Glassy carbon indicator electrode

Other -NO2 containing metabolites such as the oxamic acid, chloramphenicol base and glucuronide could not be resolved by polarographic methods alone although it is probable that metabolite (X) could be determined by amperometric detection at a glassy carbon indicator electrode after HPLC separation. 

Various molecules are capable to bind to the DNA duplex or to single-stranded DNA. The application of DNA binding molecules for the detection of base-pair mismatches is discussed below. For instance, Millan et al. demonstrated sequence-selective electrochemical DNA sensing using hybridization indicators [9]. In this detection scheme, DNA capture strands were covalently immobilized on a glassy carbon 14 electrode and [Co(bpy)3] + and [Co(phen)3] + served as hybridization indicators that display reversible redox behavior. Presumably, electrostatic interactions with the negatively charged... 

There are several types of indicator electrodes. The simplest is the electrode of some inert material such as platinum, gold, or glassy carbon. These electrodes are used to measure the oxidation-reduction (redox) potential of the solution. The electrode itself does not participate in the electrode reaction but functions only as an inert electron transferring material. 

Fig. 17. Cyclic voltammogram of the water-soluble Rieske fragment from the bci complex of Paracoccus denitrificans (ISFpd) at the nitric acid modified glassy carbon electrode. Protein concentration, 1 mg/ml in 50 mM NaCl, 10 mM MOPS, 5 mM EPPS, pH 7.3 T, 25°C scan rate, 10 mV/s. The cathodic (reducing branch, 7 < 0) and anodic (oxidizing branch, 7 > 0) peak potentisds Emd the resulting midpoint potential are indicated. SHE, standEU d hydrogen electrode.

Such reduction In overpotentlal Is the largest observed for a bare glassy carbon electrode. The presence of surface qulnones may be Indicative of activation but does not appear to mediate the heterogeneous electron transfer. XFS results support the presence of qulnones as a minor constituent on the surface. 

Although the Initial use of glassy carbon as an electrode material Indicated that It might be a viable substitute for platinum (1), subsequent Investigations have shown that glassy carbon Is quite complex as an electrode material. The conditions used to manufacture a particular sample of glassy carbon and the subsequent steps used to treat the surface for electrochemistry strongly Influence Its behavior, possibly even more so than with platinum. 

For example, the final heat treatment temperatures In the manufacture will produce different electrochemical properties, even with the same surface treatments (2-4) since the structure and electrical property of glassy carbon depends on the temperature, as Indicated by the single crystal TEM patterns and by measurement of temperature dependent conductivity (5-6). On the other hand. It Is also well established that the electrochemical properties of carbon-based electrodes are markedly affected by surface treatments. 

After the electrolysis for 5 h at —0.15 V with the bubbling of O2 into W, the amount of CO2 produced was found to be 1.6 x 10 moles. A photoabsorption spectrum of the NB after electrolysis gave a peak at 780 nm. The peak was identical with that of the one electron oxidation product of DMFC, DMFC, which had been prepared coulometrically by using a column electrode with glassy carbon fiber working electrode [40]. This fact indicates that the electrolysis product was DMFC. The DMFC produced by the electrolysis was estimated to be 3.08 x 10 moles. 

Concerted Reduction of O and Cu+ or Acr+. Figure 5 illustrates the cyclic voltammograms for O2 in MeCN(0.1M TEAP) at glassy carbon, Cu, Ag, and Au electrodes (each polished immediately prior to exposure to O2). The drawn out reduction waves and the absence of significant anodic peaks upon scan reversal for the three metal electrodes indicate that 02 reacts with the surface prior to electron transfer. 

Electrochemical oxidation-reduction of eluting mixture components is the basis for amperometric electrochemical detectors. The three electrodes needed for the detection, the working (indicator) electrode, reference electrode, and auxiliary electrode, are either inserted into the flow stream or imbedded in the wall of the flow stream. See Figure 13.13. The indicator electrode is typically glassy carbon, platinum, or gold, the reference electrode a silver-silver chloride electrode, and the auxiliary a stainless steel electrode. Most often, the indicator electrode is polarized to cause oxidation of the mixture components... 

