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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.
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.
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.
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.
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.
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.
An H2O2 sensor for the application in industrial sterilisation processes has been developed. Therefore, automated sterilisation equipment at laboratory scale has been constructed using parts from industrial sterilisation facilities. In addition, a software tool has been developed for the control of the sterilisation equipment at laboratory scale. First measurements with the developed sensor set-up as part of the sterilisation equipment have been performed and the sensor has been physically characterised by optical microscopy and SEM.
We report on the synthesis and CO gas-sensing properties of mesoporous tin(IV) oxides (SnO2). For the synthesis cetyltrimethylammonium bromide (CTABr) was used as a structure-directing agent; the resulting SnO2 powders were applied as films to commercially available sensor substrates by drop coating. Nitrogen physisorption shows specific surface areas up to 160 m2·g-1 and mean pore diameters of about 4 nm, as verified by TEM. The film conductance was measured in dependence on the CO concentration in humid synthetic air at a constant temperature of 300 °C. The sensors show a high sensitivity at low CO concentrations and turn out to be largely insensitive towards changes in the relative humidity. We compare the materials with commercially available SnO2-based sensors.
Quartz crystal nanobalance (QCN) sensors are considered as powerful masssensitive sensors to determine materials in the sub-nanogram level. In this study, a single piezoelectric quartz crystal nanobalance modified with polystyrene was employed to detect benzene, toluene, ethylbenzene and xylene (BTEX compounds). The frequency shift of the QCN sensor was found to be linear against the BTEX compound concentrations in the range about 1-45 mg l-1. The correlation coefficients for benzene, toluene, ethylbenzene, and xylene were 0.991, 0.9977, 0.9946 and 0.9971, respectively. The principal component analysis was also utilized to process the frequency response data of the single piezoelectric crystal at different times, considering to the different adsorption-desorption dynamics of BTEX compounds. Using principal component analysis, it was found that over 90% of the data variance could still be explained by use of two principal components (PC1 and PC2). Subsequently, the successful identification of benzene and toluene was possible through the principal component analysis of the transient responses of the polystyrene modified QCN sensor. The results showed that the polystyrene-modified QCN had favorable identification and quantification performances for the BTEX compounds.
An array of 50 MHz quartz microbalances (QMBs) coated with a dendronized polymer was used to detect small amounts of volatile organic compounds (VOCs) in the gas phase. The results were compared to those obtained with the commonly used 10 MHz QMBs. The 50 MHz QMBs proved to be a powerful tool for the detection of VOCs in the gas phase; therefore, they represent a promising alternative to the much more delicate surface acoustic wave devices (SAWs).