Are nanoparticles spherical or quasi-spherical?

The geometry of quasi-spherical nanoparticles is investigated. The combination of SEM imaging and electrochemical nano-impact experiments is demonstrated to allow sizing and characterization of the geometry of single silver nanoparticles

Multi-electron transfer to and from organic molecules

Herein, the influence of protonation and adsorption upon the redox and electrocatalysis of quinone species - specifically anthraquinone derivatives – is investigated.Through the comparison of the measured rate constants of one-electron reductions of a family of quinones in acetonitrile at both graphite and gold electrodes, it was confirmed that the redox potential indirectly influences the rate of electron transfer in a manner consistent with the potential-dependence of the density of states. In aqueous media, the voltammetric response of both anthraquione-2-sulfonate (AQMS) and anthraquinone-2,6-disulfonate (AQDS) was measured over the full aqueous pH range. A model is provided which is able to describe not just the variation in the formal potential but also the peak height as a function of pH. Importantly, this model predicts that the formal potential for the first (Ef1) and second (Ef2) electron transfers are comparable in magnitude (E^θ _f2−E^_θf1 equals -15mV for AQMS and -36mV for AQDS). This quantitative model is then further extended to consider the situation in which the system is not fully buffered, giving insight into the change of pH at the electrode surface during experimentation.Adsorption to graphitic electrodes can impart a strong influence on the measured voltammetric response. It is demonstrated that through the pre-exposure of a newly prepared graphitic electrode to organic solvents, these adsorption processes can be predominantly blocked. Moreover, it is shown that the electroactivity of the electrode is not significantly altered. This thesis also highlights two cases in which adsorption of the electroactive species may be used to positive effect. First, the surface adsorption of anthraquinone-2-monosulfonate is studied on a graphite electrode, where it is demonstrated that the heterogeneity of the electrode surface may be probed through studying the electrochemical response of the adsorbed species. From this work it is concluded that the rate of electron transfer at the graphitic basal plane is 2-3 orders of magnitude lower than that observed on the edge plane sites. Second, the co-adsorption of DNA and anthraquinone-2-monosulfonate is used as an indirect method to measure the solution phase concentration of DNA (LOD = 8.8μM).The reduced form of anthraquinone is also known to readily reduce oxygen. Through the use of a boron-doped diamond electrode it was possible to directly study the anthraquinone mediated reduction mechanism. Significantly, the voltammetric response indicates the reduction of the oxygen via the semi-quinone intermediate (kf = 4.8 × 10⁹ mol⁻¹ dm³ s⁻¹) is over two orders of magnitude faster than the reaction involving the di-reduced form (kf = 1 × 10⁷ mol⁻¹ dm³ s⁻¹). More importantly, this work provides voltammetric evidence for the existence of the semi-quinone species. This work is subsequently extended through the investigation of the poorly soluble anthraquinone derivative quinizarin. Not only is it possible to detect voltammetrically this biologically relevant species to concentrations as low as 5nM (100ppt), but the methodology also allows the electrochemistry of the quinizarin species to be probed, something which was not previously possible.</p

The influence of substrate effects when investigating new nanoparticle modified electrodes exemplified by the electroanalytical determination of aspirin on NiO nanoparticles supported on graphite

The apparent electrocatalytic detection of aspirin and salicylic acid is compared using NiO nanoparticles and microparticles supported on graphitic electrodes using abrasive and non-abrasive (drop-dry) immobilisation. However control experiments revealed that, the observed voltammetry is not due to the immobilised NiO materials, but is instead due to the underlying graphitic substrates. Abrasive immobilisation of NiO microparticles on a graphite electrode abrades the underlying electrode surface, introducing more electroactive edge-plane defects. Even when drop-dry immobilisation is used (i.e. non-abrasive), appropriate control experiments are still required as other experimental methods employed may change the nature of the underlying substrate

Multi-electron transfer to and from organic molecules

Herein, the influence of protonation and adsorption upon the redox and electrocatalysis of quinone species - specifically anthraquinone derivatives – is investigated. Through the comparison of the measured rate constants of one-electron reductions of a family of quinones in acetonitrile at both graphite and gold electrodes, it was confirmed that the redox potential indirectly influences the rate of electron transfer in a manner consistent with the potential-dependence of the density of states. In aqueous media, the voltammetric response of both anthraquione-2-sulfonate (AQMS) and anthraquinone-2,6-disulfonate (AQDS) was measured over the full aqueous pH range. A model is provided which is able to describe not just the variation in the formal potential but also the peak height as a function of pH. Importantly, this model predicts that the formal potential for the first (Ef1) and second (Ef2) electron transfers are comparable in magnitude (E^θ _f2−E^_θf1 equals -15mV for AQMS and -36mV for AQDS). This quantitative model is then further extended to consider the situation in which the system is not fully buffered, giving insight into the change of pH at the electrode surface during experimentation. Adsorption to graphitic electrodes can impart a strong influence on the measured voltammetric response. It is demonstrated that through the pre-exposure of a newly prepared graphitic electrode to organic solvents, these adsorption processes can be predominantly blocked. Moreover, it is shown that the electroactivity of the electrode is not significantly altered. This thesis also highlights two cases in which adsorption of the electroactive species may be used to positive effect. First, the surface adsorption of anthraquinone-2-monosulfonate is studied on a graphite electrode, where it is demonstrated that the heterogeneity of the electrode surface may be probed through studying the electrochemical response of the adsorbed species. From this work it is concluded that the rate of electron transfer at the graphitic basal plane is 2-3 orders of magnitude lower than that observed on the edge plane sites. Second, the co-adsorption of DNA and anthraquinone-2-monosulfonate is used as an indirect method to measure the solution phase concentration of DNA (LOD = 8.8μM). The reduced form of anthraquinone is also known to readily reduce oxygen. Through the use of a boron-doped diamond electrode it was possible to directly study the anthraquinone mediated reduction mechanism. Significantly, the voltammetric response indicates the reduction of the oxygen via the semi-quinone intermediate (kf = 4.8 × 10⁹ mol⁻¹ dm³ s⁻¹) is over two orders of magnitude faster than the reaction involving the di-reduced form (kf = 1 × 10⁷ mol⁻¹ dm³ s⁻¹). More importantly, this work provides voltammetric evidence for the existence of the semi-quinone species. This work is subsequently extended through the investigation of the poorly soluble anthraquinone derivative quinizarin. Not only is it possible to detect voltammetrically this biologically relevant species to concentrations as low as 5nM (100ppt), but the methodology also allows the electrochemistry of the quinizarin species to be probed, something which was not previously possible.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

