A. Agostiano

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.

Nanocomposites based on highly luminescent nanocrystals and semiconducting conjugated polymer for inkjet printing.

In this work nanocomposites based on organic-capped semiconductor nanocrystals formed of a core of CdSe coated with a shell of ZnS (CdSe@ZnS), with different sizes, and a semiconducting conjugated polymer, namely poly[(9,9-dihexylfluoren-2,7-diyl)-alt- (2,5-dimethyl-1,4-phenylene)] (PF-DMB) have been investigated. The nanocomposites are prepared by mixing the pre-synthesized components in organic solvents, thereby assisting the dispersion of the organic-coated nano-objects in the polymer host. UV-vis steady state and time-resolved spectroscopy along with (photo)electrochemical techniques have been performed to characterize the obtained materials. The study shows that the embedded nanocrystals increase the PF-DMB stability against oxidation and, at the same time, extend the light harvesting capability to the visible spectral region, thus resulting in detectable photocurrent signals. The nanocomposites have been dispensed by means of a piezo-actuated inkjet system. Such inks present viscosity and surface tension properties well suited for stable and reliable drop-on-demand printing using an inkjet printer. The fabrication of arrays of single-color pixels made of the nanocomposites and micrometers in size has been performed. Confocal and atomic force microscopy have confirmed that inkjet-printed microstructures present the intrinsic emission properties of both the embedded nanocrystals and PF-DMB, resulting in a combined luminescence. Finally, the morphology of the printed pixels is influenced by the embedded nanofillers.

Polyelectrolyte multilayers as a platform for luminescent nanocrystal patterned assemblies.

The fabrication of uniform and patterned nanocrystal (NC) assemblies has been investigated by exploiting the possibility of carefully tailoring colloidal NC surface chemistry and the ability of polyelectrolyte (PE) to functionalize substrates through an electrostatic layer-by-layer (LbL) strategy. Appropriate deposition conditions, substrate functionalization, and post-preparative treatments were selected to tailor the substrate surface chemistry to effectively direct the homogeneous electrostatic-induced assembly of NCs. Water-dispersible luminescent NCs, namely, (CdSe)ZnS and CdS, were differently functionalized by (1) ligand-exchange reaction, (2) growth of a hydrophilic silica shell, and (3) formation of a hydrophilic inclusion complex, thus providing functional NCs stable in a defined pH range. The electrostatically charged functional NCs represent a comprehensive selection of examples of surface-functionalized NCs, which enables the systematic investigation of experimental parameters in NC assembly processes carried out by combining LbL procedures with microcontact printing and also exploiting NC emission, relevant for potential applications, as a prompt and effective probe for evaluating assembly quality. Thus, an ample showcase of combinations has been investigated, and the spectroscopic and morphological features of the resulting NC-based structures have been discussed.

Isolation of Squarebop I bacteriorhodopsin from biomass of coastal salterns

Squarebop I bacteriorhodopsin is a light-activated proton pump present in the membranes of the archeon Haloquadratum walsbyi, a square-shaped organism representing 50-60% of microbial population in the crystallizer ponds of the coastal salterns. Here we describe: (1) the operating mode of a bioreactor designed to concentrate the saltern biomass through a microfiltration process based on polyethersulfone hollow fibers; (2) the isolation of Squarebop I bacteriorhodopsin from solubilized biomass by means of a single chromatographic step; (3) tightly bound lipids to the isolated and purified protein as revealed by MALDI-TOF/MS analysis; (4) the photoactivity of Squarebop I bacteriorhodopsin isolated from environmental samples by flash spectroscopy. Yield of the isolation process is 150 μg of Squarebop I bacteriorhodopsin from 1l of 25-fold concentrated biomass. The possibility of using the concentrated biomass of salterns, as renewable resource for the isolation of functional bacteriorhodopsin and possibly other valuable bioproducts, is briefly discussed.

