How Many Molecules are Required to Obtain a Steady Faradaic Current from Mediated Electron Transfer at a Single Nanoparticle on a Supporting Surface?

We investigate the chronoamperometric noise characteristics of electron‐transfer reactions occurring on single nanoparticles (NPs) and assemblies of well‐separated NPs on a supporting surface. To this end, we combine a formerly described expression for the steady‐state current of a single particle with the shot‐noise model and derive an expression for the signal‐to‐noise ratio as a function of bulk concentration and particle radius. Our findings are supported by random‐walk simulations, which closely match the analytical results.     

Fast electrodeposition of zinc onto single zinc nanoparticles

The zinc deposition reaction onto metallic zinc has been investigated at the single particle level through the electrode-particle collision method in neutral solutions, and in respect of its dependence on the applied potential and the ionic strength of a sulphate-containing solution. Depending on the concentration of sulphate ions in solution, different amounts of metallic zinc were deposited on the single Zn nanoparticles. Specifically, insights into the electron transfer kinetics at the single particles were obtained, indicating an electrically early reactant-like transition state, which is consistent with the rate-determining partial de-hydration/de-complexation process. Such information on the reaction kinetics at the nanoscale is of vital importance for the development of more efficient and long-lasting nanostructured Zn-based negative electrodes for Zn-ion battery applications.

     

Electro-oxidation of amino-functionalized multiwalled carbon nanotubes

We report the electrochemistry of amino-functionalized multiwalled carbon nanotubes (MWCNTs-NH₂) in the pH range from 0.3 to 6.4 using quantitative cyclic voltammetry (CV) and single entity electrochemistry measurements, making comparison with non-functionalized MWCNTs. CV showed the latter to both catalyze the solvent (water) decomposition and to undergo irreversible electro-oxidation forming oxygen containing surface functionality. The MWCNTs-NH₂ additionally undergo an irreversible oxidation to an extent which is dependent on the pH of the solution, reflecting the variable amount of deprotonated amino groups present as a function of pH. Nano-impact experiments conducted at the single particle level confirmed the oxidation of both types of MWCNTs, showing agreement with the CV. The pK_a of the amino groups in MWCNTs was determined via both electrochemical methods giving consistent values of ca. 2.5.

A new and generic approach to the study of the oxidation of different forms of CNTs is found by using quantitative single entity and ensemble electrochemistry measurements.     

Synthesis of Novel C/D Ring Modified Bile Acids

Bile acid receptors have been identified as important targets for the development of new therapeutics to treat various metabolic and inflammatory diseases. The synthesis of new bile acid analogues can help elucidate structure–activity relationships and define compounds that activate these receptors selectively. Towards this, access to large quantities of a chenodeoxycholic acid derivative bearing a C-12 methyl and a C-13 to C-14 double bond provided an interesting scaffold to investigate the chemical manipulation of the C/D ring junction in bile acids. The reactivity of this alkene substrate with various zinc carbenoid species showed that those generated using the Furukawa methodology achieved selective α-cyclopropanation, whereas those generated using the Shi methodology reacted in an unexpected manner giving rise to a rearranged skeleton whereby the C ring has undergone contraction to form a novel spiro–furan ring system. Further derivatization of the cyclopropanated steroid included O-7 oxidation and epimerization to afford new bile acid derivatives for biological evaluation.     

MRI of hepatic lymphoma

Thirteen patients with biopsy proven hepatic lymphoma (2 Hodgkin, 11 Non-Hodgkin) and a control group of 15 patients with hepatic metastases were analyzed quantitatively and qualitatively by MRI. Focal hepatic lymphoma was most reliably detected (eight of eight patients) and appeared hypointense relative to liver on T₁ weighted (CNR − 7.4 ± 2.3) and hyperintense on T₂ weighted (CNR + 8.4 ± 2.9) images. The mean T₁ and T₂ relaxation times of focal hepatic lymphoma (T₁ = 832 ± 234 msec, T₂ = 84 ± 16 ms) differed significantly from adjacent non-tumorous liver (T₁ = 420 ± 121 ms, T₂ = 51 ± 9 ms; p < 0.05), however CNR values and relaxation times were similar to those of hepatic metastases. Diffuse hepatic lymphoma (microscopic periportal infiltration) was undetectable by MRI in three patients by either morphologic features or quantitative criteria. A mixed pattern of hepatic lymphoma (focal lesions and diffuse infiltration) showed focal areas of slightly decreased signal intensity on T₁ weighted images (CNR = −1.7 ± 0.4) while T₂ weighted images revealed multiple regions of focal hyperintensity (CNR = +13.3 ± 8.4) superimposed on a diffusely hyperintense liver. Our experience demonstrates that either T₁ or T₂ weighted techniques are useful in detecting focal and that T₂ weighted techniques are useful in detecting mixed hepatic lymphoma. Conventional image derived relaxation time measurements and quantitative parameters were of no additional diagnostic value.     