PORTUGALIAE ELECTROCHIMICA ACTA Nanotoxicity -an electrochemist&apos;s perspective

Abstract This article highlights the fundamental role of mass-transport for interfacial reactions. First, the dissolution of particulate CaCO 3 is discussed demonstrating how the dimensions of the dissolving particle can &apos;switch&apos; the reaction mechanism from being diffusion to surface controlled. Second, the influence of mass-transoprt on electrochemical reactions is considered, specifically considering how electrode modification can alter the observed voltammetric response in the absence of changing the electrochemical mechanism or the rate of electron transfer. Finally, these observations on the chemically controlling role of mass-transport are concluded by considering nanoparticle toxicity and how &apos;size effects&apos; may be exhibited even in the absence of altered thermodynamics or interfacial kinetics of the reactions involved

The contrasting behaviour of polycrystalline bulk gold and gold nanoparticle modified electrodes towards the underpotential deposition of thallium

The underpotential deposition (UPD) of thallium onto a polycrystalline gold macroelectrode or gold nanoparticles (10 ± 5 nm in diameter) supported on multiwalled carbon nanotubes (MWCNTs) is compared both in the presence and the absence of adsorbed chloride anions. On the polycrystalline gold macrodisc electrode the UPD of thallium is observed. However, on the 10 nm gold nanoparticles supported on MWCNTs no UPD of thallium is observed despite several control experiments which confirmed that the gold nanoparticles were indeed electroactive. This is compared to the reported behaviour of larger 30–60 nm diameter gold nanoparticles at which UPD of thallium is also found to occur and the possible reasons for this are discussed. This report provides an example where the properties of metal nanoparticles differ markedly from the bulk metal and the properties of the nanoparticles vary significantly with the size of the nanoparticles

Shape and size of non-spherical silver nanoparticles: implications for calculating nanoparticle number concentrations

The international drive to measure accurate number concentrations of nanoparticles is impeded by the typically heterogeneous populations of non-spherical nanoparticles. The irregular shape and size of “50 nm” silver nanoparticles is studied using Electron Tomography. It is evidenced that even for highly symmetrical particles the volume can be over 20% less than that of the circumscribed sphere; more irregularly shaped particles can have volumes of over 45% less. On this basis, criteria are provided to determine the particle sphericity from 2D projections obtained from Electron Microscopy, including an empirical method for particle volume estimation. The results allow the visualisation of irregularly shaped particles, revealing the presence of previously unseen voids in the nanoparticle structure. Comparison of tomographic data with other commonly used particle-sizing methods exposes the limitations of these methods in studying nanoparticle populations that exhibit heterogeneity

The use of copper(II) oxide nanorod bundles for the non-enzymatic voltammetric sensing of carbohydrates and hydrogen peroxide

CuO nanorod agglomerates were synthesised via a simple hydrothermal method in the presence of polyethylene glycol (PEG; Mw 20,000). The chemical composition, size and morphology of the prepared CuO material was investigated by X-ray powder diffraction, voltammetry and transmission electron microscopy. A basal plane pyrolytic graphite electrode (bppg) was modified with the CuO nanorods and used to study the direct oxidation of glucose, fructose and sucrose in an alkaline medium (0.1 M NaOH). The CuO nanorod modified electrode was shown to have far larger analytical signals in the presence of carbohydrates than an electrode modified with CuO microparticles and gave a limit of detection for glucose of 1.2 × 10-6 M which is comparable with the literature. As such it is a non-selective, non-enzymatic, total carbohydrate sensor. The CuO nanorod modified bppg electrode was also used for the detection of H2O2, it was shown that in this case it is preferential to look at the oxidation of the analyte due to interference of oxygen in the reductive window. A limit of detection of 2.2 × 10-7 M was obtained for the sensing of hydrogen peroxide in an alkaline solution

A proof-of-concept – Using pre-created nucleation centres to improve the limit of detection in anodic stripping voltammetry

Anodic stripping voltammetry is a much-utilised method for trace metal analysis. We provide a simple proof-of-concept technique to improve the sensitivity of the method, which is illustrated by the detection of silver cations. This approach requires an electrode pre-treatment, which involves drop casting a metal nanoparticle suspension and oxidising the nanoparticles, leaving small metal nuclei on the electrode surface. In turn, the small metal nuclei act as nucleation sites for subsequent metal deposition when used to interrogate target solutions. In particular, the pre-treatment increases the amount of deposited metal in a given amount of time. Silver nitrate concentrations from 30 nM to 1 μM were tested and at silver ion concentration of 300 nM, the pre-treated electrode gave a signal, which was 40 times larger than the untreated electrode. The larger signal leads to the enhancement of sensitivity and a lowering of the detection limit of anodic stripping voltammetry without introducing other organic molecules, metals or impurities