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This paper reports a first microbial biosensor for rapid and cost-effective determination of organophosphorus pesticides fenitrothion and EPN. The biosensor consisted of recombinant PNP-degrading/oxidizing bacteria Pseudomonas putida JS444 anchoring and displaying organophosphorus hydrolase (OPH) on its cell surface as biological sensing element and a dissolved oxygen electrode as the transducer. Surfaceexpressed OPH catalyzed the hydrolysis of fenitrothion and EPN to release 3-methyl-4-nitrophenol and p-nitrophenol, respectively, which were oxidized by the enzymatic machinery of Pseudomonas putida JS444 to carbon dioxide while consuming oxygen, which was measured and correlated to the concentration of organophosphates. Under the optimum operating conditions, the biosensor was able to measure as low as 277 ppb of fenitrothion and 1.6 ppm of EPN without interference from phenolic compounds and other commonly used pesticides such as carbamate pesticides, triazine herbicides and organophosphate pesticides without nitrophenyl substituent. The applicability of the biosensor to lake water was also demonstrated.
This paper presents a two-dimensional-in-space mathematical model of biosensors based on an array of enzyme microreactors immobilised on a single electrode. The modeling system acts under amperometric conditions. The microreactors were modeled by particles and by strips. The model is based on the diffusion equations containing a nonlinear term related to the Michaelis-Menten kinetics of the enzymatic reaction. The model involves three regions: an array of enzyme microreactors where enzyme reaction as well as mass transport by diffusion takes place, a diffusion limiting region where only the diffusion takes place, and a convective region, where the analyte concentration is maintained constant. Using computer simulation, the influence of the geometry of the microreactors and of the diffusion region on the biosensor response was investigated. The digital simulation was carried out using the finite difference technique.
The applicability of differential pulse voltammetry (DPV) and adsorptive stripping voltammetry (AdSV) at a non-toxic meniscus-modified silver solid amalgam electrode (m-AgSAE) for the determination of trace amounts of genotoxic substances was demonstrated on the determination of micromolar and submicromolar concentrations of 3-nitrofluoranthene using methanol - 0.01 mol L-1 NaOH (9:1) mixture as a base electrolyte and of Ostazine Orange using 0.01 mol L-1 NaOH as a base electrolyte.
Novel organic membrane-based thin-film microsensors for the determination of heavy metal cations
(2006)
A first step towards the fabrication and electrochemical evaluation of thin-film microsensors based on organic PVC membranes for the determination of Hg(II), Cd(II), Pb(II) and Cu(II) ions in solutions has been realised. The membrane-coating mixture used in the preparation of this new type of microsensors is incorporating PVC as supporting matrix, o-nitrophenyloctylether (o-NPOE) as solvent mediator and a recently synthesized Hg[dimethylglyoxime(phene)]2+ and Bis-(4-hydroxyacetophenone)-ethylenediamine as electroactive materials for Hg(II) and Cd(II), respectively. A set of three commercialised ionophores for Cd(II), Pb(II) and Cu(II) has been also used for comparison. Thin-film microsensors based on these membranes showed a Nernstian response of slope (26-30 mV/dec.) for the respective tested cations. The potentiometric response characteristics (linear range, pH range, detection limit and response time) are comparable with those obtained by conventional membranes as well as coated wire electrodes prepared from the same membrane. The realisation of the new organic membrane-based thin-film microsensors overcomes the problem of an insufficient selectivity of solid-state-based thinfilm sensors.
In this paper, methods of sample preparation for potentiometric measurement of phenylalanine are presented. Basing on the spectrophotometric measurements of phenylalanine, the concentrations of reagents of the enzymatic reaction (10 mM L-Phe, 0,4 mM NAD+, 2U L-PheDH) were determined. Then, the absorption spectrum of the reaction product, NADH, was monitored (maximum peak at 340 nm). The results obtained by the spectrophotometric method were compared with the results obtained by the colourimetry, using pH indicators. The above-mentioned two methods will be used as references for potentiometric measurements of phenylalanine concentration.
