Emanuela Filippo

A new amperometric nanostructured sensor for the analytical determination of hydrogen peroxide

A new amperometric, nanostructured sensor for the analytical determination of hydrogen peroxide is proposed. This sensor was constructed by immobilizing silver nanoparticles in a polyvinyl alcohol (PVA) film on a platinum electrode, which was performed by direct drop-casting silver nanoparticles that were capped in a PVA colloidal suspension. UV-vis spectroscopy, X-ray diffraction and transmission electron microscopy were used to give a complete characterization of the nanostructured film. Cyclic voltammetry experiments yielded evidence that silver nanoparticles facilitate hydrogen peroxide reduction, showing excellent catalytic activity. Moreover, the cronoamperometric response of modified sensors was dependent on nanoparticle lifetime. Experiments were performed, using freshly prepared solutions, after 4 and 8 days. Results concerning the quantitative analysis of hydrogen peroxide, in terms of detection limit, linear range, sensitivity and standard deviation (STD), are discussed for each tested sensor type. Utilization of two different linear ranges (40 microM to 6mM and 1.25 microM to 1.0mM) enabled the assessment of concentration intervals having up to three orders of magnitude. Moreover, the electrode made using a 4-day-old solution showed the maximal sensitivity of 128 nA microM(-1)(4090 nA microM(-1)cm(-2)), yielding a limit of detection of 1 microuM and STD of 2.5 microAmM(-1). All of these analytical parameters make the constructed sensors suitable for peroxide determination in aqueous solution.

A novel nonenzymatic amperometric hydrogen peroxide sensor based on CuO@Cu2O nanowires embedded into poly(vinyl alcohol).

A new, very simple, rapid and inexpensive nonenzymatic amperometric sensor for hydrogen peroxide (H2O2) detection is proposed. It is based on the immobilization of cupric/cuprous oxide core shell nanowires (CuO@Cu2O-NWs) in a poly(vinyl alcohol) (PVA) matrix directly drop casted on a glassy carbon electrode surface to make a CuO@Cu2O core shell like NWs PVA embedded (CuO@Cu2O-NWs/PVA) sensor. CuO nanowires with mean diameters of 120-170nm and length in the range 2-5μm were grown by a simple catalyst-free thermal oxidation process based on resistive heating of pure copper wires at ambient conditions. The oxidation process of the copper wire surface led to the formation of a three layered structure: a thick Cu2O bottom layer, a CuO thin intermediate layer and CuO nanowires. CuO nanowires were carefully scratched from Cu2O layer with a sharp knife, dispersed into ethanol and sonicated. Then, the NWs were embedded in PVA matrix. The morphological and spectroscopic characterization of synthesized CuO-NWs and CuO@Cu2O-NWs/PVA were performed by transmission electron microscopy (TEM), selected area diffraction pattern (SAD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) analysis. Moreover a complete electrochemical characterization of these new CuO@Cu2O-NWs/PVA modified glassy carbon electrodes was performed by Cyclic Voltammetry (CV) and Cronoamperometry (CA) in phosphate buffer (pH=7; I=0.2) to investigate the sensing properties of this material against H2O2. The electrochemical performances of proposed sensors as high sensitivity, fast response, reproducibility and selectivity make them suitable for the quantitative determination of hydrogen peroxide substrate in batch analysis.

Non-functionalized silver nanoparticles for a localized surface plasmon resonance-based glucose sensor

The optical properties of non-functionalized silver nanoparticles in ethanol solution have been analyzed and a progressive shift of localized surface plasmon resonances caused by the adding of increasing quantities of glucose has been observed. To understand this occurrence, the interaction of glucose molecules with the silver nanoparticle surface has been investigated using Raman spectroscopy. In addition, high resolution transmission electron microscopy shows the presence of superstructures on the silver nanoparticle surface that can be imputed to the presence of glucose.

Structural and electrical properties of In2O3/SeO2 thin films for gas-sensing applications

In this work, we report about the analysis of structural, physical, and gas-sensing properties of a new sensing material made by mixing In2O3 and SeO2. The In2O3/SeO2 thin films have been obtained by thermal evaporation of In:Se in a 2:1 ratio and subsequent thermal annealing in an oxygen flow. In order to investigate the structure and the morphology of the films obtained, high-resolution transmission electron microscopy, small-area electron diffraction, and digital image processing were performed on thermally annealed films. The Hall effect and resistivity measurements of such films have been carefully analysed. In addition, In2O3/SeO2 mixed oxide films were tested in a controlled atmosphere and the electrical conductance changes were measured as a function of temperature. The sensing behaviour of such films has been analysed according to an adsorption kinetic model, which related the conductivity variation to gas concentrations, time exposure, and working temperature.

Enhanced Photocatalytic Activity of Pure Anatase Tio2 and Pt-Tio2 Nanoparticles Synthesized by Green Microwave Assisted Route

High-yield, rapid and facile synthesis of elongated pure anatase titania nanoparticles has been achieved through a nonaqueous microwave-based approach. The residual organics onto nanoparticles surfaces were completely removed through a new treatment under ozone flow, at room temperature in air. Such an ozone cleaning method revealed an effective inexpensive dry process of removing organic contaminants from nanoparticles surfaces. The TiO2 elongated nanoparticles having a length of 13.8 ± 5.5 nm and a diameter of 9.0 ±1.2 nm were characterized by powder X-Ray diffraction, transmission electron microscopy, selected area diffraction, BET surface area analyzer and FT-IR spectroscopy. Photocatalytic evaluation demonstrated that the as-synthesized ozone-cleaned TiO2 nanoparticles and TiO2 nanoparticles loaded with platinum possess excellent Rhodamine B performance with respect to both commercial spherical nanotitania P25 and P25 loaded with platinum. This could be attributed to the anatase phase purity, small size, large specific surface area and clean surfaces of the prepared nanoparticles.

