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.

gamma-irradiation-induced grafting of poly (styrenesulfonate) to poly(tetrafluoroethylene) shielded microelectrodes.

A new method for the fabrication and polymer modification of microelectrodes is described. These electrodes are constructed by heat sealing the electroactive material in dual shrink/melt poly(tetrafluoroethylene) (PTFE) under vacuum. The PTFE shield may be activated to provide a support upon which polymers of interest may be grafted. gamma-Irradiation was used to graft polymerize styrene to the surface. The poly-(styrene) was subsequently sulfonated with chlorosulfonic acid to form poly(styrenesulfonate). Scanning electron microscopy and Raman microspectroscopy provide evidence that the poly-(styrenesulfonate) film has been formed and extends over the electrode material. Voltammetry indicates that hexaammine-ruthenium(III) cation is preconcentrated and stabilized via an association with the polymer film.

Determination of arsenic(III) and selenium(IV) using an on-line anodic stripping voltammetry flow cell with detection by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry.

An on-line anodic stripping voltammetry (ASV) flow system, interfaced with inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICPMS) detectors, has been used for determination of arsenic(III) and selenium(IV) and for elimination of polyatomic interferences which arise from chloride in sample matrices. Details of the working electrode preparation are discussed. Arsenic signals in ICP-AES were enhanced by as much as 10 times through preconcentration of sample volumes up to 5 mL. Using ICP-AES detection, recoveries for analyte spikes in 1:10 diluted urine were 102% for As(III) (matrix-matched standards) and 91% for Se(IV) (standards in electrolyte). Using ICPMS detection, determination of certified Se(IV) and Se(IV) spikes in diluted NIST SRM 2670 elevated urine gave recoveries of 92-103%, while recoveries of As(III) spikes in diluted NIST SRM 2670 urine ranged from 94 to 113%. High levels of chloride matrix exhibited little effect on the arsenic signal with ICP-AES or ICPMS detection. Elimination of the polyatomic interference ArCl+ in ICPMS was very efficient for diluted NIST SRM 2670 urine and for a synthetic matrix of 1000 micrograms/mL chloride.

Organic electrochemical techniques having potential clinical application.

The Organic Electrochemistry Group at the National Bureau of Standards is pursuing several avenues of research of potential application to problems of clinical chemists. With one development, electrochemical detectors for liquid chromatography, organomercury species can be determined in biological tissues and other matrices. Spectroelectrochemistry is being used to characterize the redox behavior of metal complexes of bleomycin, an antitumor drug. Chemically modified electrodes are being developed as selective electrocatalytic sensors for organohalogen compounds and may lead to new sensors for clinically important analytes. Surface-enhanced Raman spectroscopy is helping characterize the polymer films used to modify the electrode surfaces. Another sensor is being developed for the detection of carboxylic acids: after the photocatalytic oxidation of the acids at a semiconductor electrode, the carbon dioxide produced is subsequently determined with a flow-through gas-sensing electrode. Finally, mathematical modeling may provide a better understanding of the fundamental processes involved in several of the above techniques.