M. L. Curri

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.

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.

Colloidal Inorganic Nanocrystal Based Nanocomposites: Functional Materials for Micro and Nanofabrication

The unique size- and shape-dependent electronic properties of nanocrystals (NCs) make them extremely attractive as novel structural building blocks for constructing a new generation of innovative materials and solid-state devices. Recent advances in material chemistry has allowed the synthesis of colloidal NCs with a wide range of compositions, with a precise control on size, shape and uniformity as well as specific surface chemistry. By incorporating such nanostructures in polymers, mesoscopic materials can be achieved and their properties engineered by choosing NCs differing in size and/or composition, properly tuning the interaction between NCs and surrounding environment. In this contribution, different approaches will be presented as effective opportunities for conveying colloidal NC properties to nanocomposite materials for micro and nanofabrication. Patterning of such nanocomposites either by conventional lithographic techniques and emerging patterning tools, such as ink jet printing and nanoimprint lithography, will be illustrated, pointing out their technological impact on developing new optoelectronic and sensing devices.

Spontaneous emission control of colloidal nanocrystals using nanoimprinted photonic crystals

The authors report on the fabrication and optical characterizations of two-dimensional photonic crystals fabricated by nanoimprint lithography in a nanocomposite polymer incorporating highly luminescent and red emitting (CdSe)ZnS core-shell colloidal nanocrystals. Photonic crystal structures enhance the light emitted from the quantum sized nanoparticles in the composite layer by slowing the propagation speed of the photons, thus increasing the coupling to the out-of-plane radiative modes. A 200% enhancement of the light collection is achieved compared to an unpatterned sample.

Photodegradation of nalidixic acid assisted by TiO2 nanorods/Ag nanoparticles based catalyst

Two different nanosized TiO2-based catalysts supported onto glass with tailored photocatalytic properties upon irradiation by UV light were successfully employed for the degradation of nalidixid acid, a widely diffused antibacterial agent of environmental relevance known to be non-biodegradable. Anatase rod-like TiO2 nanocrystals (TiO2NRs) and a semiconductor oxide-noble metal nanocomposite TiO2 NRs/Ag nanoparticles (NPs), synthesized by colloidal chemistry routes, were cast onto glass slide and employed as photocatalysts. A commercially available catalyst (TiO2 P25), also immobilized onto a glass slide, was used as a reference material. It was found that both TiO2 NRs/Ag NPs composite and TiO2 NRs demonstrated a photocatalytic efficiency significantly higher than the reference TiO2 P25. Specifically, TiO2 NRs/Ag NPs showed a photoactivity in nalidixic acid degradation 14 times higher than TiO2 P25 and 4 times higher than bare TiO2 NRs in the first 60min of reaction. Several by-products were identified by HPLC-MS along the nalidixic acid degradation, thus getting useful insight on the degradation pathway. All the identified by-products resulted completely removed after 6h of reaction.

Luminescent nanocrystals in phospholipid micelles for bioconjugation : An optical and structural investigation

Organic capped luminescent CdSe@ZnS nanocrystals (NCs) have been incorporated in block copolymer micelles, formed by polyethylene glycol modified phospholipids (PEG lipids). The obtained water soluble NC including PEG lipid micelles have been conjugated with bovine serum albumine (BSA). The entire process has been investigated by using optical, structural and electrophoretic complementary techniques. Such an integrated approach has allowed to elucidate critical issues, such as the time and temperature effects on the phase behavior of the PEG lipid/NC aggregate structures, the emitting properties of the NCs before and after micelle formation and bio-conjugation and the effect of conjugation on the biological moiety. The overall results provide relevant insight on the fabrication of the bio-conjugates, on their stability and on preparative procedure reproducibility, in view of the use of the resulting protein decorated NCs as multifunctional hybrid building blocks for the fabrication of a variety of supramolecular assemblies to exploit in biological sensing and diagnostic applications.