Her Shuang Toh

The anodic stripping voltammetry of nanoparticles: electrochemical evidence for the surface agglomeration of silver nanoparticles

Analytical expressions for the anodic stripping voltammetry of metallic nanoparticles from an electrode are provided. First, for reversible electron transfer, two limits are studied: that of diffusionally independent nanoparticles and the regime where the diffusion layers originating from each particle overlap strongly. Second, an analytical expression for the voltammetric response under conditions of irreversible electron transfer kinetics is also derived. These equations demonstrate how the peak potential for the stripping process is expected to occur at values negative of the formal potential for the redox process in which the surface immobilised nanoparticles are oxidised to the corresponding metal cation in the solution phase. This work is further developed by considering the surface energies of the nanoparticles and its effect on the formal potential for the oxidation. The change in the formal potential is modelled in accordance with the equations provided by Plieth [J. Phys. Chem., 1982, 86, 3166-3170]. The new analytical expressions are used to investigate the stripping of silver nanoparticles from a glassy carbon electrode. The relative invariance of the stripping peak potential at low surface coverages of silver is shown to be directly related to the surface agglomeration of the nanoparticles.

Electrochemical detection of chloride levels in sweat using silver nanoparticles: a basis for the preliminary screening for cystic fibrosis

Cystic fibrosis is a common disease which has an associated characteristic symptom of high sweat chloride content. Thus, chloride ion quantification in sweat is important towards the screening of cystic fibrosis. Electrochemical methods, being cost effective and convenient, can be exploited for this. The electrochemical oxidation of silver nanoparticles in the absence of chloride ions gives one voltammetric signal related to the oxidation of silver to silver ions. The presence of chloride ions in the solution causes the appearance of an additional signal at a lower potential which is related to the oxidation of silver to silver chloride. This signal has a peak height which correlates linearly with the concentration of chloride ions from 2 mM to 40 mM when the electrochemical experiments are performed on silver nanoparticle modified screen printed electrodes. Thus, reliable quantification was found to be achievable. Furthermore, chloride ion levels of diluted synthetic sweat samples are measured accurately with the modified electrodes. Thus, the detection of the chloride ion concentration with a silver nanoparticle modified electrode provides a proof-of-concept for a point-of-care system for preliminary screening of cystic fibrosis.

Chemical interactions between silver nanoparticles and thiols: a comparison of mercaptohexanol against cysteine

The interaction between citrate capped silver nanoparticles and two different thiols, mercaptohexanol (MH) and cysteine, was investigated. The thiols interacted with silver nanoparticles in a significantly contrasting manner. With MH, a sparingly soluble silver(I) thiolate complex AgSRm (Rm = −(CH2)6OH) was formed on the silver nanoparticle surface. Cyclic voltammograms and UV-vis spectra were used to infer that the AgSRm complex on the nanoparticle surface undergoes a phase transition to give a mixture of AgSRm and Ag2S-like complexes. In contrast, when silver nanoparticles were exposed to cysteine, the citrate capping agent on the silver nanoparticles was replaced by cysteine to give cysteine capped nanoparticles. As cysteine capped nanoparticles form, the electrochemical data displayed a decrease in oxidative peak charge but the UV-vis spectra showed a constant signal. Therefore, cysteine capped nanoparticles were suggested to have either inactivated the silver surface or else promoted detachment from the electrode surface.

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.

'Nano-impacts': An Electrochemical Technique for Nanoparticle Sizing in Optically Opaque Solutions.

Typical laser-dependent methods such as nanoparticle tracking analysis (NTA) and dynamic light scattering (DLS) are not able to detect nanoparticles in an optically opaque medium due to scattering or absorption of light. Here, the electrochemical technique of ‘nano-impacts’ was used to detect nanoparticles in solution in the presence of high levels of alumina particulates causing a milky white suspension. Using the ‘nano-impacts’ method, silver nanoparticles were successfully detected and sized in the model opaque medium. The results obtained compared well with those using transmission electron microscopy (TEM), an ex situ method for nanoparticle size determination. The ability to use the ‘nano-impacts’ method in media unmeasurable to competitor techniques confers a significant advantage on the electrochemical approach.

Voltammetric Study of the Influence of Various Phosphate Anions on Silver Nanoparticle Oxidation

The antibacterial properties of silver are strongly controlled by the redox couple of silver/silver(I). This work reports the influence of phosphate anions on silver nanoparticle oxidation, which is important given the abundance of phosphate species in biological systems. The three different species of anions were found to have a varying degree of influence on silver oxidation with the order PO43−>HPO42−>H2PO4−. It was found that in the presence of phosphate anions, the silver oxidation potential shifts to a less positive value, which indicated the increasing ease of the oxidation reaction of silver. Given that the interplay between silver and its cation is crucial to its antibacterial properties and significant concentrations of the HPO42− anion are present at biological pH (near neutral), it is essential that the influence of the dibasic anion (HPO42−) on silver oxidation dynamics be considered for biological systems.

Chapter 5:Electrochemical Detection of Nanoparticles

The electroanalysis of nanoparticles is summarised in a review with 172 references. A brief overview of nanoparticle properties is followed by a critical survey of the state-of-the-art methods for nanoparticle detection. The merits of electrochemistry based techniques are discussed and developed in the context of stripping voltammetry and the recently developed nanoparticle–electrode impact methodology.