Controlled-potential electrolysis of bulk solutions at a modified electrode:  application to oxidations of cysteine, cystine, methionine, and thiocyanate

Cox, James A.; Gray, T. A.

doi:10.1021/ac00223a018

Cited by 48 publications

(27 citation statements)

References 20 publications

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“…At this pH, the modified electrode did not foul and the oxidation currents were found reproducible regardless of scan rate and cysteine concentration. A similar behavior was reported by Cox and Gray at a mixed valent ruthenium-oxide ruthenium-cyanide film electrode [20,21]. Preliminary experiments were also conducted for 2-furaldehyde.…”

Section: Electrocatalysis In a Conventional Cellsupporting

confidence: 78%

“…The use of electrochemical methods for detection of As(III) has been limited by the extreme potentials required for its oxidation at most conventional electrode materials [19,20]. Figure 4, curve a, shows the voltammogram of the Ru-based modified electrode in the electrolyte containing no purposely added electroactive species.…”

Section: Electrocatalysis In a Conventional Cellmentioning

confidence: 99%

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Electrocatalysis and Amperometric Detection at a Ruthenium-Modified Indium-Hexacyanoferrate Film Electrode

1998

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The electrocatalytic activity of a glassy carbon electrode modified with electrochemically deposited indium(III)-hexacyanoferrate (InHCF) film, which has been subsequently cycled in a solution of ruthenium(III), is described. Although the resulting ruthenium-modified InHCF thin film electrode behaves in a manner analogous to the parent InHCF film, its stability was found to be greatly improved. Such a modified electrode was characterized, in acidic (pH 2) 0.5 M KCl solutions, by cyclic voltammetry and flow injection analysis. It exhibits a high catalytic activity for the electrooxidation of some inorganic and organic compounds of analytical interest, such as As(III), S 2 O 2-3 , cysteine, and 2-furaldehyde. The analytical applicability of this novel ruthenium-modified InHCF film electrode for the amperometric detection in flowing streams is discussed. Repetitive sample injections with amperometric detection of thiosulfate at +0.8 V (vs. Ag/AgCl) as applied potential produced a stable response over 8 h of operation, making it very attractive for practical applications.

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Section: Electrocatalysis In a Conventional Cellsupporting

confidence: 78%

Section: Electrocatalysis In a Conventional Cellmentioning

confidence: 99%

Electrocatalysis and Amperometric Detection at a Ruthenium-Modified Indium-Hexacyanoferrate Film Electrode

1998

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“…To emphasize the combined structure and properties of RuOx and PB, henceforth the RuMCN will be designated as mvRuOx-MCN [34]. Earlier, Cox and co-workers reported a mixed valent ruthenium oxide-cyanometallate complex for analytical sensing of alcohols, aldehydes, and nitroamines except carbohydrates, e.g., glucose [23,25,27,31]. The catalytic mechanism is also unknown.…”

Section: Introductionmentioning

confidence: 99%

Development of an Enzymeless/Mediatorless Glucose Sensor Using Ruthenium Oxide‐Prussian Blue Combinative Analogue

et al. 2005

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Presented in this work is the first step towards an enzymeless/mediatorless glucose sensor. We first observed remarkable electrocatalytic oxidation of glucose using combinative ruthenium oxide (RuOx)-Prussian blue (PB) analogues (designated as mvRuOx-RuCN, mv: mixed valent) at ca. 1.1 V (vs. Ag/AgCl) in acidic media (pH 2 Na 2 SO 4 / H 2 SO 4 ). Individual RuOx and PB analogs failed to give any such catalytic response. A high ruthenium oxidation state (i.e., oxy/hydroxy-Ru VII , E8 % 1.4 V vs. RHE), normally occurring in strong alkaline conditions at RuOx-based electrodes, was electrogenerated and stabilized (without any conventional disproportionation reaction) in the mvRuOx-RuCN matrix for glucose catalysis. Detail X-ray photoelectron spectroscopic studies can fully support the observation. The catalyst was chemically modified onto a disposable screen-printed carbon electrode and employed for the amperometric detection of glucose via flow injection analysis (FIA). This system has a linear detection range of 0.3 -20 mM with a detection limit and sensitivity of 40 mM (S/N ¼ 3) and 6.2 mA/(mM cm 2 ), respectively, for glucose. Further steps towards the elimination of interference and the extendibility to neutral pHs were addressed.

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“…When the concentration was varied with individual injections of 50 to 300 ppm MMH, a steady-state current, i ss , was reached after each injection (Figure 3). The time for the current to reach 90 % of i ss , T 90 , was 75 s. Although the oxidation product was not identi®ed, other studies have shown that oxygen transfer accompanied electron transfer at mvRuOx, thereby forming polar products [24]. Facile desorption of these products was considered a factor in the long term stability of mvRuOx-modi®ed electrodes.…”

Section: Slope [Naappm]mentioning

confidence: 99%

Mediated Oxidation and Determination of Gaseous Monomethyl Hydrazine in a Solid-State Voltammetric Cell Employing a Sol-Gel Electrolyte

et al. 2000

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Mesoporous silica that was prepared by a sol-gel process was used as the electrolyte for the amperometric determination of vapor-phase monomethyl hydrazine (MMH). Three detection strategies were tested, namely cyclic voltammetry at a Pt working electrode with the oxidation mediated by Fe II,III that was hosted by the silica, pulsed electrochemical detection with a gold working electrode, and potentiostatic oxidation at a mixed-valence ruthenium oxide (mvRuOx) ®lm that was deposited on a Pt working electrode prior to casting the solid electrolyte overlayer. The sensitivities (and linear dynamic ranges) for the respective methods were 1.4 nA/ppm (500±1400 ppm), 0.49 nA/ppm (70±1050 ppm), and 0.30 nA/ppm (1±1050 ppm). With pulsed electrochemical detection and mvRuOx, respective detection limits of 20 ppm and 0.3 ppm were calculated on the basis of a concentration that yielded a response three times the standard deviation of the blank. Because of high uncertainty of the intercept of the Fe II,III -mediated method, a detection limit was not calculated for this technique. A cell design that provided a three-phase boundary at a mvRuOx-modi®ed electrode yielded a response of 90 % of the steady-state current at 11 s.

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Controlled-potential electrolysis of bulk solutions at a modified electrode: application to oxidations of cysteine, cystine, methionine, and thiocyanate

Cited by 48 publications

References 20 publications

Electrocatalysis and Amperometric Detection at a Ruthenium-Modified Indium-Hexacyanoferrate Film Electrode

Electrocatalysis and Amperometric Detection at a Ruthenium-Modified Indium-Hexacyanoferrate Film Electrode

Development of an Enzymeless/Mediatorless Glucose Sensor Using Ruthenium Oxide‐Prussian Blue Combinative Analogue

Mediated Oxidation and Determination of Gaseous Monomethyl Hydrazine in a Solid-State Voltammetric Cell Employing a Sol-Gel Electrolyte

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