Voltammetric detection of organohalides by redox catalysis: improved sensitivity by immobilisation within a cubic phase liquid crystal

Two combined strategies are reported for improving the sensitivity of organohalide detection by redox catalysis. These are, improvement of the second order rate constant (k) for catalytic reduction of the organohalide, and improvement of the rate of substrate diffusion. Values of k are calculated for both alkyl and aryl halides, from slow scan rate cyclic voltammograms in homogeneous solution. It is shown that a Zn(ii) porphyrin exhibits higher catalytic rates than the previously used Co(ii) porphyrin or Co(i) salen. Amperometric and rotating disk electrode studies of electropolymerised films of the Zn(ii) porphyrin, reveal that at optimum thickness, mediator-substrate reaction and substrate diffusion are the rate limiting steps. Hence, immobilisation of the Zn(ii) porphyrin within the more open structure of a cubic phase liquid crystal produces an increase in sensitivity of approx. 10 times, and lowers the limit of detection by one order of magnitude. The optimised sensor responds linearly to seven organohalides in the range 0.1 microM to 1.0 microM with a sensitivity of 6.95 A M(-1) cm(-2). Chronoamperometric experiments with a microdisk electrode show that the rate of charge transport in the cubic phase films (apparent diffusion coefficient, D(E)= 5.65 x 10(-10)+/- 0.11 x 10(-10) cm(2) s(-1)) is faster than in the electropolymerised films (D(E)= 3.64 x 10(-11)+/- 0.02 x 10(-11) cm(2) s(-1)). The variation of D(E) with the concentration of Zn(ii) in the cubic phase suggests that diffusion of charge is predominantly by electron self-exchange, rather than by physical movement.     

Electrochemical immunoassay platform for high sensitivity protein detection based on redox-modified carbon nanotube labels

We report a highly sensitive immunoassay protocol based on the use of redox-modified multi-walled carbon nanotubes (MWNTs) as electrochemical labels. The MWNTs were coated with methylene blue (MB) at an optically-determined loading of 3.41 × 10(-3) mol g(-1), and were then attached to secondary antibodies (Ab(2)) by adsorption. As a model analyte mouse IgG was collected by primary antibody (Ab(1))-coated magnetic beads. Following binding of the MB-MWNT-Ab(2) conjugates, IgG could be measured by MB reduction. Using differential pulse voltammetry for quantification, IgG was calibrated with a dynamic range of 0.1 pg mL(-1) to 100 pg mL(-1). Given the different possible Ab(1)-MB-MWNT-Ab(2) orientations on the magnetic beads, it was likely that not all the MB communicated with the electrode. A greater quantity of MB could be accessed by using the Fe(CN)(6)(3-/4-) redox couple as a solution phase mediator. This enabled us to lower the dynamic range down to 5 fg mL(-1) to 100 fg mL(-1).     

Use of 3-D plots to avoid mutual interference in bianalyte ASV determinations: application to cadmium and lead detection

We have examined the anodic stripping voltammetry (ASV) of Cd and Pb at carbon screen printed electrodes modified by an in situ deposited Bi film, and have demonstrated significant cross talk between the stripping peaks of the two metals. A simple and generally applicable method for dealing with this problem is described, based on curve-fitting three-dimensional calibration plots using MATLAB. Non-linear fitting to the calibrations produced coefficients of determination R² > 0.99 for both metals. We have illustrated use of the plots in conjunction with Bi-plated electrodes by measuring 15 randomly selected mixtures of Cd and Pb of known concentration.     

Enhanced Sensitivity of 4‐Chlorophenol Detection by Use of Nitrobenzene as a Liquid Membrane over a Carbon Nanotube‐Modified Glassy Carbon Electrode

The analytical utility of nitrobenzene as a liquid membrane for the detection of hydrophobic compounds was examined with a glassy carbon electrode, using 4‐chlorophenol as the model analyte. Electrochemical experiments indicated a large partition coefficient for the entry of 4‐chlorophenol into the nitrobenzene (7.6×10²±1.5×10²). This was combined with an increase in effective electrode area by coating with single‐walled nanotubes. Differential pulse voltammetry produced a linear response across the range 0.3 nM to 1.5 nM with a sensitivity of 1.1×10^?5 A nM^?1 cm^?2. To the best of our knowledge, this limit of detection for phenol is lower than other nonenzymatic modifications of carbon.     

The steady-state current at microcylinder electrodes modified by enzymes immobilized in conducting or non-conducting material

A diffusion-kinetic model is presented for an enzyme-modified microcylinder electrode, where the enzyme reaction generates an electro-active product. Simple, approximate expressions are derived for the steady-state current in cases where the enzyme is immobilized in a metallically conducting, or a non-conducting matrix. The model is also extended to the chemical sensor case, of a conducting polymer without enzyme. The model is used to analyze steady-state signals for glucose produced by Pt-coated carbon fibres, on which glucose oxidase has been entrapped in poly(1,2-diaminobenzene).     

Measurement of sulfite at oxide-coated copper electrodes

The amperometric determination of sulfite was performed using copper electrodes in alkaline media. A mechanism for the oxidation of sulfite at these electrodes is suggested, based on the formation of superficial CuO(.OH), which acted as an electron transfer mediator to the analyte. At 0.5 V versus SCE in 1 M NaOH, sulfite could be calibrated at a sensitivity of 0.2 A l mol-1 cm-2, with a response time for the steady state of 30 s. The limit of detection (three times the signal-to-noise ratio) was 2.5 x 10(-6) M and the response was linear up to 5 x 10(-4) M (r2 = 0.9996, n = 15). The standard deviation (n = 10) at 1 x 10(-5) and 1 x 10(-4) M was 3.27 x 10(-7) A cm-2 (mean = 3.62 x 10(-6) A cm-2) and 1.07 x 10(-13) A cm-2 (mean = 2.25 x 10(-5) A cm-2), respectively.     

Study of the underlying electrochemistry of polycrystalline gold electrodes in aqueous solution and electrocatalysis by large amplitude fourier transformed alternating current voltammetry

Polycrystalline gold electrodes of the kind that are routinely used in analysis and catalysis in aqueous media are often regarded as exhibiting relatively simple double-layer charging/discharging and monolayer oxide formation/removal in the positive potential region. Application of the large amplitude Fourier transformed alternating current (FT-ac) voltammetric technique that allows the faradaic current contribution of fast electron-transfer processes to be emphasized in the higher harmonic components has revealed the presence of well-defined faradaic (premonolayer oxidation) processes at positive potentials in the double-layer region in acidic and basic media which are enhanced by electrochemical activation. These underlying quasi-reversible interfacial electron-transfer processes may mediate the course of electrocatalytic oxidation reactions of hydrazine, ethylene glycol, and glucose on gold electrodes in aqueous media. The observed responses support key assumptions associated with the incipient hydrous oxide adatom mediator (IHOAM) model of electrocatalysis.     

Passivating reactions at a microdisk electrode as a model of passivation at a microparticle: theory and experiment

Journal of Solid State Electrochemistry - We have described the use of a microelectrode to simulate a passivating reaction taking place at a micro or nanoparticle. Reaction at the microelectrode is...