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C J Seliskar

Publications and source records attributed to C J Seliskar.

6 recordsLinked to original sources
PubMed2000

Spectroelectrochemical sensing based on multimode selectivity simultaneously achievable in a single device. 9. Incorporation of planar waveguide technology.

Incorporation of planar waveguide technology into a spectroelectrochemical sensor is described. In this sensor design, a potassium ion-exchanged BK7 glass waveguide was over-coated with a thin film of indium tin oxide (ITO) that served as an optically transparent electrode. A chemically selective film was spin-coated on top of the ITO film. The sensor supported five optical modes at 442 nm and three at 633 nm. Investigations on the impact of the ITO film on the optical properties of the waveguide and on the spectroelectrochemical performance of the sensor are reported. Sensing was based on the change in attenuation of light propagated through the waveguide resulting from an optically absorbing analyte. By applying either a triangular or square wave excitation potential waveform, electromodulation of the optical signal has been demonstrated with Fe(CN)6(3-/4-) as a model electroactive couple that partitions into a PDMDAAC-SiO2 film [where PDMDAAC = poly(dimethyldiallylammonium chloride)] and absorbs at 442 nm.

Journal Article↗
PubMed2000

Spectroelectrochemical sensing based on multimode selectivity simultaneously achievable in a single device. 5. Simulation of sensor response for different excitation potential waveforms.

The simulation of the optical response in spectroelectrochemical sensing has been investigated. The sensor consists of a sensing film coated on an optically transparent electrode (OTE). The mode of detection is attenuated total reflection. Only species that partition into the sensing film, undergo electrochemistry at the potentials applied to the OTE, and have changes in their absorbance at the wavelength of light propagated within the glass substrate of the OTE can be sensed. A fundamental question arises regarding the excitation potential waveforms employed to initiate the electrochemical changes observed. Historically, selection has been based solely upon the effectiveness of the waveform to quickly electrolyze any analyte observable by the optical detection method employed. In this report, additional requirements by which the waveform should be selected for use in a remote sensing configuration are discussed. The effectiveness of explicit finite difference simulation as a tool for investigating the applicability of three different excitation potential waveforms (square, triangle, sinusoid) is demonstrated. The simulated response is compared to experimental results obtained from a prototype sensing platform consisting of an indium tin oxide OTE coated with a cation-selective, sol-gel-derived Nafion composite film designed for the detection of a model analyte, tris(2,2'-bipyridyl)ruthenium(II) chloride. Using a diffusion coefficient determined from experimental data (5.8 x 10(-11) cm2 s for 5 x 10(-6) M Ru(bipy)3(2+)), the simulator program was able to accurately predict the magnitude of the absorbance change for each potential waveform (0.497 for square, 0.403 for triangular, and 0.421 for sinusoid), but underestimated the number of cycles required to approach steady state. The simulator program predicted 2 (square), 3 (triangle), and 5 cycles (sinusoid), while 5 (square), 15 (triangle), and 10 (sinusoid) cycles were observed experimentally.

Journal Article↗
PubMed1998

Spectroscopic and electrochemical evaluation of a perfluorosulfonated ionomer and its gel as preconcentrating media for [ReI(DMPE)3]+, where DMPE = 1,2-bis(dimethylphosphino)ethane.

The interaction of [ReI(DMPE)3]+, where DMPE = 1,2-bis(dimethylphosphino)ethane, a nonradioactive analogue of a heart imaging agent, with Nafion gel, which is Nafion plasticized with tri-n-butyl phosphate, has been evaluated spectroscopically and electrochemically. Thin-layer spectroelectrochemistry on the rhenium compound yields a linear Nernst plot with an n value of 0.99 and E degree' of 0.049 V vs Ag/AgCl. The electrochemistry is consistent with a reversible one-electron transfer between the mono- and dicationic forms of the complex. The UV-visible spectrum of electrogenerated [ReII(DMPE)3]2+ is identical to that obtained by air oxidation of [ReI(DMPE)3]+. Thin, free-standing films of Nafion gel and Nafion that were sufficiently clear to record visible spectra were cast. Spectroscopic measurement of the partitioning of [ReI-(DMPE)3]+ from aqueous solution into these films shows a more rapid uptake of the complex by the Nafion gel. Preconcentration factors into Nafion gel and Nafion were 350 and 50, respectively, after 4 h of soaking. Cyclic voltammetry of 1.0 x 10(-4)-1.0 x 10(-7) M (ReI(DMPE)3]+ in 0.15 M supporting electrolyte aqueous solution at bare gold and spectroscopic graphite electrodes suggests that the complex adsorbs to these electrodes. By comparison, the well-defined cyclic voltammograms at Nafion gel-modified electrodes exhibit diffusion-controlled behavior. The formal reduction potential at Nafion gel-modified electrodes is shifted positively compared to bare electrodes. A current enhancement of approximately 4 was observed at Nafion gel-modified spectroscopic graphite over a bare electrode. A calibration plot of peak current for differential pulse voltammetry vs concentration at Nafion gel-modified spectroscopic graphite was linear in the 10(-7)-10(-5) M concentration range, with a detectable signal down into the 10(-9) M range.

Electrochemistry↗
PubMed1997

Electrochemical behavior of [ReI(DMPE)3]+, where DMPE = 1,2-bis(dimethylphosphino)ethane, at perfluorosulfonated ionomer-modified electrodes.

The perfluorosulfonated ionomer Nafion shows potential utility as a polymer film to enhance the electrochemical detection of [ReI(DMPE)3]+, where DMPE = 1,2-bis-(dimethylphosphino)ethane. [ReI(DMPE)3]+, a nonradioactive radiopharmaceutical analog for heart imaging, partitions strongly into Nafion films on glassy carbon. Well-defined, chemically reversible cyclic voltammograms are obtained for the [ReI(DMPE)3]+/[ReII(DMPE)3]2+ couple with Eo' shifted positively by 60 mV relative to its value on bare glassy carbon. [ReI(DMPE)3]+ partitions into Nafion more strongly than the oxidized form, [ReII-(DMPE)3]2+. The detection limit for [ReI(DMPE)3]+ by cyclic voltammetry was improved by 2-3 orders of magnitude by the Nafion film. Differential pulse voltammetry for oxidation of [ReI(DMPE)3]+ at the Nafion-modified electrode has a detection limit of 2.5 x 10(-9) M compared to 1.0 x 10(-7) M at the bare electrode. A preconcentration factor of 1 x 10(6) for partitioning of [ReI(DMPE)3]+ from 0.05 M NaCl into Nafion on a glassy carbon electrode was measured.

Electrochemistry↗