Diffusional transport to and through thin-layer nanoparticle film modified electrodes: capped CdSe nanoparticle modified electrodes.

We present a simple and general theoretical model which accounts fully for the influence of an electrode modifying non-electroactive layer on the voltammetric response of a diffusional redox probe. The layer is solely considered to alter the solubilities and diffusion coefficients of the electroactive species within the thin layer on the electrode surface. On this basis it is demonstrated how, first, the apparent electrochemical rate constant can deviate significantly from that measured at an unmodified electrode. Second, depending on the conditions within the layer the modification of the electrode may lead to either apparent 'negative' or 'positive' electrocatalytic effects without the true standard electrochemical rate constant for the electron transfer at the electrode surface being altered. Having presented the theoretical model three experimental cases are investigated, specifically, the reductions of ruthenium(III) hexaamine, oxygen and boric acid on a gold macro electrode with and without a multi-layer organic capped nanoparticle film. In the latter case of the reduction of boric acid the voltammetric reduction is found to be enhanced by the presence of the organic layer. This result is interpreted as being due to an increase in the solubility of the analyte within the non-electroactive layer and not due to an alteration of the standard electrochemical rate constant.

Carbon nanotube-ionic liquid composite sensors and biosensors.

A new composite electrode has been fabricated using multiwall carbon nanotubes (MWCNT) and the ionic liquid n-octylpyridinum hexafluorophosphate (OPFP). This electrode shows very attractive electrochemical performances compared to other conventional electrodes using graphite and mineral oil, notably improved sensitivity and stability. One major advantage of this electrode compared to other electrodes using carbon nanotubes and other ionic liquids is its extremely low capacitance and background currents. A 10% (w/w) loading of MWCNT was selected as the optimal composition based on voltammetric results, as well as the stability of the background response in solution. The new composite electrode showed good activity toward hydrogen peroxide and NADH, with the possibility of fabricating a sensitive biosensor for glucose and alcohol using glucose oxidase and alcohol dehydrogenase, respectively, by simply incorporating the specific enzyme within the composite matrix. The marked electrode stability and antifouling features toward NADH oxidation was much higher for this composite compared to a bare glassy carbon electrode. While a loading of 2% MWCNT showed very poor electrochemical behavior, a large enhancement was observed upon gentle heating to 70 degrees C, which gave a response similar to the optimum composition of 10%. The ease of preparation, low background current, high sensitivity, stability, and small loading of nanotubes using this composite can create new novel avenues and applications for fabricating robust sensors and biosensors for many important species.

Carbon nanotube-based electrochemical sensors for quantifying the 'heat' of chilli peppers: the adsorptive stripping voltammetric determination of capsaicin.

A sensitive electroanalytical methodology for the determination of capsaicin using adsorptive stripping voltammetry (AdsSV) at a multiwalled carbon nanotube modified basal plane pyrolytic graphite electrode (MWCNT-BPPGE) is presented. This analytical method is then further developed using a multiwalled carbon nanotube screen-printed electrode (MWCNT-SPE) demonstrating the proof-of-concept that this approach can easily be incorporated into a sensing device which is both facile to use and inexpensive to produce. Capsaicin is the chemical responsible for the hot taste of chilli peppers, and measuring the concentration of capsaicin is an indicator of how hot any given chilli pepper, hot sauce and other related foodstuffs are. Standard additions plots for AdsSV of capsaicin at open circuit potential at a MWCNT-BPPGE exhibits two linear ranges, from 0.5 to 15 microM and from 15 to 60 microM. Using the first range of calibration curve, a detection limit of 0.31 microM (based on 3sigma) is obtained. The plot of standard additions of capsaicin determined using the disposable MWCNT-SPE shows a linear range between 0.5 and 35 microM and a detection limit of 0.45 microM. MWCNT-BPPGE and MWCNT-SPE are successfully utilized for the determination of capsaicin in real samples, such as a few commercially available hot pepper sauces, and the determined values are in excellent agreement and correlation with the average Scoville unit values reported in the literature for these sauces. To the best of our knowledge, this is the first electroanalytical method using MWCNT-BPPGE or MWCNT-SPE reported for the determination of capsaicin. This method offers advantages such as precision and objectivity over the well-known but potentially subjective Scoville method (based on organoleptic testing by human tasting panels) and is facile and inexpensive compared to existing HPLC methods.

Sensitive adsorptive stripping voltammetric determination of paracetamol at multiwalled carbon nanotube modified basal plane pyrolytic graphite electrode.