Hydrophobic magnetic nanoparticles (NPs) consisting of undecanoate-capped magnetite (Fe3O4, average diameter ca. 5 nm) are used to control quantized electron transfer to surface-confined redox units and metal NPs. A two-phase system consisting of an aqueous electrolyte solution and a toluene phase that includes the suspended undecanoatecapped magnetic NPs is used to control the interfacial properties of the electrode surface. The attracted magnetic NPs form a hydrophobic layer on the electrode surface resulting in the change of the mechanisms of the surface-confined electrochemical processes. A quinone-monolayer modified Au electrode demonstrates an aqueous-type of the electrochemical process (2e-+2H+ redox mechanism) for the quinone units in the absence of the hydrophobic magnetic NPs, while the attraction of the magnetic NPs to the surface results in the stepwise single-electron transfer mechanism characteristic of a dry nonaqueous medium. Also, the attraction of the hydrophobic magnetic NPs to the Au electrode surface modified with Au NPs (ca. 1.4 nm) yields a microenvironment with a low dielectric constant that results in the single-electron quantum charging of the Au NPs.
Micromachined thermal heater platforms offer low electrical power consumption and high modulation speed, i.e. properties which are advantageous for realizing nondispersive infrared (NDIR) gas- and liquid monitoring systems. In this paper, we report on investigations on silicon-on-insulator (SOI) based infrared (IR) emitter devices heated by employing different kinds of metallic and semiconductor heater materials. Our results clearly reveal the superior high-temperature performance of semiconductor over metallic heater materials. Long-term stable emitter operation in the vicinity of 1300 K could be attained using heavily antimony-doped tin dioxide (SnO2:Sb) heater elements.
Various planar technologies are employed for developing solid-state sensors having low cost, small size and high reproducibility; thin- and thick-film technologies are most suitable for such productions. Screen-printing is especially suitable due to its simplicity, low-cost, high reproducibility and efficiency in large-scale production. This technology enables the deposition of a thick layer and allows precise pattern control. Moreover, this is a highly economic technology, saving large amounts of the used inks. In the course of repetitions of the film-deposition procedure there is no waste of material due to additivity of this thick-film technology. Finally, the thick films can be easily and quickly deposited on inexpensive substrates. In this contribution, thick-film ion-selective electrodes based on ionophores as well as crystalline ion-selective materials dedicated for potentiometric measurements are demonstrated. Analytical parameters of these sensors are comparable with those reported for conventional potentiometric electrodes. All mentioned thick-film strip electrodes have been totally fabricated in only one, fully automated thickfilm technology, without any additional manual, chemical or electrochemical steps. In all cases simple, inexpensive, commercially available materials, i.e. flexible, plastic substrates and easily cured polymer-based pastes were used.
Multi-interface level sensors and new development in monitoring and control of oil separators
(2006)
In the oil industry, huge saving may be made if suitable multi-interface level measurement systems are employed for effectively monitoring crude oil separators and efficient control of their operation. A number of techniques, e.g. externally mounted displacers, differential pressure transmitters and capacitance rod devices, have been developed to measure the separation process with gas, oil, water and other components. Because of the unavailability of suitable multi-interface level measurement systems, oil separators are currently operated by the trial-and-error approach. In this paper some conventional techniques, which have been used for level measurement in industry, and new development are discussed.
In this paper, methods of surface modification of different supports, i.e. glass and polymeric beads for enzyme immobilisation are described. The developed method of enzyme immobilisation is based on Schiff’s base formation between the amino groups on the enzyme surface and the aldehyde groups on the chemically modified surface of the supports. The surface of silicon modified by APTS and GOPS with immobilised enzyme was characterised by atomic force microscopy (AFM), time-of-flight secondary ion mass spectroscopy (ToF-SIMS) and infrared spectroscopy (FTIR). The supports with immobilised enzyme (urease) were also tested in combination with microreactors fabricated in silicon and Perspex, operating in a flow-through system. For microreactors filled with urease immobilised on glass beads (Sigma) and on polymeric beads (PAN), a very high and stable signal (pH change) was obtained. The developed method of urease immobilisation can be stated to be very effective.