Flow injection analysis as a diagnostic technique for development and testing of chemical sensors

An immobilized urease sensor is developed for continuous, on-line analysis. The sensor consists of the enzyme urease, cross-linked with bovine serum albumin into a cellulose pad, with an acid-base indicator dye covalently bound to the surface of the cellulose. The sensor is placed within a flow-injection optosensing system to monitor the change in pH, and subjected to a through evaluation, using the flow-injection technique; sensor stability (both dye and enzyme stability), speed of sensor response, sensor sensitivity, sensor-to-sensor reproducibility, response to a typical interferent, and sensor lifetime data are obtained. Sensor poisoning upon exposure to low levels of mercury, and subsequent regeneration of the immobilized enzyme pad, is investigated for use as an on-line mercury sensor. The urea sensor is also evaluated for use as a continuous monitor for urea in kidney dialysate. Enzyme Michaelis-Menten constants are determined for the immobilized urease, under given assay conditions, using a stopped-flow flow-injection technique.     

TDDFT Study on Different Sensing Mechanisms of Similar Cyanide Sensors Based on Michael Addition Reaction

The solvents and substituents of two similar fluorescent sensors for cyanide, 7-diethylamino-3-formylcoumarin (sensor a) and 7-diethylamino-3-(2-nitrovinyl)coumarin (sensor b), are proposed to account for their distinct sensing mechanisms and experimental phenomena. The time-dependent density functional theory has been applied to investigate the ground states and the first singlet excited electronic states of the sensor as well as their possible Michael reaction products with cyanide, with a view to monitoring their geometries and photophysical properties. The theoretical study indicates that the protic water solvent could lead to final Michael addition product of sensor a in the ground state, while the aprotic acetonitrile solvent could lead to carbanion as the final product of sensor b. Furthermore, the Michael reaction product of sensor a has been proved to have a torsion structure in its first singlet excited state. Correspondingly, sensor b also has a torsion structure around the nitrovinyl moiety in its first singlet excited state, while not in its carbanion structure. This could explain the observed strong fluorescence for sensor a and the quenching fluorescence for the sensor b upon the addition of the cyanide anions in the relevant sensing mechanisms.     

Novel membrane-based sensor for online membrane integrity monitoring

A novel membrane-based sensor device for upstream membrane integrity monitoring has been developed and evaluated in this study. The sensor is based on relative trans-membrane pressures created by two membranes in series inside the sensor device that detects deposition from the sample stream onto the first of the sensor membranes. The sensor pressure signals can distinguish between intact or damaged membranes in the upstream membrane filtration process. Studies were conducted to evaluate both stabilities and sensitivities of the relative trans-membrane pressure monitoring technique. Sensitivity, based on the response times of the membrane sensor for particle detection, was determined for a range of operating conditions, membrane sandwich configurations, and particle concentrations in both simulated membrane failures and for actual pin-hole defects on a submerged MF membrane. The results showed that both sensitivities and stability strongly depended on membrane sandwich configurations (membrane characteristics) in the sensor, and mode of operation (pressurized or vacuum). The membrane sensor detected bentonite particles with a concentration of 0.3 mg/L (turbidity ∼0.3 NTU) in approximately 35 min in the vacuum mode. The sensor is reliable, sensitive and low cost. It has potential applications in decentralized systems or in multichannel monitoring of local conditions in a large plant. Possible applications of the membrane sensor for fouling monitoring are also discussed.     

The first fluorescent sensor for boronic and boric acids with sensitivity at sub-micromolar concentrations--a cautionary tale

The first reported fluorescent sensor for boronic and boric acids is actually not a sensor for boronic and boric acids but rather is a sensor for protons; the system is also not the first fluorescent sensor since Alizarin has been used as a fluorescent sensor for boric acids since 1936.     

An electrochemical peptide-based Ara h 2 antibody sensor fabricated on a nickel(II)-nitriloacetic acid self-assembled monolayer using a His-tagged peptide

We report, for the first time, the use of a Ni(II)-nitriloacetic acid (NTA) self-assembled monolayer (SAM) in the fabrication of an electrochemical peptide-based (E-PB) sensor for detection of anti-Ara h 2 antibodies. We compared the performance of the sensor fabricated on a Ni(II)-NTA SAM using a His-tagged peptide with the sensor fabricated using the conventional approach via direct immobilization of a thiolated peptide. While both sensors responded only to the correct antibody in the presence of random antibodies, we observed differences between the sensors. Specifically, the detection limit of the His-tagged sensor was 1 pM, significantly lower than the 200 pM detection limit of the conventional thiolated sensor. More importantly, unlike our previously developed E-PB sensors, both sensors are regenerable and reusable. The thiolated sensor can be readily regenerated using guanidine hydrochloride; whereas the His-tagged sensor can be regenerated by direct displacement of the His-tagged probes using Ni(II) ions. Overall, our results show that both approaches are well-suited for E-PB sensor fabrication; more importantly, specific sensor properties such as detection limit and dynamic range can be tuned by simply using a different probe immobilization method.     

