Angela Agostiano

Colloidal oxide nanoparticles for the photocatalytic degradation of organic dye

Abstract In this work, easily processable and highly crystalline ZnO and TiO2 nanoparticles, with a narrow size distribution, obtained by using novel non-hydrolytic synthetic approaches were both tested for the photocatalyzed degradation of an organic dye, methyl red (2-(4-Dimethylamino-phenylazo)-benzoic acid)—C.I. 13020) and their behaviour comparatively examined with respect to TiO2 and ZnO commercial powders. The experiments were carried out using semiconducting oxides under UV and visible light illumination. Preliminary studies on the influence of various experimental factors as pH and dye concentration were performed. The obtained results demonstrated a high photocatalytic efficiency of nanosized semiconducting particles.

Optical properties of hybrid composites based on highly luminescent CdS nanocrystals in polymer

High quality luminescent CdS nanocrystals (NCs), with band edge emission tunable in the blue region of the visible spectrum, were synthesized by means of thermal decomposition of precursors with oleic acid as the surfactant and incorporated in optically transparent polystyrene (PS) and poly(methyl methacrylate) (PMMA). The optical properties of the obtained nanocomposite films were investigated by absorption and emission spectroscopies. Enhancement of the band edge luminescence of CdS quantum dots was observed in both polymer matrices and the fluorescence of the composites retained narrow emission profiles. Capping exchange at the NC surface with octylamine, demonstrated to improve the luminescence properties in solution, was performed in order to investigate the role played by surface ligands in the nanocomposite. Octylamine capped NCs immobilized in the polymers showed high defect state emission and visible quenching of band edge luminescence, indicating an effective interaction between oleic acid and PMMA and PS polymeric chains.

Development of a novel enzyme/semiconductor nanoparticles system for biosensor application

Abstract Nanosized semiconductor crystals can increase efficiency of photochemical reactions and can be effectively coupled to biomolecular units, such as enzyme, to generate novel photoelectrochemical systems. In this work, nanocrystalline CdS has been synthesized by using a microemulsive system and immobilised by self-assembling on a gold electrode in order to prepare, combined with formaldehyde dehydrogenase (FDH) enzyme, a biological-inorganic hybrid able to perform catalytic oxidation of formaldehyde. The preliminary results indicate that quantum-sized CdS layer on gold, in close contact with the enzyme, is an effective photoactive material to replace the NAD+/NADH role as charge transfer in the enzymatic reaction.

An electrochemical sewage treatment process

Electrolysis of mixtures of sea water and waste water from a secondary treatment plant has been studied; the current density and the inter-electrode gap were varied. The results show a fast elimination of phosphorus compounds under favourable conditions. The rate of nitrogen removal is dependent on the formation, and subsequent degradation, of chloramines. In order to avoid the diffusion of the anodic products to the cathode, diaphragms of different materials were used; the best results were obtained with a cellulose pressed diaphragm. The energy consumptions for a phosphorus removal of 40 and 60% were 0.075 and 0.1 kWh m−3 of treated sewage, respectively.

TiO2 nanorods/PMMA copolymer-based nanocomposites: highly homogeneous linear and nonlinear optical material

Original nanocomposites have been obtained by direct incorporation of pre-synthesized oleic acid capped TiO(2) nanorods into properly functionalized poly(methyl methacrylate) copolymers, carrying carboxylic acid groups on the repeating polymer unit. The presence of carboxylic groups on the alkyl chain of the host functionalized copolymer allows an highly homogeneous dispersion of the nanorods in the organic matrix. The prepared TiO(2)/PMMA-co-MA nanocomposites show high optical transparency in the visible region, even at high TiO(2) nanorod content, and tunable linear refractive index depending on the nanoparticle concentration. Finally measurements of nonlinear optical properties of TiO(2) polymer nanocomposites demonstrate a negligible two-photon absorption and a negative value of nonlinear refractive index, highlighting the potential of the nanocomposite for efficient optical devices operating in the visible region.

Spectroscopic study on imidazolium-based ionic liquids: effect of alkyl chain length and anion.