A sensitive electroanalytical methodology for the determination of paracetamol using adsorptive stripping voltammetry (AdsSV) at a multiwalled carbon nanotube modified basal plane pyrolytic graphite electrode (MWCNT-BPPGE) is presented. Both cyclic voltammetric and square wave adsorptive stripping voltammetric techniques are compared. The adsorption occurs at open circuit potential with a 1 min accumulation time. The effect of scan rate and pH were investigated and an optimal scan rate of 100 mVs(-1) and a pH 7.5, 0.05 M phosphate buffer solution (PBS) was used. Additions of paracetamol using cyclic voltammetry exhibits a linear detection range over a wide range of paracetamol concentrations (0.1-25 microM) with a detection limit of 45 nM (based on 3sigma). Additions of paracetamol using square wave adsorptive stripping voltammetry show two linear ranges for paracetamol detection. The first linear range is from 0.01 microM to 2 microM and the second linear range is from 2 microM to 20 microM. Using the first range of this calibration plot, a detection limit of 10nM is obtained for paracetamol. To the best of our knowledge, this limit of detection is the lowest limit of detection has been reported for paracetamol using electrochemical techniques. The method was then successfully utilised for the determination of paracetamol in a real sample of "ANADIN EXTRA" tablets and a recovery of 95% was obtained without interference from aspirin or caffeine. The proposed electroanalytical method using MWCNT-BPPGE is the most sensitive method for determination of paracetamol with lowest limit of detection to date. It has also advantages such as easy handling, resistance against surface fouling, and low cost.

Ionic liquid-carbon composite glucose biosensor.

The use of ionic liquids that are solid at room temperature such as n-octyl-pyridinium hexafluorophosphate (nOPPF(6)) is shown to be advantageous in the fabrication of new form of biocomposite materials with attractive performance over other types of composites and pastes involving non-conductive binders. The resulting IL/graphite material brings new capabilities for electrochemical devices by combining the advantages of ILs and "bulk" composite electrodes. The electrocatalytic properties of the ILs are not impaired by their association with the graphite powder. The marked electrocatalytic activity towards hydrogen peroxide permits effective amperometric biosensing of glucose in connection with the incorporation of glucose oxidase within the three-dimensional IL/graphite matrix. The accelerated electron transfer is coupled with low background current and improved linearity. The advantages of these IL-based biocomposite devices are illustrated from comparison to conventional mineral oil/graphite biocomposite. The influence of the IL and glucose oxidase (GOx) loading upon the amperometric and voltammetric data, as well as the electrode capacitance and resistance, is examined. The preparation of IL/graphite composites overcomes a major obstacle for creating IL-based biosensing devices and expands the scope of IL-based electrochemical devices.

Enhanced stability and sensitivity of ionic liquid-carbon paste electrodes at elevated temperatures.

We describe the operation of ionic liquid-carbon paste electrodes at elevated temperatures and the effect of heating on the electrode performance and response. Using cyclic and square wave voltammetry and amperometry, it is shown that signals can be enhanced and stabilized by increasing the temperature of the operating solution. At low temperature, the electrode was susceptible to electrode fouling and showed poor stability, sensitivity, and linearity. An order of magnitude improvement of response for ascorbic acid was possible by operating the electrode at 60 degrees C compared to 0 degrees C. This study represents the first report showing that the analytical response of ionic liquid-carbon paste electrodes can be improved by operating them at elevated temperatures for a number of applications.

Electroanalytical determination of cadmium(II) and lead(II) using an in-situ bismuth film modified edge plane pyrolytic graphite electrode.

A highly sensitive and simple electroanalytical methodology is presented using an in-situ bismuth film modified edge plane pyrolytic graphite electrode (BiF-EPPGE) which is exemplified with the simultaneous determination of cadmium(II) and lead(II). Square-wave anodic stripping voltammetry is utilised with the effects of several experimental variables studied. Simultaneous additions of cadmium(II) and lead(II) were investigated where two linear ranges between 0.1-100 and 0.1-300 microg/L and also detection limits of 0.062 and 0.084 microg/L were obtained, respectively. The method was then successfully applied to the simultaneous determination of cadmium(II) and lead(II) in spiked river water, where recoveries of 100.5 and 98% were obtained, respectively. This electroanalytical protocol using edge plane pyrolytic graphite electrodes is one of the simplest methodologies to date using non-mercury based electrodes and is simpler and cheaper than alternatives such as carbon nanotube electrode arrays, suggesting the use of edge plane pyrolytic graphite electrode for routine sensing.

A simple electroanalytical methodology for the simultaneous determination of dopamine, serotonin and ascorbic acid using an unmodified edge plane pyrolytic graphite electrode.

A simple method using an unmodified edge plane pyrolytic graphite electrode (EPPGE) is reported for the simultaneous determination of dopamine (DA), serotonin (ST) and ascorbic acid (AA). The performance of this electrode is superior to other unmodified carbon-based electrodes and also to many modified electrodes in terms of detection limit, sensitivity and peak separation for determination of DA, ST and AA. Using this method, detection limits of 90 nM, 60 nM and 200 nM were obtained for DA, ST and AA respectively. No electrode fouling is observed during a set of experiments and good sensitivity is obtained for the simultaneous determination of DA, ST and AA. The peaks for the three species are well resolved from each other and the electrode is successfully utilised for their determination in standard and real samples.