A Mid-Infrared Sensor for Monitoring of Chlorinated Hydrocarbons in the Marine Environment

Abstract

As part of the European research project SOFIE - “Spectroscopy using Optical Fibres in the Marine Environment”, a portable sensor system for chlorinated hydrocarbons in seawater is being developed. This novel analytical tool for real-time in-situ monitoring of a particularly important class of seawater pollutants consists of a robust, miniaturised FT-IR spectrometer in a sealed aluminium pressure vessel and a fibre optic sensor head. In a laboratory set-up using an ATR-crystal as a simplified sensor head, the effect of potentially interfering substances, both of natural and anthropogenic origin, on the sensor response was tested. It was found that the sensor readings for a specific analyte are not susceptible to aliphatic and aromatic components as well as other chlorinated hydrocarbons up to concentrations well above the average levels to be encountered in the oceans. The same applies for the parameters salinity and turbidity. Consequently, the proposed sensor system should be well suited for real-world sub-sea applications.     

Evaluation of the performance of sensors based on optical imaging of a chemically sensitive layer

Interest in the use of the optical properties of chemical indicators is growing steadily. Among the optical methods that can be used to capture changes in sensing layers, those producing images of large-area devices are particularly interesting for chemical sensor array development. Until now, few studies addressed the characterization of image sensors from the point of view of their chemical sensor application. In this paper, a method to evaluate such performance is proposed. It is based on the simultaneous measurement of absorption events in a metalloporphyrin layer with an image sensor and a quartz microbalance (QMB). Exploiting the well-known behaviour of QMB, comparison of signals enables estimation of the minimum amount of absorbed molecules that the image sensor can detect. Results indicate that at the single pixel level a standard image sensor (for example a webcam) can easily detect femtomoles of absorbed molecules. It should therefore be possible to design sensor arrays in which the pixels of images of large-area sensing layers are regarded as individual chemical sensors providing a ready and simple method for large sensor array development.     

Submicrometer cavity surface plasmon sensors

A miniaturized spherical surface plasmon sensor for measuring the binding kinetics of unlabeled molecules is introduced. The sensor has a submicrometer footprint with a sensitivity that rivals that of state-of-the-art commercial planar surface plasmon sensors, which makes it valuable for applications requiring integration of detection of molecular species in microfluidic channels. The basic principle of the sensor is exploiting the wavelength shifts of the cavity resonances of a metal-coated submicrometer sphere embedded in an opaque metal film due to molecular adsorption. The sensor has been found to be exquisitely responsive in air to water and ethanol vapor adsorption on the bare gold sensor surface. When immersed in a liquid, the sensor can detect the adsorption of less than one monolayer of dodecanethiol (approximately 1.5 nm) on the gold coating of the sphere.     

Development of an Electrochemical Sensor for Selective Determination of Dopamine Based on Molecularly Imprinted Poly(p-aminothiophenol) Polymeric Film

In this study, a molecularly imprinted electrochemical sensor (MIP/DA) was investigated for selective and sensitive determination of dopamine (DA) by electrochemical polymerization of p-aminothiophenol in the presence of DA on gold electrode. According to electrochemical behaviour of the sensor, gained through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), MIP/DA sensor showed distinctive electron transfer characteristics in comparison to the non-imprinted (NIP/DA) sensor. Besides the MIP/DA sensor showed high selectivity for dopamine through its analyte specific cavities. The sensor had a broad working range of 5.0×10⁻⁸–2.0×10⁻⁷ M with a limit of detection (LOD) of 1.8×10⁻⁸ M and the developed sensor was successfully applied for determination of dopamine in pharmaceutical samples.     

A High‐Affinity Fluorescent Sensor for Catecholamine: Application to Monitoring Norepinephrine Exocytosis

A fluorescent sensor for catecholamines, NS510, is presented. The sensor is based on a quinolone fluorophore incorporating a boronic acid recognition element that gives it high affinity for catecholamines and a turn‐on response to norepinephrine. The sensor results in punctate staining of norepinephrine‐enriched chromaffin cells visualized using confocal microscopy indicating that it stains the norepinephrine in secretory vesicles. Amperometry in conjunction with total internal reflection fluorescence (TIRF) microscopy demonstrates that the sensor can be used to observe destaining of individual chromaffin granules upon exocytosis. NS510 is the highest affinity fluorescent norepinephrine sensor currently available and can be used for measuring catecholamines in live‐cell assays.     

