Anodic stripping voltammetry of silver nanoparticles: aggregation leads to incomplete stripping.

The influence of nanoparticle aggregation on anodic stripping voltammetry is reported. Dopamine-capped silver nanoparticles were chosen as a model system, and melamine was used to induce aggregation in the nanoparticles. Through the anodic stripping of the silver nanoparticles that were aggregated to different extents, it was found that the peak area of the oxidative signal corresponding to the stripping of silver to silver(I) ions decreases with increasing aggregation. Aggregation causes incomplete stripping of the silver nanoparticles. Two possible mechanisms of 'partial oxidation' and 'inactivation' of the nanoparticles are proposed to account for this finding. Aggregation effects must be considered when anodic stripping voltammetry is used for nanoparticle detection and quantification. Hence, drop casting, which is known to lead to aggregation, is not encouraged for preparing electrodes for analytical purposes.

Selective electrochemical determination of cysteine with a cyclotricatechylene modified carbon electrode.

We report the selective electrochemical detection of cysteine in the presence of homocysteine and glutathione with the use of an electrode modified with cyclotricatechylene (CTC). A carbon electrode was first modified with cyclotriveratrylene (CTV) and then electrochemically converted into CTC. Using cyclic voltammetry, the redox activity of CTC was investigated along with its electrochemical response to cysteine and the closely related compounds, glutathione and homocysteine which are commonly found in biological media alongside cysteine. The selective detection of cysteine was achieved with the use of the electrocatalytic oxidation reaction and exploiting the different rates of reaction of each thiol with the oxidized CTC via variable scan rate studies. The analytical parameters consisting of sensitivity, range of linear detection, and limit of detection were determined for selective cysteine detection in phosphate buffer solution and tissue culture media where the sensitivity of the system is ca. 0.023 µA µM(-1) and ca. 0.031 µA µM(-1) with a limit of detection of ca. 0.6 µM and ca. 0.9 µM for buffer solution and tissue culture media respectively. Practical assessment of this analytical method was carried out in mixed solutions containing a combination of cysteine, homocysteine and glutathione in both media. The determined results agree well with the added cysteine content. This work presents a novel way of utilizing CTC into detecting cysteine, and is well-suited for bio-marker sensing.

A joint experimental and computational search for authentic nano-electrocatalytic effects: electrooxidation of nitrite and L-ascorbate on gold nanoparticle-modified glassy carbon electrodes.

The investigation of electrocatalytic nanoeffects is tackled via joint electrochemical measurements and computational simulations. The cyclic voltammetry of electrodes modified with metal nanoparticles is modeled considering the kinetics of the electrochemical process on the bulk materials of the different regions of the electrode, that is, the substrate (glassy carbon) and the nanoparticles (gold). Comparison of experimental and theoretical results enables the detection of changes in the electrode kinetics at the nanoscale due to structural and/or electronic effects. This approach is applied to the experimental assessment of electrocatalytic effects by gold nanoparticles (Au NPs) in the electrooxidation of nitrite and L-ascorbate. Glassy carbon electrode is modified with Au NPs via seed-mediated growth method. Divergence between the kinetics of these processes on gold macroelectrodes and gold nanoparticles is examined. Whereas claimed catalytic effects are not observed in the electrooxidation of nitrite, electrocatalytic nanoeffects are verified in the case of L-ascorbate. This is probably due to that the electron transfer process follows an adsorptive mechanism. The combination of simulation with experiments is commended as a general strategy of authentification, or not, of nanoelectrocatalytic effects.

Facile in situ characterization of gold nanoparticles on electrode surfaces by electrochemical techniques: average size, number density and morphology determination.

A fast and cheap in situ approach is presented for the characterization of gold nanoparticles from electrochemical experiments. The average size and number of nanoparticles deposited on a glassy carbon electrode are determined from the values of the total surface area and amount of gold obtained by lead underpotential deposition and by stripping of gold in hydrochloric acid solution, respectively. The morphology of the nanoparticle surface can also be analyzed from the "fingerprint" in lead deposition/stripping experiments. The method is tested through the study of gold nanoparticles deposited on a glassy carbon substrate by seed-mediated growth method which enables an easy control of the nanoparticle size. The procedure is also applied to the characterization of supplied gold nanoparticles. The results are in satisfactory agreement with those obtained via scanning electron microscopy.