The electroneutrality approximation in electrochemistry

The electroneutrality approximation assumes that charge separation is impossible in electrolytic solutions. It has a long and successful history dating back to 1889 and may be justified because of the small absolute values for the permittivities of typical solvents. Dimensional analysis shows that the approximation becomes invalid only at nanosecond and nanometre scales. Recent work, however, has taken advantage of the capabilities of modern numerical simulation in order to relax this approximation, with concomitant advantages such as avoiding paradoxes and permitting a clear and consistent ??physical picture?? to describe charge dynamics in solution. These new theoretical techniques have been applied to liquid junction potentials and weakly supported voltammetry, with strong experimental corroboration for the latter. So long as dynamic processes are being studied, for which analytical solutions are unavailable in any case, numerical simulation is shown to render electroneutrality unnecessary as an a priori assumption.     

Atomic force microscopy studies of the KF (100) surface: formation of water-rich surface phases in moist N,N-dimethylformamide

A water rich surface phase is observed in the system KF-DMF-H2O by atomic force microscopy; the effects on surface morphology and likely implications for halogen exchange reactions using KF are discussed.     

Microelectrode study of single cavitational bubbles induced by 500 kHz ultrasound

Insight is gained into about the processes governing cavitational activity and acoustic streaming induced by high frequency (500 kHz) ultrasound by the use of microelectrodes with short time resolution electrochemical equipment to allow monitoring of the activity of single cavitating bubbles. Current transients are interpreted as showing the flux of solution towards the electrode surface due to microstreaming. In order to explain the current amplitude, a simplified model is produced. Important parameters such as bubble size and shape on the surface as well as the boundary layer thickness for microstreaming are taken into account. This model leads to the amplitude of the oscillations of the cavitating bubble. Introducing realistic bubble sizes, this amplitude is found to be in the order of 1 micron. The conclusions arising from this work allow a further interpretation of previous observations at millimeter scale electrodes.     

An AFM Study of the Correlation of Lead Dioxide Electrocatalytic Activity with Observed Morphology

PbO2 is widely employed as an electrocatalyst for anodic oxidation processes including the generation of oxygen and the degradation of various organic species in aqueous solution. However, despite extensive investigation, the precise mechanism of action remains obscure. In this paper we establish a previously unrecognized strong correlation between the morphology of the PbO2 deposits and their electrocatalytic activity. Cyclic voltammetric results are described for the electrodeposition of PbO2 on boron-doped diamond (BDD) electrodes from 2.5 mM solutions of lead(II) nitrate in nitric acid at pH values between approximately 0 and 7. A likely change in mechanism is observed around pH 4, consistent with the Pourbaix diagram of lead. The morphology of the PbO2 films is observed as a function of time and potential, using in situ AFM in each of the lead solutions. Information on the growth rates of the films is extracted, and the limitations of using AFM in such an application are discussed. It is shown that the deposit morphology depends strongly on the specific conditions used. The oxidation of a 100 mM glucose solution on electrodes modified by PbO2 deposition at a range of potentials and pH values is used as an indicator of the catalytic activity of the corresponding films, leading to the observation of the correlation between deposit morphology and catalytic activity mentioned above.     

Investigation of modified basal plane pyrolytic graphite electrodes: definitive evidence for the electrocatalytic properties of the ends of carbon nanotubes

The basis of the electrocatalytic nature of multi-wall carbon nanotubes is suggested to reside in electron transfer from the ends of nanotubes, which structurally resemble the behaviour of edge plane (as opposed to basal plane) graphite, and is demonstrated via the comparison of the electrochemical oxidation of epinephrine and the electrochemical reduction of ferricyanide at nanotube-modified electrodes using different types of graphite electrodes and with C(60)-modified electrodes.