Toluene chemiresistor sensor based on nano-porous toluene-imprinted polymer

In this work, the application of molecularly imprinted polymer (MIP) as the recognition element of a chemiresistor sensor was introduced. Toluene-imprinted polymer and non-imprinted polymer (NIP) were synthesized and then mixed with carbon black powder in the presence of melted n-eicosane as the binder agent. The obtained composites were applied for the construction of chemiresistor sensors. The sensor, fabricated with toluene-imprinted polymer, showed a significant response towards toluene. Moreover, the response of the NIP-based (polymer synthesized without solvent) chemiresistor sensor was very small and negligible. The components of the MIP-based sensing composite were found to strongly influence the sensor sensitivity. Response surface experimental design methodology was applied to optimize the important parameters of the proposed sensor. Cross-sensitivity of the MIP-based chemiresistor sensor for different vapours was investigated and a satisfactory result was found for toluene vapour recognition. It was shown that the sensor response to toluene concentration in air was linear in the concentration range of 3.8 to 46.4?ppm. The detection limit and relative standard deviation (for five separate determinations) of the designed sensor were calculated equal to 0.8?ppm and 5.6%, respectively.     

A coated piezoelectric crystal sensor for acetic acid vapour determination

A novel sensor for acetic acid vapour determination is proposed. This sensor is based on a piezoelectric crystal covered with a film of diethylenetriamine. For the sensor development a system of our own design-consisting of testing chamber, oscillator circuit and measure instruments-has been employed. The sensor shows its activity to the acetic acid vapours for more than 60 days. The selectivity is adequate although some vapours interfere: hydrochloric acid, formic acid, formaldehyde, tributyl phosphate, chloroform, chlorobenzene, acetone and isobutylmethylketone. The sensor described can be applied to detect acetic acid vapours in the presence of other vapours: acetonitrile, acrolein, benzene, n-hexane, ethanol, propanol, n-butyl acetate, isopropyl ether, isoamyl alcohol, ethyl ether, methylene chloride, carbon tetrachloride and toluene. The major advantages of the proposed sensor over other existing techniques are its simplicity, reduced cost and capacity for use in situ.     

Nonenzymatic Electrochemical Sensor for Wearable Interstitial Fluid Glucose Monitoring

We report on a nonenzymatic electrochemical sensor for wearable glucose monitoring in interstitial fluid. The sensor exhibited acceptable selectivity and reliability for continuous glucose detection for up to 30 days. The sensor tip is coated with polyurethane, and the biocompatibility of the tip is investigated by tissue staining. A fully integrated wearable glucose monitoring system is developed with a wireless connection with a smartphone. The test results are in agreement with reference methods. So, we believe the sensor is promising for the development of a continuous glucose monitoring system and diabetes management.     

A wireless pH sensor using magnetoelasticity for measurement of body fluid acidity.

The determination of body fluid acidity using a wireless magnetoelastic pH-sensitive sensor is described. The sensor was fabricated by casting a layer of pH-sensitive polymer on a magnetoelastic ribbon. In response to an externally applied time-varying magnetic field, the magnetoelastic sensor mechanically vibrates at a characteristic frequency that is inversely dependent upon the mass of the pH polymer film, which varies as the film swells and shrinks in response to pH. As the magnetoelastic sensor is magnetostrictive, the mechanical vibrations of the sensor launch magnetic flux that can be detected remotely using a pickup coil. The sensor can be used for direct measurements of body fluid acidity without a pretreatment of the sample by using a filtration membrane. A reversible and linear response was obtained between pH 5.0 and 8.0 with a measurement resolution of pH 0.1 and a slope of 0.2 kHz pH(-1). Since there are no physical connections between the sensor and the instrument, the sensor can be applied to in vivo and in situ monitoring of the physiological pH and its fluctuations.     

Coulometric sensors,the application of a sensor-actuator system for long-term stability in chemical sensing

We present a new type of chemical transducer, the coulometric sensor. This sensor is in fact an integrated sensor-actuator system that is able to measure the concentration of acids and bases by means of coulometric titration. An ISFET is used as the sensor to monitor the pH changes induced by the actuator, which is a gold electrode that fits closely around the ISFET's gate area. Coulometry is an absolute method and therefore the output of the new sensor is only determined by its dimensions and is not subject to changes in offset and sensitivity of the indicator electrode. It is thus expected that the operation of the sensor will be stable for a long time, so that only a one-time calibration is needed. As a first example of this new class of chemical transducers, a carbon dioxide sensor is presented. It is shown that the stability is some orders of magnitude better than that for a ‘classical” potentiometric sensor.     