Room temperature ionic liquids are currently used as functional materials in several application and their optical investigation can provide a better understanding of their physical and chemical behavior. Absorption and emission properties of imidazolium-based ILs have been attributed to the imidazolium moiety and related to the presence of energetically different aggregates. Here, time-integrated and time-resolved investigation has been carried out on 1-alkyl-3-methylimidazolium tetrafluoroborate and hexafluorophosphate ionic liquids with different chain lengths in order to probe the occurrence of energy transfer processes, and hence to disclose the presence of various states with different energy. Such a study contributes to provide relevant insight on the effect of alkyl chain and anion type on the emission characteristics, and, hence, on the presence of associated structures.

High quality CdS nanocrystals: surface effects

Stable and highly luminescent CdS nanocrystals (NCs) have been synthesized by means of decomposition of suitable precursors (CdO and elemental sulphur) in octadecene (ODE) and oleic acid at high temperature. Absorption and steady state photoluminescence (PL) measurements have been carried out to study the intrinsic properties of nanocrystals and the effect of ligand and solvent on emission properties. Ageing of nanocrystals has been investigated, and an efficient mechanism of emission recovery has been identified, showing the active role of non coordinating solvent and oleic acid in modifying the surface states.

Inkjet‐Printed Multicolor Arrays of Highly Luminescent Nanocrystal‐Based Nanocomposites

Inkjet technology is a compelling method for the flexible and cost-effective printing of functional inks. We show that nanocomposite solutions based on polystyrene and differently sized core/shell-type nanocrystals (NCs) formed by a CdSe core coated with a shell of ZnS (CdSe@ZnS) in a single solvent, chloroform, can be reliably dispensed into luminescent, multicolor pixel arrays. This study demonstrates the relevance of parameters like polymer concentration and nozzle diameter, highlighting how the optimal conditions to print NCs embedded in 5 wt% polystyrene nanocomposite are given by a 70-microm-diameter nozzle. The obtained structures show that the bright size-dependent emission of the NCs in the nanocomposite is retained in the printed pixels.

Instrumental and multivariate statistical analyses for the characterisation of the geographical origin of Apulian virgin olive oils.

In this paper, virgin olive oils (VOOs) coming from three different geographic origins of Apulia, were analysed for free acidity, peroxide value, spectrophotometric indexes, chlorophyll content, sterol, fatty acid, and triacylglycerol compositions. In order to predict the geographical origin of VOOs, different multivariate approaches were applied. By performing principal component analysis (PCA) a modest natural grouping of the VOOs was observed on the basis of their origin, and consequently three supervised techniques, i.e., general discriminant analysis (GDA), partial least squares-discriminant analysis (PLS-DA) and soft independent modelling of class analogy (SIMCA) were used and the results were compared. In particular, the best prediction ability was produced by applying GDA (average prediction ability of 82.5%), even if interesting results were obtained also by applying the other two classification techniques, i.e., 77.2% and 75.5% for PLS-DA and SIMCA, respectively.

Non-targeted 1H NMR fingerprinting and multivariate statistical analyses for the characterisation of the geographical origin of Italian sweet cherries.

In this study, non-targeted (1)H NMR fingerprinting was used in combination with multivariate statistical techniques for the classification of Italian sweet cherries based on their different geographical origins (Emilia Romagna and Puglia). As classification techniques, Soft Independent Modelling of Class Analogy (SIMCA), Partial Least Squares Discriminant Analysis (PLS-DA), and Linear Discriminant Analysis (LDA) were carried out and the results were compared. For LDA, before performing a refined selection of the number/combination of variables, two different strategies for a preliminary reduction of the variable number were tested. The best average recognition and CV prediction abilities (both 100.0%) were obtained for all the LDA models, although PLS-DA also showed remarkable performances (94.6%). All the statistical models were validated by observing the prediction abilities with respect to an external set of cherry samples. The best result (94.9%) was obtained with LDA by performing a best subset selection procedure on a set of 30 principal components previously selected by a stepwise decorrelation. The metabolites that mostly contributed to the classification performances of such LDA model, were found to be malate, glucose, fructose, glutamine and succinate.