Elisabetta Fanizza

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.

A New Complex of Curcumin with Sulfobutylether‐β‐Cyclodextrin: Characterization Studies and In Vitro Evaluation of Cytotoxic and Antioxidant Activity on HepG‐2 Cells

Curcumin (CR) is a natural polyphenol with antioxidative, anti-inflammatory, and anticancer properties but its therapeutic potential is substantially hindered by the rather low-water solubility and bioavailability. Thus, in this work, a new soluble inclusion complex of CR with sulfobutylether-β-cyclodextrin (SBE-β-CD) was prepared in solution and at the solid state using different preparation techniques and characterized by Fourier transform infrared, nuclear magnetic resonance, differential scanning calorimetry, scanning electron microscopy, phase solubility studies, and Jobs plot method. Results clearly indicate that CR reacts with SBE-β-CD to form a host-guest complex with an apparent formation constant of 1455 M(-1) . Moreover, SBE-β-CD strongly increases water solubility of CR (from 0.56 to 102.78 μg/mL, at 25°C), and lyophilization method seems to be the best preparation technique to obtain the complex at the solid state. Finally, an in vitro test on a human hepatic cancer cell line (HepG-2) shows that complexation positively influences CR anticancer and antioxidant activity.

Red-emitting AIEgen for luminescent solar concentrators

This study reports for the first time the use of a red-emitting AIEgen, i.e. TPE-AC, for the realization of efficient luminescent solar concentrators (LSCs) based on poly(methyl methacrylate) (PMMA) and polycarbonate (PC) thin films (25 ± 5 μm). TPE-AC is an AIEgen with D–A features that absorbs visible light in the range between 400 and 550 nm and emits fluorescence peaked at 600–620 nm, with a maximum quantum yield (QY) of 50% when dispersed (0.1–1.5 wt%) in PMMA and PC matrices. QY and lifetime investigations demonstrated that fluorescence quenching occurred with varying the TPE-AC concentration, even if the optical features were still significant even at the highest fluorophore content. Study of the LSCs’ performances yielded worthy optical efficiencies of 6.7% for the TPE-AC/PC systems due to their superior light harvesting features and the compatibility of the AIEgen within the PC matrix.

Cost-effective solar concentrators based on red fluorescent Zn(II)–salicylaldiminato complex

Sunlight concentration is a promising path to cost-effective photovoltaic (PV) technologies. Compared to standard concentrators based on geometrical optics, luminescent solar concentrators (LSCs) appear to be viable and convenient alternatives because sunlight concentration to PV occurs with diffuse light and there is no need for sun tracking or cooling apparatuses. In this study, we report on the optical efficiencies of luminescent solar concentrators (LSCs) based on poly(methyl methacrylate) (PMMA) thin films doped with a red-emitting zinc(II) complex of the D–A–D type ligand N,N′-bis(2-hydroxy-1-naphthylidene)-diaminomaleonitrile (ZnL). ZnL is attractive for use in LSC owing to its easy and cheap synthesis. ZnL in PMMA shows an emission band at 624 nm, a Stokes shift of 34 nm and an average QY of 23%, data comparable to those recorded in solution and efficiently predicted by DFT calculations. A study of ZnL/PMMA LSC yields optical efficiencies of 7%, which is comparable to those based on the near unity QY fluorophores such as Lumogen Red. These performances were attributed to the higher emission red-shift and larger Stokes shift of ZnL that prevent the loss of efficiencies due to self-absorption and possibly circumvent its lower QY.

Spray-dried mucoadhesives for intravesical drug delivery using N-acetylcysteine- and glutathione-glycol chitosan conjugates.

UNLABELLED This work describes N-acetylcysteine (NAC)- and glutathione (GSH)-glycol chitosan (GC) polymer conjugates engineered as potential platform useful to formulate micro-(MP) and nano-(NP) particles via spray-drying techniques. These conjugates are mucoadhesive over the range of urine pH, 5.0-7.0, which makes them advantageous for intravesical drug delivery and treatment of local bladder diseases. NAC- and GSH-GC conjugates were generated with a synthetic approach optimizing reaction times and purification in order to minimize the oxidation of thiol groups. In this way, the resulting amount of free thiol groups immobilized per gram of NAC- and GSH-GC conjugates was 6.3 and 3.6mmol, respectively. These polymers were completely characterized by molecular weight, surface sulfur content, solubility at different pH values, substitution and swelling degree. Mucoadhesion properties were evaluated in artificial urine by turbidimetric and zeta (ζ)-potential measurements demonstrating good mucoadhesion properties, in particular for NAC-GC at pH 5.0. Starting from the thiolated polymers, MP and NP were prepared using both the Büchi B-191 and Nano Büchi B-90 spray dryers, respectively. The resulting two formulations were evaluated for yield, size, oxidation of thiol groups and ex-vivo mucoadhesion. The new spray drying technique provided NP of suitable size (<1μm) for catheter administration, low degree of oxidation, and sufficient mucoadhesion property with 9% and 18% of GSH- and NAC-GC based NP retained on pig mucosa bladder after 3h of exposure, respectively. STATEMENT OF SIGNIFICANCE The aim of the present study was first to optimize the synthesis of NAC-GC and GSH-GC, and preserve the oxidation state of the thiol moieties by introducing several optimizations of the already reported synthetic procedures that increase the mucoadhesive properties and avoid pH-dependent aggregation. Second, starting from these optimized thiomers, we studied the feasibility of manufacturing MP and NP by spray-drying techniques. The aim of this second step was to produce mucoadhesive drug delivery systems of adequate size for vesical administration by catheter, and comparable mucoadhesive properties with respect to the processed polymers, avoiding thiolic oxidation during the formulation. MP with acceptable size produced by spray-dryer Büchi B-191 were compared with NP made with the apparatus Nano Büchi B-90.

