A flow method with photocatalytic oxidation of dissolved organic matter using a solid-phase (TiO2) reactor followed by amperometric detection of consumed oxygen

A photocatalytic sensor for the determination of chemical oxygen demand (COD) using titanium dioxide, based on the use of a pair of oxygen electrodes and flow injection analysis, is described. The measuring principle is based on the direct determination of the oxygen concentration change resulting from photocataltic oxidation of organic compounds. One of the two oxygen electrodes, the reference oxygen electrode, was utilized to measure the reference signal responding only to oxygen present in the injected samples. Oxygen consumption due to the TiO2-catalyzed photochemical oxidation of organic compounds in samples was monitored with the working oxygen electrode. The COD value of this sensor was calculated as the difference of the currents at reference and working oxygen electrodes, respectively. The operation characteristics of the sensor are demonstrated using artificially treated wastewater as a substrate. The sensor was also applied to the determination of COD in real water samples from dam reservoirs (n = 20) all over Japan. The results were in good agreement with those from the conventional COD methods (i.e., permanganate and dichromate methods).     

Development of a selective gas sensor utilizing a perm-selective zeolite membrane

Reported here is a novel sensor that utilizes a zeolite film to selectively limit gas exposure of the sensing surface. A unique amperometric sensor design based on a non-porous mixed conducting sensing electrode enables the formation of a continuous zeolite film covering the entire sensor surface. The sensor was tested in a variety of oxygen containing gases. The sensor without a zeolite film responded strongly to both oxygen and carbon dioxide at a bias of 1.8 V. In contrast, the sensor coated with a zeolite film showed a discernable, but diminished response to oxygen, and a more marked drop in response to CO₂ indicating that the diffusion of oxygen through the zeolite film is preferential to that of CO₂. The response of the zeolite coated sensor to a mixture of oxygen and carbon dioxide gases is attributed primarily to the oxygen content. Expanding this concept using a variety of different zeolite structures covering an array of sensors, complete analyses of complex gaseous mixtures could be performed in a very small device.     

Photocatalytic sensor for chemical oxygen demand determination based on oxygen electrode

The construction and performance evaluation of a novel Chemical Oxygen Demand (COD) sensor is described. The sensor measures, using an oxygen electrode, a decrease of dissolved oxygen of a given sample resulting from photocatalytic oxidation of the organic compounds therein. As the photocatalyst, titanium dioxide (TiO2) fine particles adsorbed on a translucent poly(tetrafluoroethylene) (PTFE) membrane was used. The oxygen electrode with the membrane attached on its tip was used as the sensor probe. The operation characteristics of the sensor are demonstrated using an artificial wastewater and real water samples from lakes in Japan. This method is considered to be reliable, in that the observed parameter is close to the theoretical definition of chemical oxygen demand (COD), the amount of oxygen consumed for oxidation of organic compounds.     

Polyelectrolyte microshells as carriers for fluorescent sensors: loading and sensing properties of a ruthenium-based oxygen indicator

A strategy for the design and fabrication of microcapsule-based fluorescent biosensors containing indicators and internal references is described. The rationale for this work is the physical immobilization and chemical separation of assay chemistry for use in biological environments. Using the general approach of depositing oppositely charged species on colloidal micro/nanotemplates, a sensor system employing polyelectrolyte microshells for uptake of functional molecules is proposed, and experiments to demonstrate the feasibility of nanoengineering the sensor properties are described in the context of an oxygen sensor. Methods for immobilization and entrapment of fluorescent indicator and reference dyes are shown, along with the pH dependence of this process. Embedded dyes are shown to be stable and retain their function, as demonstrated with oxygen-sensitivity experiments of loaded microcapsules. Although oxygen sensitivity is presented as an example of a specific application, the overall strategy is likely more generally useful. The work suggests that polyelectrolyte microshells may be used as a platform to develop novel sensors by entrapment of functional materials.     

