Simultaneous electrochemical measurement of metal and organic propellant constituents of gunshot residues.

The simultaneous electrochemical measurement of heavy-metal and organic propellants relevant to gunshot residues (GSRs) is demonstrated. Cyclic voltammetry (CV) and cyclic square-wave stripping voltammetry (C-SWV) are shown to detect, in a single run, common propellants, such as nitroglycerin (NG) and dinitrotoluene (DNT), along with the heavy metal constituents of GSR, antimony (Sb), lead (Pb), zinc (Zn) and barium (Ba). The voltammetric detection of the stabilizer diphenylamine (DPA) along with inorganic constituents has also been examined. The resulting electrochemical signatures combine -in a single voltammogram- the response for the various metals and organic species, based on the reduction and oxidation peaks of the constituents. Cyclic square-wave voltammetry at the glassy carbon electrode (GCE), involving an intermittent accumulation at the reversal potentials of -0.95 V (for Sb, Pb, DNT and NG) and -1.3 V (for Sb, Pb, Zn and DPA) is particularly useful to offer distinct electrochemical signatures for these constituents of GSR mixtures, compared to analogous cyclic voltammetric measurements. Simultaneous voltammetric measurements of barium (at thin-film Hg GCE) and DNT (at bare GCE) are also demonstrated in connection to intermittent accumulation at the reversal potential of -2.4 V. Such generation of unique, single-run, information-rich inorganic/organic electrochemical fingerprints holds considerable promise for 'on-the-spot' field identification of individuals firing a weapon, as desired for diverse forensic investigations.

Amplified potentiometric transduction of DNA hybridization using ion-loaded liposomes.

Amplified potentiometric transduction of DNA hybridization based on using liposome 'nanocarriers' loaded with the signaling ions is reported. The liposome-amplified potentiometric bioassay involved the duplex formation, followed by the capture of calcium-loaded liposomes, a surfactant-induced release and highly-sensitive measurements of the calcium signaling ions using a Ca(2+) ion-selective electrode (ISE). The high loading yield of nearly one million signaling ions per liposome leads to sub-fmol DNA detection limits. Factors affecting the ion encapsulation efficiency and signal amplification are evaluated and discussed. The influence of the surfactant lysing agent is also examined. Such use of 'green' calcium signaling ions addresses the inherent toxicity of Ag and CdS nanoparticle tags used in previous potentiometric bioassays. The new strategy was applied for the detection of low levels of E. coli bacteria. It could be readily extended to trace measurements of other important biomolecules in connection to different biorecognition events. The attractive analytical performance makes liposomes a useful addition to the armory of potentiometric bioassays.

Integrated explosive preconcentrator and electrochemical detection system for 2,4,6-trinitrotoluene (TNT) vapor.

This article reports on an integrated explosive-preconcentration/electrochemical detection system for 2,4,6-trinitrotoluene (TNT) vapor. The challenges involved in such system integration are discussed. A hydrogel-coated screen-printed electrode is used for the detection of the thermally desorbed TNT from a preconcentration device using rapid square wave voltammetry. Optimization of the preconcentration system for desorption of TNT and subsequent electrochemical detection was conducted yielding a desorption temperature of 120 degrees C under a flow rate of 500 mL min(-1). Such conditions resulted in a characteristic electrochemical signal for TNT representing the multi-step reduction process. Quantitative measurements produced a linear signal dependence on TNT quantity exposed to the preconcentrator from 0.25 to 10 microg. Finally, the integrated device was successfully demonstrated using a sample of solid TNT located upstream of the preconcentrator.

High-temperature potentiometry: modulated response of ion-selective electrodes during heat pulses.

