃ clusters on its surface) is slower compared to the structures with Pd electrodes. Slower sensor responses of WO₃-based gas sensors may be associated with different mechanism of gas sensitivity of given structures. The enhanced sensitivity and selectivity to H₂S action of WO₃/Pd MIS-structures can also be explained by the chemical reaction that occurs at the catalytic active surface of gate electrodes. The possible mechanisms of enhanced sensitivity and selectivity to H₂S adsorption of MIS gas sensors with WO₃/Pd composite gate electrodes compared to pure Pd have been analyzed.     

Ceramic-based chemical sensors, probes and field-tests in automobile engines

The monitoring and control of combustion-related emissions is a top priority in many industries. The major methods used to detect combustion gases fall short of practical applications for in-situ measurements in industrial environments involving high temperature and chemical contaminants. The real challenge is not only to develop highly sensitive and selective sensors, but to maintain long-term stability in such aggressive environments. This article presents an overview of a multidisciplinary research effort in ceramic-based chemical sensors, highlighting opportunities as well as challenges. The group of sensors (CO, NO _x , O₂, and CO₂) selected for this article can, in general, be used to determine the state of combustion in a wide variety of applications. Fabrication of sensor probes and their field-test results in automobile engines are also presented.