A carbon dioxide gas sensor by combination of multivalent cation and anion conductors with a water-insoluble oxycarbonate-based auxiliary electrode

A compact and inexpensive carbon dioxide gas sensor was successfully realized by the combination of a divalent magnesium ionic conductor of Mg0.7(Zr0.85Nb0.15)4P6O24 and a divalent oxide anion conducting ZrO2-Y2O3 solid electrolyte with the water-insoluble Li- and Ba-codoped Nd2O2CO3 solid solution as the auxiliary electrode. The sensor response was continuous and reproducible, and the present sensor also demonstrated a theoretical Nernst response in the atmosphere where water vapor, nitrogen oxides, ammonia, etc., coexist. The exposure of the present sensor to water dew and variation in oxygen concentration does not interfere with the sensor response, which will be a great advantage in applying the in situ practical CO2 detection in combustion exhaust gas atmospheres.     

Design of an open path near-infrared diode laser sensor: application to oxygen, water, and carbon dioxide vapor detection

An open path diode laser sensor was constructed with near-infrared diode lasers and two-tone frequency-modulation spectroscopy. The sensor incorporates several novel features (such as digital signal-processing algorithms, a computerized line-locking routine, and discontinuous wavelength scanning) that are important in a field instrument. The sensor was used to monitor oxygen, water, and carbon dioxide in the near-infrared spectral range. For oxygen, an absorbance detection sensitivity of 2 × 10(-6) in a 10-Hz bandwidth was demonstrated with a GaALAs laser at 760.56 nm. The stability of the sensor was 0.1% over a period of 10 h when an absorbance of 6 × 10(-3) was monitored.     

Manipulation of microenvironment with a built-in electrochemical actuator in proximity of a dissolved oxygen microsensor

Biochemical sensors for continuous monitoring require dependable periodic self diagnosis with acceptable simplicity to check its functionality during operation. An in-situ self-diagnostic technique for a dissolved oxygen microsensor is proposed in an effort to devise an intelligent microsensor system with an integrated electrochemical actuation electrode. With a built-in platinum microelectrode that surrounds the microsensor, two kinds of microenvironments, called the oxygen-saturated or oxygen-depleted phases, can be created by water electrolysis, depending on the polarity. The functionality of the microsensor can be checked during these microenvironment phases. The polarographic oxygen microsensor is fabricated on a flexible polyimide substrate (Kapton) and the feasibility of the proposed concept is demonstrated in a physiological solution. The sensor responds properly during the oxygen-generating and oxygen-depleting phases. The use of these microenvironments for in-situ self-calibration is discussed to achieve functional integration, as well as structural integration, of the microsensor system.     

Oxygen optrode for use in a fiber-optic glucose biosensor

An optical fiber oxygen sensor, based on the dynamic quenching of the luminescence of tris(1,10-phenanthroline)-ruthenium(II) cation by molecular oxygen, is presented. The complex is adsorbed onto silica gel, incorporated in a silicone matrix possessing a high oxygen permeability, and placed at the tip of the optical fiber. Oxygen has been monitored continuously in the 0-750 Torr range, with the detection limit being as low as 0.7 Torr. The device has been applied to the development of a fast responding and highly sensitive fiber-optic glucose biosensor based on this highly sensitive oxygen transducer. The sensor relates oxygen consumption (as a result of enzymatic oxidation) to glucose concentration. The enzyme is immobilized on the surface of the oxygen optrode; carbon black is used as an optical isolation in order to prevent ambient light and sample fluorescence to interfere. Measurements have been performed in a flow-through cell in air-equilibrated glucose standard solutions of pH 7.0. The effects of enzyme immobilization procedures (including enzyme immobilization on carbon black) as to response times (around 6 min), analytical ranges (0.06-1 mM glucose), reproducibility in sensor construction, and long-term stability have been studied as well.     

Modeling the effect of oxygen on the amperometric response of immobilized organoselenium-based S-nitrosothiol sensors