The concept of locally heated polymeric membrane potentiometric sensors is introduced here for the first time. This is accomplished in an all solid state sensor configuration, utilizing poly(3-octylthiophene) as the intermediate layer between the ion-selective membrane and underlying substrate that integrates the heating circuitry. Temperature pulse potentiometry (TPP) gives convenient peak-shaped analytical signals and affords an additional dimension with these sensors. Numerous advances are envisioned that will benefit the field. The heating step is shown to give an increase in the slope of the copper-selective electrode from 31 to 43 mV per 10-fold activity change, with a reproducibility of the heated potential pulses of 1% at 10 microM copper levels and a potential drift of 0.2 mV/h. Importantly, the magnitude of the potential pulse upon heating the electrode changes as a function of the copper activity, suggesting an attractive way for differential measurement of these devices. The heat pulse is also shown to decrease the detection limit by half an order of magnitude.

Potentiometric detection of DNA hybridization using enzyme-induced metallization and a silver ion selective electrode.

Here, we report on a highly sensitive potentiometric detection of DNA hybridization. The new assay uses a low-volume solid-contact silver ion-selective electrode (Ag(+)-ISE) to monitor the depletion of silver ions induced by the biocatalytic reaction of the alkaline-phosphatase enzyme tag. The resultant potential change of the Ag(+)-ISE, thus, serves as the hybridization signal. Factors affecting the potentiometric hybridization response have been optimized to offer a detection limit of 50 fM (0.2 amol) DNA target. The new potentiometric assay was applied successfully to the monitoring of the 16S rRNA of E. coli pathogenic bacteria to achieve a low detection limit of 10 CFU in the 4 microL sample. Such potentiometric transduction of biocatalytically induced metallization processes holds great promise for monitoring various bioaffinity assays involving common enzyme tags.

Thermally Stable Improved First-Generation Glucose Biosensors based on Nafion/Glucose-Oxidase Modified Heated Electrodes.

We illustrate how the use of heated electrodes enhances the performance of glucose biosensors based on amperometric detection of the glucose-oxidase generated hydrogen peroxide. Nafion is shown to be an excellent matrix to protect glucose oxidase from thermal inactivation during the heating pulses. The influence of the electrode temperature upon the amperometric response is examined. Temperature pulse amperometry (TPA) has been used to obtain convenient peak-shaped analytical signals. Surprisingly, up to 67.5 °C, the activity of Nafion-entrapped glucose oxidase is greatly enhanced (24 -fold) by accelerated kinetics rather than decreased by thermal inactivation. Amperometric signals even at elevated temperatures are stable upon prolonged operation involving repetitive measurements. The linear calibration range is significantly extended.

Stripping voltammetric determination of platinum metals at a carbon paste electrode modified with cationic surfactants.

In this contribution, a novel method is described for the determination of platinum metals. The procedure developed employs a carbon paste electrode modified in situ with cationic surfactants of the quaternary ammonium salt type. The pre-concentration step is based on a specific accumulation mechanism involving ion-pair formation; the detection being performed by cathodic scanning in the differential pulse voltammetric mode. Regarding the individual forms of platinum metals, the method has been found convenient for the determination of three heavy platinum metals in the form of Pt(IV), Ir(III) and Os(IV), whereas for the remaining elements (Ru, Rh, and Pd) was almost inapplicable. Platinum metals of the former group can be pre-concentrated in chloride-containing supporting media via PtCl(6)(2-), IrCl(6)(3-) and OsCl(6)(2-) complex anions, the central atom of each species being fairly reducible during the voltammetric scan. Stripping signals for both platinum and iridium were proportional to the concentration in a range of 1-10x10(-6)M Pt(IV) and Ir(III); the response for osmium being linear within 0.1-6x10(-7)M Os(IV) with a detection limit of about 5x10(-9)moll(-1). During optimisation, special attention was paid to the accumulation mechanism, choice of key experimental conditions, and to interference effects from foreign ions with potentially ion-pairing capabilities (AuCl(4)(-), TlCl(4)(-), CrO(4)(2-), MnO(4)(-), SCN(-), and I(-)). The method elaborated has been tested on both model solutions and real samples of industrial waste water, showing in both cases satisfactory analytical performance.