Biofouling and performance of boron-doped diamond electrodes for detection of dopamine and serotonin in neuron cultivation media.

Boron doped diamond has been considered as a fouling-resistive electrode material for in vitro and in vivo detection of neurotransmitters. In this study, its performance in electrochemical detection of dopamine and serotonin in neuron cultivation media Neurobasal™ before and after cultivation of rat neurons was investigated. For differential pulse voltammetry the limits of detection in neat Neurobasal™ medium of 2 µM and 0.2 µM for dopamine and serotonin, respectively, were achieved on the polished surface, which is comparable with physiological values. On oxidized surface twofold higher values, but increased repeatabilities of the signals were obtained. However, in Neurobasal™ media with peptides-containing supplements necessary for cell cultivation, the voltammograms were notably worse shaped due to biofouling, especially in the medium isolated after neuron growth. In these complex media, the amperometric detection mode at +0.75 V (vs. Ag/AgCl) allowed to detect portion-wise additions of dopamine and serotonin (as low as 1-2 µM), mimicking neurotransmitter release from vesicles despite the lower sensitivity in comparison with neat NeurobasalTM. The results indicate substantial differences in detection on boron doped diamond electrode in the presence and absence of proteins, and the necessity of studies in real media for successful implementation to neuron-electrode interfaces.

Simultaneous determination of tert-butylhydroquinone, propyl gallate, and butylated hydroxyanisole by flow-injection analysis with multiple-pulse amperometric detection.

We report the first amperometric method for the simultaneous determination of tert-butylhydroquinone (tBHQ), propyl gallate (PG), and butylated hydroxyanisole (BHA) using flow injection analysis coupled to multiple-pulse amperometry. A sequence of potential pulses was selected in order to detect tBHQ, PG, and BHA separately in a single injection step at a glassy carbon electrode without the need of a preliminary separation. A mixture of methanol and 0.040M Britton-Robinson buffer was used both as a carrier solution and for dilution of analyzed solutions before injection. The method is precise (RSD < 5%, n = 10), fast (a frequency of 140 injections h-1), provides sufficiently low quantification limits (2.51, 1.45, and 0.85µmolL-1 for tBHQ, PG, and BHA, respectively) and can be easily applied without high demands on instrumentation. As a practical application, the determination of these antioxidants contained in commercial chewing gum samples was carried out by applying a simple extraction procedure.

Voltammetric and amperometric determination of 2,4-dinitrophenol metabolites.

Methods for determination of 2-amino-4-nitrophenol and 4-amino-2-nitrophenol, metabolites of 2,4-dinitrophenol, were developed using differential pulse (DP) voltammetry and HPLC with amperometric and spectrophotometric detection. The applicability of these methods was tested by the determination of the analytes in model samples of urine after preliminary separation by solid-phase extraction. Voltammetry enabled parallel determination of both analytes, but its application in real matrix was severely limited due to the interference of other compounds present in urine. HPLC allowed the determination in real urine matrix down to micromolar concentrations; amperometric detection proved to be more sensitive and selective than the spectrophotometric one.

Voltammetric determination of aminobiphenyls at a boron-doped nanocrystalline diamond film electrode.

Voltammetric behavior of 2-aminobiphenyl, 3-aminobiphenyl, and 4-aminobiphenyl at a boron-doped nanocrystalline diamond film electrode was investigated using cyclic voltammetry and differential pulse voltammetry. Optimum conditions have been found for the determination of those genotoxic substances by differential pulse voltammetry at the above given electrode in the concentration range of 2 x 10(-7) to 1 x 10(-5) mol/L.

Interaction of tin(II) and arsenic(III) with DNA at the nanostructure film modified electrodes.

Biosensors based on DNA and DNA-carbon nanotubes film immobilized at the surface of a screen-printed carbon electrode were used for simple in vitro tests of chemical toxicity. The damage to DNA caused by tin(II) and arsenic(III) compounds as components of specific reaction media was evaluated by means of an electrochemical DNA marker, [Co(phen)3](3+), as the portion of original dsDNA which survives an incubation of the biosensor in the cleavage medium. The results were confirmed by the electrically heated electrode and by the measurement of the DNA guanine moiety signal.

Determining the vapour pressures of plant volatiles from gas chromatographic retention data.

The frequently used vapour pressure versus Kováts retention index relationship has been evaluated in terms of its universal applicability, highlighting the problems associated with predicting the vapour pressures of structurally divergent organic compounds from experimentally measured isothermal Kováts retention indices. Two models differing in approximations adopted to express the activity coefficient ratio have been evaluated using 32 plant volatiles of different structural types as a test set. The validity of these models was established by checking their ability to reproduce 22 vapour pressures known from independent measurements. Results of the comparison demonstrated that (i) the original model, based on the assumption of equal activity coefficients for the test and reference substances, led, as expected, to a poor correlation (r2 = 89.1% only), with significantly deviating polar compounds and (ii) the model showed significant improvement after incorporating a new empirical term related to vaporization entropy and boiling point. The addition of this term allowed more than 99% of the vapour pressure variance to be accounted for. The proposed model compares favourably with existing correlations, while having an added advantage of providing a convenient tool for vapour pressure determination of chemically divergent chemicals.