Monitoring prion protein expression in complex biological samples by SERS for diagnostic applications.

Surface-enhanced Raman spectroscopy (SERS) allows a new insight into the analysis of cell physiology. In this work, the difficulty of producing suitable substrates that, besides permitting the amplification of the Raman signal, do not interact with the biological material causing alteration, has been overcome by a combined method of hydrothermal green synthesis and thermal annealing. The SERS analysis of the cell membrane has been performed with special attention to the cellular prion protein PrP(C). In addition, SERS has also been used to reveal the prion protein-Cu(II) interaction in four different cell models (B104, SH-SY5Y, GN11, HeLa), expressing PrP(C) at different levels. A significant implication of the current work consists of the intriguing possibility of revealing and quantifying prion protein expression in complex biological samples by a cheap SERS-based method, replacing the expensive and time-consuming immuno-assay systems commonly employed.

Photoconductivity of packed homotype bundles formed by aligned single-walled carbon nanotubes.

Photoconductivity properties of aggregated single-walled carbon nanotubes have been studied by performing measurements on macroscopic ribbons, obtained by the aggregation of a large number of SWCNT bundles. Structural analysis performed by electron diffraction revealed that the nanotubes forming each bundle have the same chirality. The experimental results, regarding the region 1.2-3.6 eV and the pressure range 10(3)-10(-3) mbar, suggest that the photoexcitation of nanotubes, packed in bundles and organized in ribbons, generates electron-hole pairs within a band structure and that bond excitons are formed by Coulomb interactions between spatially confined charge carriers.

High ordered biomineralization induced by carbon nanoparticles in the sea urchin Paracentrotus lividus

A surprising and unexpected biomineralization process was observed during toxicological assessment of carbon nanoparticles on Paracentrotus lividus (sea urchin) pluteus larvae. The larvae activate a process of defense against external material, by incorporating the nanoparticles into microstructures of aragonite similarly to pearl oysters. Aiming at a better understanding of this phenomenon, the larvae were exposed to increasing concentrations of carbon nanoparticles and the biomineralization products were analyzed by electron microscopy, x-ray diffraction and Raman spectroscopy. In order to evaluate the possible influence of Sp-CyP-1 expression on this biomineralization process by larvae, analyses of gene expression (Sp-CyP-1) and calcein labeling were performed. Overall, we report experimental evidence about the capability of carbon nanoparticles to induce an increment of Sp-CyP-1 expression with the consequent activation of a biomineralization process leading to the production of a new pearl-like biomaterial never previously observed in sea urchins.

Properties of nanocrystals-formulated aluminosilicate bricks

In the present work, seven different types of nanocrystals were studied as additives in the formulation of aluminosilicate bricks. The considered nanocrystals consisted of anatase titanium dioxide (two differently shaped types), boron modified anatase, calcium carbonate (in calcite phase), aluminium hydroxide and silicon carbide (of two diverse sizes), which were prepared using different methods. Syntheses aim to give a good control over a particles size and shape. Anatase titania nanocrystals, together with the nano-aluminium hydroxide ones, were synthesized via microwave-assisted procedures, with the use of different additives and without the final calcination steps. The silicon carbide nanoparticles were prepared via laser pyrolysis. The nano-calcium carbonate was prepared via a spray drying technique. All of the nanocrystals were tested as fillers (in 0.5, 1 and 2 wt. % amounts) in a commercial aluminosilicate refractory (55 % Al2O3, 42 % SiO2). They were used to prepare bricks that were thermally treated at 1300 °C for 24 hours, according to the international norms. The differently synthesized nanocrystals were added for the preparation of the bricks, with the aim to improve their heat-insulating and/or mechanical properties. The nanocrystals-modified refractories showed variations in properties, with respect to the untreated aluminosilicate reference in heat-insulating performances (thermal diffusivities were measured by the “hot disk” technique). In general, they also showed improvements in mechanical compression resistance for all of the samples at 2 wt. %. The best heat insulation was obtained with the addition of nano-aluminium hydroxide at 2 wt. %, while the highest mechanical compression breaking resistance was found with nano-CaCO3 at 2 wt. %. These outcomes were investigated with complementary techniques, like mercury porosimetry for porosity, and Archimedes methods to measure physical properties like the bulk and apparent densities, apparent porosities and water absorption. The results show that the nano-aluminium hydroxide modified bricks were the most porous, which could explain the best heat-insulating performances. There is a less straightforward explanation for the mechanical resistance results, as they may have relations with the characteristics of the pores. Furthermore, the nanoparticles may have possible reactions with the matrix during the heat treatments.

Optical, morphological and structural characterization of Langmuir–Schaefer films of a functionalized copper phthalocyanine

Langmuir-Schaefer (LS) films of copper(II) tetrakis-(isoprpoxy-carbonyl)-phthalocyanine (TiPCuPc) have been deposited onto various solid supports. Its floating film have been characterized at the air-water interface by means of Brewster Angle Microscopy and Langmuir curves. Vibrational modes of multilayer transferred LS film have been studied by Raman spectroscopy and the optical parameters (refractive index n and extinction coefficient k) have been determined in the visible range of the electromagnetic spectrum. Linearly polarized light absorbance measurements have been performed at room temperature in the 400-800 nm spectral range and the average orientation of the phthalocyanine rings have been estimated. Transmission electron microscopy has been also used to characterize the morphological properties of the LS film and a close packed arrangement of the deposited molecules has been observed.