Amperometric detection of S-nitrosothiols (RSNOs) at submicromolar levels in blood samples is of potential importance for monitoring endothelial function and other disease states that involve changes in physiological nitric oxide (NO) production. It is shown here that the elimination of dissolved oxygen from samples is critical when covalently attached diselenocystamine-based amperometric RSNO sensors are used for practical RSNO measurements. The newest generation of RSNO sensors utilizes an amperometric NO gas sensor with a thin organoselenium modified dialysis membrane mounted at the distal sensing tip. Sample RSNOs are catalytically reduced to NO within the dialysis membrane by the immobilized organoselenium species. In the presence of oxygen, the sensitivity of these sensors for measuring low levels of RSNOs (<μM) is greatly reduced. It is demonstrated that the main scavenger of the generated nitric oxide is not the dissolved oxygen but rather superoxide anion radical generated from the reaction of the reduced organoselenium species (the reactive species in the catalytic redox cycle) and dissolved oxygen. Computer simulations of the response of the RSNO sensor using rate constants and diffusion coefficients for the reactions involved, known from the literature or estimated from fitting to the observed amperometric response curves, as well as the specific geometric dimensions of the RSNO sensor, further support that nitric oxide and superoxide anion radical quickly react resulting in near zero sensor sensitivity toward RSNO concentrations in the submicromolar concentration range. Elimination of oxygen from samples helps improve sensor detection limits to ca. 10 nM levels of RSNOs.     

Oxygen sensor based on the fluorescence quenching of a ruthenium complex immobilized in a biocompatible Poly(Ethylene glycol) hydrogel

An optically based system has been developed for use as an oxygen sensor for a cell culture bioreactor. Electrochemical sensors based on the Clark oxygen electrode are typically used with cell-culture bioreactors. These sensors, however, are subject to long-term drift, due in part to biofouling, and require penetrating the bioreactor with the probe in order to perform a measurement. We report an implantable sensor that, when used with an external fiber-optic probe, takes advantage of the oxygen stimulated fluorescence quenching of dichloro(tris-1,10-phenanthroline) ruthenium (II) hydrate. This fluorophore was immobilized in a photopolymerized hydrogel made from poly(ethylene glycol) diacrylate (PEG-DA), a polymer known to minimize protein and cell adhesion. A low-average molecular weight PEG-DA (MW = 575) was employed to hinder the fluorophore from leaching. The PEG-DA precursor solution contained 40% H/sub 2/O such that, upon polymerization, the gel was already in the hydrated state. Sensor hydrogels stored in H/sub 2/O for several months retained their physical shape and sensitivity to oxygen. The sensor showed a high degree of reproducibility across a range of oxygen concentrations that are typical for cell culture experiments (0-9.1 ppm O/sub 2/), and a linear model produced a strong correlation (R /sup 2/= 0.995) compared with a commercial electrochemical probe. No drift or hysteresis was identified in the sensor across cycles of varying oxygen concentrations in this range.     

Open air calibration with temperature compensation of a luminescence quenching-based oxygen sensor for portable instrumentation

This report addresses the task of calibrating an optical sensor for oxygen determination. Detailed analyses of the functional dependences from our measurement system results have been carried out with the additional aim of temperature compensation. As a result, an empirical calibration function has been successfully derived for the luminescent quenching-based oxygen sensor included in a self-designed portable instrument. This function also compensates for the temperature influence on the quenching luminescence process in the range from 0 to 45 degrees C. Moreover, the calibration procedure is extremely simple because only a single standard is needed. In fact, the oxygen measurement system can be calibrated with exposure to an open air atmosphere, and therefore, neither laboratory standards nor trained personnel are required. The method has been applied to a set of 11 units of the mentioned sensor (up to 24% oxygen concentration) giving an overall deviation between our calibrated system results and the laboratory standards of 0.3% oxygen concentration (calculated with 95% confidence level). The proposed calibration function has shown itself to be applicable for different sensing film thicknesses and luminophore concentrations using the same fittings parameter. Additionally, this function has been successfully applied to other oxygen dyes. Good agreement has also been found when the performance of the instrument was compared to a commercially available portable instrument based on an electrochemical sensor. We believe that this work could be an interesting finding for spreading the use of optical sensors for atmospheric oxygen determination in commercial measurement equipment for different purposes in confined working atmospheres, such as mines, undergrounds, warehouses, vehicles, and ships.     