One final issue remains to be resolved Of the portion of the AEpi that is due to resistance, what part is caused by solution resistance and what part is caused by film resistance To explore this issue we examined the electrochemistry of a reversible redox couple (ferrocene/ferricinium) at a polished glassy carbon electrode in the electrolyte used for the TiS 2 electrochemistry. At a peak current density essentially identical to the peak current density for the thin film electrode in Fig. 27 (0.5 mV see ), this reversible redox couple showed a AEpi of 0.32 V (without application of positive feedback). Since this is a reversible couple (no contribution to the peak separation due to slow kinetics) and since there is no film on the electrode (no contribution to the peak separation due to film resistance), the largest portion of this 0.32 V is due to solution resistance. However, the reversible peak separation for a diffusional one-electron redox process is —0.06 V. This analysis indicates that we can anticipate a contribution of 0.32 V -0.06 V = 0.26 V from solution resistance in the 0.5 mV sec control TiS2 voltammogram in Fig. 27. 

The PFg" salts of [Ru(bpy)2(110)] and [Ru(110)3] and analogous complexes containing 4,4 -bis(substituted) ferrocenyl ligands (110 ), have been synthesized and characterized the tris(chelate) complexes are either poorly soluble or insoluble. Electropolymerization of [Ru(110 )3][PF6]2 produces an electrochromic film. The complex [Ru(bpy)2(lll)] undergoes electropolymerization on Pt and glassy carbon electrodes, although the related complex [Ru(bpy)2(112)] does not. Electrochemical and spectroscopic properties of the films indicate that they form by both head-to-tail and tail-to-tail monomer coupling. ... 

I. 4-methoxyacetophenone (30 //moles) was added as an internal standard. The reaction was stopped after 2 hours by partitioning the mixture between methylene chloride and saturated sodium bicarbonate solution. The aqueous layer was twice extracted with methylene chloride and the extracts combined. The products were analyzed by GC after acetylation with excess 1 1 acetic anhydride/pyridine for 24 hours at room temperature. The oxidations of anisyl alcohol, in the presence of veratryl alcohol or 1,4-dimethoxybenzene, were performed as indicated in Table III and IV in 6 ml of phosphate buffer (pH 3.0). Other conditions were the same as for the oxidation of veratryl alcohol described above. TDCSPPFeCl remaining after the reaction was estimated from its Soret band absorption before and after the reaction. For the decolorization of Poly B-411 (IV) by TDCSPPFeCl and mCPBA, 25 //moles of mCPBA were added to 25 ml 0.05% Poly B-411 containing 0.01 //moles TDCSPPFeCl, 25 //moles of manganese sulfate and 1.5 mmoles of lactic acid buffered at pH 4.5. The decolorization of Poly B-411 was followed by the decrease in absorption at 596 nm. For the electrochemical decolorization of Poly B-411 in the presence of veratryl alcohol, a two-compartment cell was used. A glassy carbon plate was used as the anode, a platinum plate as the auxiliary electrode, and a silver wire as the reference electrode. The potential was controlled at 0.900 V. Poly B-411 (50 ml, 0.005%) in pH 3 buffer was added to the anode compartment and pH 3 buffer was added to the cathode compartment to the same level. The decolorization of Poly B-411 was followed by the change in absorbance at 596 nm and the simultaneous oxidation of veratryl alcohol was followed at 310 nm. The same electrochemical apparatus was used for the decolorization of Poly B-411 adsorbed onto filter paper. Tetrabutylammonium perchlorate (TBAP) was used as supporting electrolyte when methylene chloride was the solvent. 

The voltammetric reduction of a series of dialkyl and arylalkyl disulfides has recently been studied in detail, in DMF/0.1 M TBAP at the glassy carbon electrode The ET kinetics was analyzed after addition of 1 equivalent of acetic acid to avoid father-son reactions, such as self-protonation or nucleophilic attack on the starting disulfide by the most reactive RS anion. Father-son reactions have the consequence of lowering the electron consumption from the expected two-electron stoichiometry. Addition of a suitable acid results in the protonation of active nucleophiles or bases. The peak potentials for the irreversible voltammetric reduction of disulfides are strongly dependent on the nature of the groups bonded to the sulfur atoms. Table 11 summarizes some relevant electrochemical data. These results indicate that the initial ET controls the electrode kinetics. In addition, the decrease of the normalized peak current and the corresponding increase of the peak width when v increases, point to a potential dependence of a, as discussed thoroughly in Section 2. 

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