PEDOT‐Modified Microelectrodes. Preparation,Characterisation and Analytical Performances

Poly(3,4‐ethylenedioxythiophene) (PEDOT) modified microelectrodes were prepared by electropolymerisation of the relevant monomer from CH₃CN or H₂O solutions. The electrochemical behaviour of the obtained coatings was investigated by cyclic voltammetry in both organic and aqueous media. The anodic responses obtained for a typical benchmark analyte such as ascorbic acid was used to test the different coatings; calibration curves were built up in order to evaluate the repeatability of the response and the reproducibility of the prepared sensing system. Moreover, the ability of the modified microelectrodes to work in low conductivity media was studied, and exploratory tests in dense food matrix was performed.     

A novel class of tetrairon(III) single-molecule magnets with graphene-binding groups

Tripods of general formula R’–O–CH₂C(CH₂OH)₃ are excellent site-specific ligands for the preparation of functionalized Fe₄ single-molecule magnets. Herein, we describe the synthesis and characterization of two novel complexes designed to bind graphene surfaces, in which the R group consists of an alkyl spacer –(CH₂)_n– (n = 6 and 10) and a terminal pyrenyl moiety. The site-specific ligand substitution on [Fe₄(OMe)₆(dpm)₆] (Hdpm = dipivaloylmethane) with the new tripods has been studied with ²H NMR on isotopically-enriched samples, revealing that, once formed, these clusters are stable in solution over long timescales. It was not possible to isolate the new compounds as crystalline solids, nevertheless they were chemically characterized by elemental analysis and ¹H NMR. The presence of the pyrenyl ending groups prompted us to investigate the effect of metal complexation on fluorescence, and a full pyrene-to-iron cluster excitation energy transfer was observed. The analysis of the magnetic behaviour revealed an S = 5 ground spin state with a negative zero-field splitting parameter D = ?0.42 cm^?1.     

Layer-by-layer deposition of a polythiophene/Au nanoparticles multilayer with effective electrochemical properties

Multilayers consisting of a water soluble polythiophene derivative and Au nanoparticles have been deposited onto different electrode substrates by means of layer-by-layer deposition technique. The assembly of the films has been performed by taking advantage of the electrostatic interactions between the positively charged imidazolic moiety of the polythiophene chain and the negative charges of citrate ions surrounding Au nanoparticles, as well of the affinity of S to Au. The nanoparticles result stably grafted to the organic matrix. The resulting modified electrodes have been characterised through electrochemical, spectroelectrochemical and microscopic techniques. The results evidenced that a high number of individual nanoparticles is present inside the multilayer. The presence of nanoparticles is of chief importance for most effective charge percolation through the multilayer, as suggested by the responses to electroactive probe species in solution. The electrocatalytic performances of the modified electrodes have been tested with respect to the oxidation of ascorbic acid.     

Recent advances in the direct electrochemical detection of drugs of abuse

In the last decade, the trafficking and use of illicit drugs showed a continuous incremental trend, remaining worldwide a challenging problem for the consequences on society, health, criminality, and environment. The introduction on the market of new products and of illicit synthetic compounds represents a new challenging task for analytical chemistry, looking for rapid and accurate methods for the detection of illicit substances in seized street samples, biological fluids, and wastewater. In this context, electrochemical sensors have shown promising results as an alternative to standard chromatographic and spectroscopic methods. This review aims at highlighting the most recent progresses in the use of electrochemistry for the detection of drugs of abuse, mainly including well consolidated substances like cannabinoids, cocaine, opioids, ecstasy, and methamphetamine as well as new psychoactive molecules widely diffused at the present time. Different strategies have been described particularly consisting in the direct electrochemical oxidation of the target analyte. The implementation of tailor-made portable instruments with electrochemical detection methods constitutes an added value to improve the effectiveness of electrochemical sensors for the identification of psychoactive substances when performing large-scale sampling tests.

     

Aromatische Verbindungen

Ohne Zusammenfassung     

Layer-by-layer deposition of a polythiophene/Au nanoparticles multilayer with effective electrochemical properties

Multilayers consisting of a water soluble polythiophene derivative and Au nanoparticles have been deposited onto different electrode substrates by means of layer-by-layer deposition technique. The assembly of the films has been performed by taking advantage of the electrostatic interactions between the positively charged imidazolic moiety of the polythiophene chain and the negative charges of citrate ions surrounding Au nanoparticles, as well of the affinity of S to Au. The nanoparticles result stably grafted to the organic matrix. The resulting modified electrodes have been characterised through electrochemical, spectroelectrochemical and microscopic techniques. The results evidenced that a high number of individual nanoparticles is present inside the multilayer. The presence of nanoparticles is of chief importance for most effective charge percolation through the multilayer, as suggested by the responses to electroactive probe species in solution. The electrocatalytic performances of the modified electrodes have been tested with respect to the oxidation of ascorbic acid.