Dual fluorescence sensor for trace oxygen and temperature with unmatched range and sensitivity

An optical dual sensor for oxygen and temperature is presented that is highly oxygen sensitive and covers a broad temperature range. Dual sensing is based on luminescence lifetime measurements. The novel sensor contains two luminescent compounds incorporated into polymer films. The temperature-sensitive dye (ruthenium tris-1,10-phenanthroline) has a highly temperature-dependent luminescence and is incorporated in poly(acrylonitrile) to avoid cross-sensitivity to oxygen. Fullerene C70 was used as the oxygen-sensitive probe owing to its strong thermally activated delayed fluorescence at elevated temperatures that is extremely oxygen sensitive. The cross-sensitivity of C70 to temperature is accounted for by means of the temperature sensor. C70 is incorporated into a highly oxygen-permeable polymer, either ethyl cellulose or organosilica. The two luminescent probes have different emission spectra and decay times, and their emissions can be discriminated using both parameters. Spatially resolved sensing is achieved by means of fluorescence lifetime imaging. The response times of the sensor to oxygen are short. The dual sensor exhibits a temperature operation range between at least 0 and 120 degrees C, and detection limits for oxygen in the ppbv range, operating for oxygen concentrations up to at least 50 ppmv. These ranges outperform all dual oxygen and temperature sensors reported so far. The dual sensor presented in this study is especially appropriate for measurements under extreme conditions such as high temperatures and ultralow oxygen levels. This dual sensor is a key step forward in a number of scientifically or commercially important applications including food packaging, for monitoring of hyperthermophilic microorganisms, in space technology, and safety and security applications in terms of detection of oxygen leaks.     

A Magnetically Controlled Wireless Optical Oxygen Sensor for Intraocular Measurements

The influence of oxygen on various ophthalmological complications is not completely understood and intraocular oxygen measurements are essential for better diagnosis and treatment. A magnetically controlled wireless sensor device is proposed for minimally invasive intraocular oxygen concentration measurements. This device will make it possible to make measurements at locations that are currently too invasive for human intervention by integrating a luminescence optical sensor and a magnetic steering system. The sensor works based on quenching of luminescence in the presence of oxygen. A novel iridium phosphorescent complex is designed and synthesized for this system. A frequency-domain lifetime measurement approach is employed because of the intrinsic nature of the lifetime of luminescence. Experimental results of the oxygen sensor together with magnetic and hydrodynamic characterization of the sensor platform are presented to demonstrate the concept. In order to use this sensor for in vivo intraocular applications, the size of the sensor must be reduced, which will require an improved signal-to-noise ratio.     

Reagentless enzyme electrode for the determination of manganese through biocatalytic enhancement.

An amperometric enzyme electrode is described for the detection and determination of manganese(II). The biosensor is based on the stimulation by manganese of the aerobic oxidation of substrates by horseradish peroxidase. A mediator, 1,2-naphthoquinone, is used as the substrate and is incorporated with the enzyme into a carbon-paste electrode. The resulting electrode acts as an enzyme-based oxygen sensor, which is sensitive to manganese. Electrochemical control of enzyme activity is achieved through substrate promotion of catalysis. Enzyme modulation by manganese can be switched on and off or adjusted through the appropriate selection of the applied potential. Currents are generated due to the bioelectrocatalytic reduction of oxygen in response to the introduction of manganese sulfate. A sustained current is achieved which is dependent on manganese concentration. Concentrations of 0.5 microM manganese or greater can be measured, and the sensor is reversible, as demonstrated by manganese removal. Biological selectivity for manganese provides a sensor which does not respond to other divalent cations tested, with the possible exception of cobalt. Reagentless, continuous sensing is achieved through substrate cycling.     

Mass transfer and gas-phase calibration of implanted oxygen sensors

A protocol is described for validation of implanted oxygen sensors, in which sensors are calibrated in the gas phase where concentration boundary layers are absent. Calibration prior to sensor implantation and confirmation after sensor explantation allows separation of tissue mass transfer effects from sensor variance and drift. A model is given here that describes the oxygen-dependent signal current in terms of oxygen mass transfer to the sensor, permeability of the sensor membrane, and electrode area. The parameter used in the model to describe mass transfer to implanted sensors is consistent with experimental observations and allows comparisons with nonimplanted sensors. This method provides a bridge between the complementary approaches of empirical calibration and model-based calculation for determining oxygen concentration from the sensor response.     

