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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Electroanalysis 9 (1997), S. 1397-1402 
    ISSN: 1040-0397
    Keywords: Pulsed amperometric detection ; Cysteine ; Platinum electrode ; Sulfhydryl compounds ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Anodic voltammetric detection of sulfhydryl compounds, represented here by cysteine, at Pt electrodes in acidic media occurs concomitantly with anodic generation of surface oxide. It is speculated that the adsorbed hydroxyl species (PtOH), proposed to be the intermediate product in formation of the inert oxide (PtO), is the source of O-atoms transferred to the sulfonic acid produced by oxidation of the sulfhydryl moiety. However, as a consequence of this electrocatalytic response mechanism, application of the traditional three-step waveform for pulsed amperometric detection (PAD) of sulfhydryl compounds is accompanied by a large background signal resulting from PtO formation. To diminish the background signal, the traditional three-step PAD waveform has been modified by insertion of a brief (100 ms) anodization step prior to the detection step to activate the Ptsurface by the generation of PtOH with minimal conversion to PtO. The subsequent negative step from the activation potential (Eact) to the detection detection potential (Edet 〈 Eact) permits the PtOH to be harvested within the detection mechanism without significant background signal.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Electroanalysis 6 (1994), S. 193-199 
    ISSN: 1040-0397
    Keywords: Platinum ; Platinum oxide ; Chronocoulometry ; Pulsed amperometric detection ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Results of a potential-step chronocoulometric study of oxide formation at a Pt-rotated minidisk electrode (0.00785 cm2) indicate that the anodic charge (qa) grows ca. as a linear function of the log time (t) for t = ca. 2-30 ms. Furthermore, the slope of the linear qa - log (t/ms) plot is proportional to the applied overpotential for oxide formation. The anodic peak current observed during linear potential-scan voltammetric experiments is nearly a linear function of scan rate (φ) for small φ (1000 〈 mV s-1) but shows substantial negative deviation from linearity for φ 〉 1000 mV s-1. The peak potential for oxide formation shifts in a positive direction for increasing values of φ, suggesting that this process is kinetically slow relative to large φ values. Reverse potential-step chronocoulometric measurements demonstrate that the background current in so-called “reverse-pulsed amperometric detection (RPAD)” can be decreased by inhibiting the conversion of the hydrous oxide (PtOH) to the inert oxide (PtO). Data also indicate that the rate of cathodic dissolution of surface oxide is dependent on applied potential for t 〈 2 to 30 ms. Oxide reduction continues even for t 〉 1000 ms.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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