Combinatorial electrochemistry using metal nanoparticles: from proof-of-concept to practical realisation for bromide detection.

Principles and practical application of combinatorial electrochemistry in search for new electroactive materials in electroanalysis have been explored. Nanoparticles of three different metals: silver, gold and palladium have been independently synthesized on the glassy carbon spherical powder surface by electroless deposition process and characterized using both spectroscopic and electrochemical techniques. These three materials were then combined together onto basal plane pyrolytic graphite electrode surface and the application of the combinatorial approach to find the electrode material for bromide detection as model target analyte was demonstrated. The component electroactive for bromide detection was next identified and it was found that silver nanoparticles were the active ones. A composite electrode based on silver nanoparticle modified glassy carbon powder and epoxy resin was then fabricated and it was found to allow accurate determination of bromide. The electroactivity for the bromide determination of the composite electrode was compared with that of a bulk silver electrode and it was shown that the composite electrode is very efficient with a comparable electroactivity with only a portion of precious metals being used for its construction.

Ultrastructural evaluation of explanted opacified Hydroview (H60M) intraocular lenses.

AIM: To describe the ultrastructural appearance of explanted opacified Hydroview H60M intraocular lenses. METHODS: 14 explanted lenses were examined by scanning electron microscopy, and their appearance compared with a non-implanted H60M lens from the same time period. Wavelength-dispersive x ray spectroscopy (WDX) was performed on two opacified lenses. RESULTS: Subsurface deposits were seen in all explanted opacified lenses. These deposits broke only onto the surface of more densely opacified lenses. WDX confirmed that the deposits contained both calcium and phosphorous, consistent with their being calcium apatite. CONCLUSION: These findings challenge the widely accepted opinion that H60M intraocular lens opacification begins on the surface of the optic.

Electroanalysis using macro-, micro-, and nanochemical architectures on electrode surfaces. Bulk surface modification of glassy carbon microspheres with gold nanoparticles and their electrical wiring using carbon nanotubes.

Gold nanoparticles (approximately 30-60 nm in diameter) were deposited onto the surface of glassy carbon microspheres (10-20 microm) through electroless plating to produce bulk (i.e., gram) quantities of nanoparticle surface-modified microspheres. The gold nanoparticle-modified powder was then characterized by means of scanning electron microscopy and cyclic voltammetry. The voltammetric response of a macroelectrode consisting of a film of gold nanoparticle-modified glassy carbon microspheres, bound together and "wired-up" using multiwalled carbon nanotubes (MWCNTs), was investigated. We demonstrate that by intelligently exploiting both nano- and microchemical architectures and wiring up the electroactive centers using MWCNTs in this way, we can obtain macroelectrode voltammetric behavior while only using approximately 1% by mass of the expensive gold material that would be required to construct the equivalent gold film macrodisk electrode. The potential utility of electrodes constructed using chemical architectures such as this was demonstrated by applying them to the analytical determination of arsenic(III) concentration. An optimized limit of detection of 2.5 ppb was obtained.

Electrochemically polymerised composites of multi-walled carbon nanotubes and poly(vinylferrocene) and their use as modified electrodes: application to glucose sensing.

We report electrochemical composites of multi-walled carbon nanotubes (MWCNTs) with poly(vinylferrocene) (PVF). The polymeric architecture is prepared by first immobilising the MWCNTs onto a glassy carbon substrate, which acts to introduce electrical current into the composite, with the MWCNTs acting as 'molecular wires'. PVF films of varying surface coverages can be obtained by simply controlling the time a constant potential of +0.7 V (vs. Ag) wire is applied; with the characteristics of the derivatised MWCNTs examined by cyclic voltammetry and scanning electron microscopy. The application of the composite for glucose determination in aqueous solutions was investigated using linear sweep voltammetry, where it was found that the composites supported on glassy carbon substrates are superior to bare glassy carbon electrodes polymerised with PVF, likely due to the comparatively higher number of electrocatalytic centres in the former. This protocol was successfully transferred to prepare a PVF-MWCNT-paste electrode which was applied to glucose detection in diluted laked horse blood. The obtained results show potential and promising practical application for the polymer-derivatised MWCNT-modified electrodes in amperometric sensors for glucose determination.