Lifetime-based pH sensor system based on a polymer-supported ruthenium(II) complex

A new luminescence lifetime-based pH sensor system is described. The system is based on [Ru(Ph2phen)2DCbpy]2+ (DCbpy = 4,4'-dicarboxy-2,2'-bipyridine) immobilized in a mixed domain network copolymer utilizing hydrophobic regions in a hydrophilic, water-swellable, poly(ethylene oxide) matrix. The metal complex binds irreversibly to the hydrophobic domains leaving the pH-sensing COOHs projecting into an aqueous-rich poly(ethylene oxide) region. The complex shows a strong pH dependence of its lifetime (3-4-fold) and provides a usable pH range of about 3-5. The long (approximately 1 micros) excited-state lifetime and visible absorption of the sensor simplifies measurements. A model for the combined pH and oxygen-quenching sensitivity of the complex is provided; this allows use of the pH system over a wide range of oxygen concentrations. The combined polymer sensor is easy to prepare and requires no covalent chemistry. Further, the polymers enhance the luminescence of the complex and minimize interference from oxygen quenching.     

Development of a differential, optical, reflective displacement sensor by use of a multilayered waveguide

A noncontact and compact optical displacement sensor is proposed and demonstrated. The principle of this system is based on the differential optical-fiber displacement sensor [Appl. Opt. 38, 1103 (1999)]. The waveguide of the sensor consists of three thin plate glasses. This approach can miniaturize and lighten the system. The performance of the sensor is geometrically analyzed. The linearity and working range of the sensor are significantly improved compared with those of the optical fiber.     

Microbial sensor for preliminary screening of mutagens utilizing a phage induction test

For the preliminary screening of mutagens, a novel microbial sensor system was developed utilizing a phage induction test. Escherichia coli lysogenic strain GY5027 and nonlysogenic strain GY5026 were used in this study. The number of living cells was determined by measuring the respiration of cells immobilized onto an oxygen electrode. The injection of a mutagen, such as AF-2 and MNNG, caused the phage induction in the lysogenic strain, resulting in the decreased respiration of only the lysogenic strain immobilized onto the oxygen electrode but not of nonlysogenic strain. The rate of current increase correlated well with the concentration of mutagens. The sensor responses to the antibiotics and bactericides were definitely different from those of mutagens. Therefore, utilization of this microbial sensor system makes possible the estimation of a substrate's mutagenicity.     

Analysis of ternary mixtures with a single dynamic microbial sensor and chemometrics using a nonlinear multivariate calibration

An amperometric biosensor based on immobilized bacterial cells of Alcaligenes eutrophus KT02 and an oxygen electrode was integrated in a flow-through system. Because microorganisms metabolize various organic analytes in a specific manner, the sensor shows for different pure analytes distinct time-dependent oxygen consumption rates that can be treated as characteristic patterns. This behavior is conserved also when the biosensor is exposed to a mixture of these organic analytes; the sensor with a particular type of microorganisms responds with a total signal. The respiration curves as time-dependent amplitudes were subdivided into several time channels. This procedure creates an additional data dimension and makes the single sensor "dynamic". Using multivariate calibration models with only one single biosensor, simultaneous quantitative analysis of ternary mixtures of acetate, L-lactate, and succinate was realized. A nonlinear algorithm that compensated for conceivable interactions of the analytes was superior to a partial least-squares algorithm. Each analyte was predicted more precisely by the nonlinear approach resulting in root-mean-square errors of prediction of 0.20 mg/L for acetate, 0.43 mg/L for L-lactate, and 0.73 mg/L for succinate.     

Applications of quantum dots in optical fiber luminescent oxygen sensors

The potential applications of luminescent semiconductor nanocrystals to optical oxygen sensing are explored. The suitability of quantum dots to provide a reference signal in luminescence-based chemical sensors is addressed. A CdSe-ZnS nanocrystal, with an emission peak at 520 nm, is used to provide a reference signal. Measurements of oxygen concentration, which are based on the dynamic quenching of the luminescence of a ruthenium complex, are performed. Both the dye and the nanocrystal are immobilized in a solgel matrix and are excited by a blue LED. Experimental results show that the ratio between the reference and the sensor signals is highly insensitive to fluctuations of the excitation optical power. The use of CdTe, near-infrared quantum dots with an emission wavelength of 680 nm, in combination with a ruthenium complex to provide a new mechanism for oxygen sensing, is investigated. The possibility of creating oxygen sensitivity in different spectral regions is demonstrated. The results obtained clearly show that this technique can be applied to develop a wavelength division multiplexed system of oxygen sensors.