Electrophoretic separations with polyether ether ketone capillaries and capacitively coupled contactless conductivity detection

The Raipore R1030 membrane, an anion-exchange membrane containing ammonium groups as ionogenic groups, was evaluated as the interface of an optical sensor for Cr(VI), and the effect of chemical parameters affecting Cr(VI) transport were studied. Good transport features were obtained, demonstrating the suitability of the Raipore R1030 membrane for this application. Thus, an optical sensor for chromium(VI) monitoring in industrial process waters was developed. The sensor is based on the renewable reagent approach and uses the Raipore R1030 membrane as the interface between the sample and the sensor head, which contains 1,5-diphenylcarbazide as spectrophotometric reagent for chromium. Chromium(VI) crosses the membrane and reacts with the reagent inside the sensor head, resulting in changes in the absorption of light. These changes are monitored in situ through a system of optical fibers. The sensor performance was tested by analysing samples from a waste water treatment plant for effluents from electroplating industries.     

Cetyltrimethylammonium Bromide(CTAB)-Ionic Liquid Composite Modified Electrode for Sensitive Cyclic Voltammetric Determination of Bisphenol A

A sensitive electrochemical sensor for determining bisphenol A(BPA) was designed. The sensor was a glassy carbon electrode modified with the surfactant cetyltrimethylammonium bromide and the ionic liquid 1-decyl-3-methylimidazolium tetrafluoroborate. The ability of the new sensor to measure BPA was investigated in cyclic voltammetry experiments. Under optimized conditions, the sensor gave a linear response range for BPA of 2.19×10^-7-3.28×10^-5 mol/L and a detection limit of 7.31×10^-8 mol/L(S/N=3). BPA could be determined with a lower detection limit, a wider linear range, and more sensitivity using the sensor than using other electrochemical sensors or high performance liquid chromatography with UV detection. The new sensor was used to determine BPA in tap water with recoveries of 97.5%-98.7% and a relative standard deviation <2.9%. The results show that the sensor can be used to determine trace BPA concentrations in tap water.     

Determination of Bisphenol A Using an Electrochemical Sensor Based on a Molecularly Imprinted Polymer-Modified Multiwalled Carbon Nanotube Paste Electrode

A novel electrochemical sensor for bisphenol A was developed through the combination of a molecular imprinting technique with a multiwalled carbon nanotube paste electrode. A molecularly imprinted polymer and nonimprinted polymer were synthesized in the presence and absence of bisphenol A, and then used to prepare the electrode. The bisphenol A imprinted polymer was applied as a selective recognition element in the electrochemical sensor. Differential pulse voltammetry was used to characterize the electrochemical behavior of bisphenol A at the modified electrodes. The results showed that the imprinted sensor had highest response for bisphenol A. Parameters including the carbon paste composition, pH, and adsorption time for the imprinted sensor were optimized. Under the optimized conditions, the differential pulse voltammetry peak current was linear with the concentration of bisphenol A from 0.08 to 100.0 µM, with a detection limit of 0.022 µM. The imprinted sensor for bisphenol A exhibited good selectivity, stability, and reproducibility. This sensor was successfully used for the determination of bisphenol A in real water samples.     

DNA-directed protein immobilization on mixed self-assembled monolayers via a streptavidin bridge

The simultaneous detection of multiple analytes is an important consideration for the advancement of biosensor technology. Currently, few sensor systems possess the capability to accurately and precisely detect multiple antigens. This work presents a simple approach for the functionalization of sensor surfaces suitable for multichannel detection. This approach utilizes self-assembled monolayer (SAM) chemistry to create a nonfouling, functional sensor platform based on biotinylated single-stranded DNA immobilized via a streptavidin bridge to a mixed SAM of biotinylated alkanethiol and oligo(ethylene glycol). Nonspecific binding is minimized with the nonfouling background of the sensor surface. A usable protein chip is generated by applying protein-DNA conjugates which are directed to specific sites on the sensor chip surface by utilizing the specificity of DNA hybridization. The described platform is demonstrated in a custom-built surface plasmon resonance biosensor. The detection capabilities of a sensor using this protein array have been characterized using human chorionic gonadotropin (hCG). The platform shows a higher sensitivity in detection of hCG than that observed using biotinylated antibodies. Results also show excellent specificity in protein immobilization to the proper locations in the array. The vast number of possible DNA sequences combine with the selectivity of base-pairing makes this platform an excellent candidate for a sensor capable of multichannel protein detection.     

Integrated-optic ammonia sensor

Fibre coupled optical sensors for chemical and biologial species are important for process control, environmental control and pollution detection. An integrated optic ammonia sensor is described here; this is based on evanescent field absorption. The sensitive element of this sensor is a strip waveguide, fabricated by field assisted ion exchange, coated with a immobilized indicator dye. The sensor has a short response time and a long lifetime. An experimental arrangement is shown which has been built up for the characterization of different integrated optic sensor elements. Spectral response characteristics, response times and the generation of reference signals are reported in detail. The simple temperature dependence, the humidity independence and the very low cross sensitivity of this ammonia sensor is illustrated.