Microchip capillary electrophoresis with amperometric detection for rapid separation and detection of seleno amino acids.

This article describes an effective microchip capillary-electrophoresis protocol for rapid and effective measurements of food-related seleno amino acids, including Se-methionine (Se-Met), Se-ethionine (Se-Eth), Se-methyl cysteine (Se-Cys), utilizing o-phtaldialdeyde/2-mercaptoethanol (OPA/2-ME) derivatization. Relevant parameters of the chip separation and amperometric detection are examined and optimized using a response surface methodology (RSM). Under optimum conditions, the analytes could be separated and detected in a 30 mM borate buffer (pH 9.3, with 28 mM sodium dodecul sulfate) within 300 s using a separation voltage of 2000V and a detection voltage of +0.9 V. Linear calibration plots are observed for micromolar concentrations of the Se-amino acid compounds. The negligible sample volumes used in the microchip procedure obviates surface fouling common to amperometric measurements of selenoamino-acid compounds. The new microchip protocol offers great promise for a wide range of food applications requiring fast measurements and negligible sample consumption.

Polarographic and voltammetric determination of trace amounts of 2-nitronaphthalene.

The polarographic behaviour of 2-nitronaphthalene was investigated by DC tast polarography (DCTP) and differential pulse polarography (DPP), both at a dropping mercury electrode, and differential pulse voltammetry and adsorptive stripping voltammetry, both at a hanging mercury drop electrode. Optimum conditions have been found for the determination of 2-nitronaphthalene by the given methods in the concentration ranges of 2 x 10(-6) - 1 x 10(-4), 2 x 10(-7) - 1 x 10(-4), 1 x 10(-8) - 1 x 10(-4) and 2 x 10(-9) - 1 x 10(-8) M, respectively. Practical applicability of these techniques was demonstrated by the determination of 2-nitronaphthalene in drinking and river water after its preliminary separation and preconcentration using liquid-liquid and solid-phase extraction with limits of determination of 3 x 10(-10) M (drinking water) and 3 x 10(-9) M (river water).

Microchip capillary electrophoresis with electrochemical detection of thiol-containing degradation products of V-type nerve agents.

A microchip protocol for the capillary electrophoresis separation and electrochemical detection of thiol-containing degradation products of V-type nerve agents is described. The microchip assay relies on the derivatization reaction of 2-(dimethylamino)ethanethiol (DMAET), 2-(diethylamino)ethanethiol (DEAET), and 2-mercaptoethanol (ME) with o-phthaldialdehyde in the presence of the amino acid valine along with amperometric monitoring of the isoindole derivatives. Both off-chip and on-chip derivatization reactions have led to highly sensitive and rapid detection of the thiol degradation products. Various parameters influencing the derivatization, separation, and detection processes were examined and optimized. These include the amino acid co-reagent, reagent-mixing ratio, reaction time, injection time, separation voltage, and detection potential. The chip microsystem offers a rapid (<4 min) simultaneous detection of micromolar concentrations of DMAET, DEAET, and ME. Linear calibration plots were observed for the V-type nerve agent thiol degradation products, along with good stability and reproducibility (RSD < 8.0%). Detection limits of 5 and 8 microM were obtained for the off-chip reaction of DMAET and DEAET, respectively, following a 2-s injection. The suitability for assays of environmental matrixes was demonstrated for the determination of DMAET and DEAET in untreated tap and river water samples. The favorable analytical performance makes the new microfluidic device attractive for addressing the needs of various security scenarios.

Photodegradation of 1-nitropyrene in solution and in the adsorbed state.

The photodegradation of the 1-nitropyrene (NPy) has been studied using conventional (Xe and medium pressure Hg lamps) and laser sources (XeCl excimer and Nd-YAG UV). Low energy monochromatic light sources were used to study the early stages of degradation (up to 50% conversion). The medium pressure Hg lamp was used for longer periods of irradiation (up to 6h) and for greater degradation of NPy. The results of our work confirm that degradation occurs by radical mechanism. Aromatic hydroxymethyl, methoxy, hydroxy and nitroso derivatives of pyrene (Py) are created by low energy UV irradiation. After a massive UV irradiation, the Py aromatic system is destroyed and more polar low-molecular compounds are generated. The photochemical method described in this paper, based on irradiation by UV lamp, is therefore, suitable for degradation of fused benzene ring(s) and thus should also be effective for degradation of other nitrated polycyclic aromatic compounds.