Michael Ongaro

Bioelectroanalysis with nanoelectrode ensembles and arrays

This review deals with recent advances in bioelectroanalytical applications of nanostructured electrodes, in particular nanoelectrode ensembles (NEEs) and arrays (NEAs). First, nanofabrication techniques, principles of function, and specific advantages and limits of NEEs and NEAs are critically discussed. In the second part, some recent examples of bioelectroanalytical applications are presented. These include use of nanoelectrode arrays and/or ensembles for direct electrochemical analysis of pharmacologically active organic compounds or redox proteins, and the development of functionalized nanoelectrode systems and their use as catalytic or affinity electrochemical biosensors.

Arrays of templated TiO2 nanofibres as improved photoanodes for water splitting under visible light

Arrays of TiO2 nanofibres (NFs) were successfully prepared by template sol-gel synthesis, using track-etched polycarbonate membranes as structure directing agent. The control of the sol-gel kinetic was crucial in order to homogeneously fill the pores with a continuous framework. For this reason acetylacetone was added to the sol-gel mixture as chelating agent. The band edge positions of TiO2 NFs were determined by a Mott-Schottky plot and diffuse reflectance analysis. The results support the presence of trace dopants which can act favorably with respect to the photoelectrochemical properties. The TiO2 NFs array showed enhanced photoelectrochemical activity both under UV light and visible light when used as photoanodes for the water splitting reaction.

Sensor arrays: arrays of micro- and nanoelectrodes

This chapter deals with the principles of functioning and electroanalytical usefulness of arrays of micrometer and nanometer-sized electrodes. We discuss arrays of microelectrodes both individually shaped and interdigitated. In the field of nanostructured electrodes, both nanoelectrode ensembles (random arrays) and ordered arrays are presented. A comparison between the fabrication methods, characteristics as well as advantages and limits of each kind of array are critically evaluated.

Electrochemical preparation of standard solutions of Pb(II) ions in ionic liquid for analysis of hydrophobic samples: The olive oil case

In this paper we present an electrochemical approach to prepare standard solutions of metal ions in a room temperature ionic liquid (IL), which can find useful application for analysis in hydrophobic matrices. The method, developed here for the case of lead ions, is based on the galvanostatic dissolution of a lead anode dipped directly in a suitable IL, namely tri-hexyl(tetradecyl)phosphonium bis (trifluoromethylsulfonyl) imide ([P14,6,6,6]+[NTf2]-). After each oxidation step, the metal dissolution process in the IL solutions was monitored by cyclic voltammetric measurements at a glassy carbon disk electrode. The results indicated that the peak current relevant to the reduction of the electro-generated Pb(II) increased linearly while increasing the oxidation time. By varying the oxidation time from 200 to 6000s, a set of Pb(II)/[P14,6,6,6]+[NTf2]- solutions at concentrations ranging between 10 and 300μgg-1 was prepared. To validate the efficiency of the electrochemical procedure to produce metal ion standard solutions, the Pb content was quantified by developing a microwave digestion procedure specifically suitable for the IL medium, followed by ICP-QMS analysis in the digested standards. The results indicated a satisfactory agreement between concentrations found by ICP-QMS and calculated from electrochemical data, with a coulometric efficiency of Pb(II) generation in ionic liquid ≥95.6%. Finally, the applicability of the Pb(II)/IL solutions as standards for analyses in hydrophobic media was tested by determining, by ICP-QMS, the Pb content in an extra-virgin olive oil spiked with known amounts of a Pb(II)/IL standard. Satisfactory Pb recoveries, ≥96%, were measured.