Needle-type glucose microbiosensor based on glucose oxidase immobilised in an overoxidised polypyrrole film (an in-vitro study)

A fast response, needle-type glucose microbiosensor has been fabricated by a one-step electrochemical immobilisation of glucose oxidase in a polypyrrole film. The sensor shows a remarkable rejection of electroactive interferences, especially paracetamol. The maximum bias observed in the worst situation never exceeded the value of 6%. The fabrication procedure delivered very reproducible devices and the sensitivity of a newly prepared biosensor was typically 650 nA mM(-1) cm(-2). The kinetic parameters, obtained from an existing model, permitted to understand the sensor behaviour.     

Analytical characterization of poly(pyrrole-3-carboxylic acid) films electrosynthesised on Pt, Ti and Ti/Al/V substrates

With the aim of developing a polymeric multilayer film for application in advanced biomaterials, as a first step poly(pyrrole-3-carboxylic acid) films (abbreviated as PPy-3-carbox) were electropolymerised from pyrrole-3-carboxylic acid solutions by cyclic voltammetry and chronoamperometry on platinum, titanium and Ti90Al6V4 substrates and characterised both electrochemically (cyclic voltammetry) and spectroscopically (X-Ray Photoelectron Spectroscopy, XPS). Electrochemical experiments showed that the potential range adopted for electropolymerization affects the polymer electroactivity, by analogy with unsubstituted polypyrrole. The combination of conventional and chemical derivation-XPS provided information on PPy-3-carbox surface structure, showing no significant difference between films grown on different substrates and an increase of the COOH groups amount (one group over three pyrrole rings, as an average) with respect to unsubstituted polypyrrole (PPy), as expected. Finally, a preliminary Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) investigation was performed in order to get further information on the polymer structure and electroactivity.     

Catalytic currents in fused salts: Discharge mechanism of nitrite in molten alkali nitrates(II)

The electrooxidation of NO₂^? ion in the (Na,K)NO₃ eutectic mixture containing water in the concentration range 10^?6–10^?2 mol kg^?1 has been studied on a platinum RDE. More work was done to confirm the preliminary mechanism reported by the authors:

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In the course of the present study step (a) was found to be potential determining under all experimental conditions while step (b) behaves as a “true” equilibrium reaction. By an approximate method based on the reaction layer concept the equilibrium constant for reaction (b) K=K′/[NO₃^?]=[H⁺]²[NO₂^?]/[NO₂]²[H₂O] was calculated. In the given nitrate solvent it was found to be K=(2.90±0.56)×10^?1 at 520 K. A value of ΔH equal to ?125.2 kJ mol^?1 was obtained on the basis of the temperature dependence of the equilibrium constant in the range 505–566 K.     

Oxygen electrodes in fused salts: Investigation and mechanistic remarks on the system (Ni)CO2, O2/CO32− in molten (Na,K)NO3

A potentiometric investigation on the system (Ni)CO₂, O₂/CO₃^2? was carried out at 507–637 K in the (Na, K)NO₃ equimolar mixture containing carbonate ions in the range 10^?5≤[CO₃^2?]≤10^?2 mol kg^?1 and under a mixture of O₂ and CO₂ at variable partial pressure. The potential behaviour of the nickel electrodes was found largely dependent on the working temperature. At the highest tested temperature the system behaves irreversibly under potentiometric conditions and the potential was found to be independent of the oxygen concentration. At lower temperatures a large irreversibility of the system was still found, while a certain dependence (different from the theoretical one) of the potential on both oxygen and carbon dioxide partial pressure was experimentally demonstrated. The entire set of results was interpreted on the basis of the two following mechanistic models involving, in the potential determining step, solid species formed on the electrode surface by contact with the melt. Mechanism 1 (high temperature)

Mechanism 2 (low temperature)

     

Surface spectroscopic characterization of advanced polymer materials

The potential of a complementary use of X-ray photoelectron spectroscopy and static ToF-SIMS has been exploited with reference to the characterization of electron conducting polymers (polybithiophene) electrochemically synthetized. Particular attention has been focused on the problem of material stability under electrochemical switching.A coherent picture could be drawn showing that irreversible modifications of the surface chemistry occur, strongly dependent on the dryness of the solvent; moreover, the pathway of doping-undoping process can vary noticeably in dependence on the experimental conditions.     

An electrospray ionization ion trap mass spectrometric (ESI-MS-MSn) study of dehydroascorbic acid hydrolysis at neutral pH

The hydrolysis of dehydroascorbic acid (DAAH) at neutral pH and 27 degrees C was investigated by direct infusion electrospray ionisation ion trap mass spectrometry (ESI-MS). This approach permitted derivatisation and elution procedures to be avoided, reducing to the minimum extent sample manipulation and allowing a rapid and direct observation of the species involved in the reaction. Six main peaks, related to hydrated dehydroascorbate (HyDAA-) and diketogulonate (HyDKG-) anions, were observed in the mass spectra of DAAH solutions at different times of incubation and were characterised by MSn experiments. The relevant signal intensities changed with time and a model, based on the irreversible pseudo-first order HyDAA(-)-->HyDKG- conversion, fitted successfully the data obtained for dehydroascorbate. The kinetic constant of the process was (3.2 +/- 0.5) x 10(-2) min-1. The influence of metal ion traces on the hydrolysis rate was also checked, performing experiments in the presence of EDTA, and was found to be negligible.     

Determination of Commercial Animal and Vegetable Milks’ Lipid Profile and Its Correlation with Cell Viability and Antioxidant Activity on Human Intestinal Caco-2 Cells

Lipids from milk are important nutritional components, although their health effects, especially for animal milks, are still questioned. Four types of commercial milks, two semi-skimmed animal milks (bovine and goat) and two vegetable ones (soy and rice), along with their total and free lipid fractions recovered by sequential centrifugation or by ethyl acetate extraction, respectively, have been analyzed. A higher antioxidant ability, reported as Trolox equivalent antioxidant capacity, was found for all raw milks compared to that of rice. This trend was confirmed, except for soy milk, as ROS reduction in Caco-2 cells. The free lipid fraction was shown to have the highest antioxidant potential in both chemical and biological tests. Moreover, goat and soy raw milks positively regulated Caco-2 cell viability after an inflammatory stimulus. This effect was lost when their total lipid fraction was tested. Finally, only the free lipid fraction from rice milk preserved the Caco-2 viability after LPS stimulation. Our data demonstrated that the lipid profile of each milk, characterized by GC-MS analysis, could contribute to dictate its biological effects, and, although additional in vitro and in vivo studies are needed, they could support the literature re-evaluating the health effects of animal-based versus plant-based milks in the intestinal cellular model.