Phase transfer of CdS nanocrystals mediated by heptamine Beta-cyclodextrin

A fundamental and systematic study on the fabrication of a supramolecularly assembled nanostructure of an organic ligand-capped CdS nanocrystal (NC) and multiple heptamine β-cyclodextrin ((NH(2))(7)βCD) molecules in aqueous solution has been here reported. The functionalization process of presynthesized hydrophobic CdS NCs by means of (NH(2))(7)βCD has been extensively investigated by using different spectroscopic and structural techniques, as a function of different experimental parameters, such as the composition and the concentration of CD, the concentration of CdS NCs, the nature of the NC surface capping ligand (oleic acid and octylamine), and the organic solvent. The formation of a complex based on the direct coordination of the (NH(2))(7)βCD amine groups at the NC surface has been demonstrated and found responsible for the CdS NC phase transfer process. The amine functional group in (NH(2))(7)βCD and the appropriate combination of pristine capping agent coordinating the NC surface and a suitable solvent have been found decisive for the success of the CdS NC phase transfer process. Furthermore, a layer-by-layer assembly experiment has indicated that the obtained (NH(2))(7)βCD functionalized CdS NCs are still able to perform the host-guest chemistry. Thus, they offer a model of a nanoparticle-based material with molecular receptors, useful for bio applications.

First-principles study of trimethylamine adsorption on anatase TiO2 nanorod surfaces

Titanium dioxide (TiO2) nanorods are widely employed in many energy-related applications thanks to their peculiar electronic and physicochemical properties. Here we report a periodic DFT and DFT-D study of the three most exposed surfaces of stoichiometric anatase TiO2 nanorods, i.e., (100), (001) and (101). On these surfaces, we investigated the adsorption of a tertiary amine (trimethylamine, TMA): Energetic, structural and electronic features have been characterized, paying particular attention on the effects of dispersion forces on the adsorption process. We found evidence of the formation of a coordinative bond between the molecules and the titanium site of adsorption. As expected, the inclusion of dispersion correction strongly enhances the adsorption process. Moreover, in some cases TMA adsorption introduces new electronic states at the edge of the valence band. Overall, our results provide new insights on the interactions between TiO2 nanorods and nitrogen compounds, which have many scientific and technological implications.

Semiquinone oscillations as a tool for investigating the ubiquinone binding to photosynthetic reaction centers.

Semiquinone oscillations induced by light pulses in the presence of exogenous electron donors are a valuable source of information on the kinetics and thermodynamics of ubiquinone chemistry relevant to the QB site of the photosynthetic reaction center (RC). In previous attempts to achieve the quantitative interpretation of data, the ubiquinone concentration was considered constant during the experiment since it was much bigger than that of RC. In this work, we extended existing models to low ubiquinone concentrations revealing several hidden processes taking place during the ubiquinone photoreduction and enabling the evaluation of the ubiquinone binding constant KQ at the QB site. The proposed approach provides for the first time the evaluation of KQ without any preliminary treatment of ubiquinone extraction from the binding site, thereby better preserving its native structure.

Plasmonics Meets Biology through Optics

Plasmonic metallic nanoparticles (NPs) represent a relevant class of nanomaterials, which is able to achieve light localization down to nanoscale by exploiting a phenomenon called Localized Plasmon Resonance. In the last few years, NPs have been proposed to trigger DNA release or enhance ablation of diseased tissues, while minimizing damage to healthy tissues. In view of the therapeutic relevance of such plasmonic NPs; a detailed characterization of the electrostatic interaction between positively charged gold nanorods (GNRs) and a negatively charged whole-genome DNA solution is reported. The preparation of the hybrid biosystem has been investigated as a function of DNA concentration by means of ζ-potential; hydrodynamic diameter and gel electrophoresis analysis. The results have pointed out the specific conditions to achieve the most promising GNRs/DNA complex and its photo-thermal properties have been investigated. The overall study allows to envisage the possibility to ingeniously combine plasmonic and biological materials and, thus, enable design and development of an original non invasive all-optical methodology for monitoring photo-induced temperature variation with high sensitivity.