Electroactive layer-by-layer plasmonic architectures based on Au nanorods.

Nanostructured films based on Au nanorods (NRs) have been obtained by layer-by-layer (LbL) assembly driven by electrostatic interaction between metal nanoparticles and polyelectrolytes. Multilayer films have been fabricated by using LbL assembly of poly(sodium styrenesulfonate) (PSS) and positively charged Au NRs on a polyelectrolyte-modified substrate. The effect of fabrication parameters, including the nature of the substrate, the polyelectrolyte initial anchoring layer, and the number of layers has been investigated by means of UV-vis absorbance spectroscopy and atomic force microscopy (AFM). The results demonstrated the dependence of morphology and plasmonic features in the multilayered nanostructured architectures from the nature of the anchoring polyelectrolyte on the substrate, the number of layers, and the kind of NR mutual assembly. In addition, a study of the electrochemical activity at the solid/liquid interface has been carried out in order to assess charge transport through the NR multilayer by using two molecular probes in solution, namely, potassium ferricyanide, a common and well-established redox mediator with reversible behavior, and cytochrome C, a robust model redox protein. The presented systematic study of the immobilization of Au NRs opens the venue to several application areas, such as (bio)chemical sensing.

Selective confinement of oleylamine capped Au nanoparticles in self-assembled PS-b-PEO diblock copolymer templates

Amphiphilic polystyrene-block-polyethylene oxide (PS-b-PEO) block copolymers (BCPs) have been demonstrated to be effective in directing organization of colloidal Au nanoparticles (NPs). Au NPs have been incorporated into the polymer and the different chemical affinity between the NP surface and the two blocks of the BCP has been used as a driving force of the assembling procedure. The morphology of the nanocomposites, prepared and fabricated as thin films, has been investigated by means of atomic force and scanning electron microscopies as a function of the NP content and BCP molecular weight. NPs have been effectively dispersed in PS-b-PEO hosts at any investigated content (up to 17 wt%) and a clear effect of the BCP properties on the final nanocomposite morphology has been highlighted. Finally, electrostatic force microscopy has demonstrated the conductive properties of the nanocomposite films, showing that the embedded Au NPs effectively convey their conductive properties to the film. The overall investigation has confirmed the selective confinement of the as-prepared surfactant-coated metal NPs in the PS block of PS-b-PEO, thus proposing a very simple and prompt assembling tool for nanopatterning, potentially suitable for optoelectronic, sensing and catalysis applications.

Integrin-targeting with peptide-bioconjugated semiconductor-magnetic nanocrystalline heterostructures

Binary asymmetric nanocrystals (BNCs), composed of a photoactive TiO2 nanorod joined with a superparamagnetic γ-Fe2O3 spherical domain, were embedded in polyethylene glycol modified phospholipid micelle and successfully bioconjugated to a suitably designed peptide containing an RGD motif. BNCs represent a relevant multifunctional nanomaterial, owing to the coexistence of two distinct domains in one particle, characterized by high photoactivity and magnetic properties, that is particularly suited for use as a phototherapy and hyperthermia agent as well as a magnetic probe in biological imaging. We selected the RGD motif in order to target integrin expressed on activated endothelial cells and several types of cancer cells. The prepared RGD-peptide/BNC conjugates, comprehensively monitored by using complementary optical and structural techniques, demonstrated a high stability and uniform dispersibility in biological media. The cytotoxicity of the RGD-peptide/BNC conjugates was studied in vitro. The cellular uptake of RGD-peptide conjugates in the cells, assessed by means of two distinct approaches, namely confocal microscopy analysis and emission spectroscopy determination in cell lysates, displayed selectivity of the RGD-peptide-BNC conjugate for the αvβ3 integrin. These RGD-peptide-BNC conjugates have a high potential for theranostic treatment of cancer.

Single white light emitting hybrid nanoarchitectures based on functionalized quantum dots

Colloidal white emitting nanostructures were successfully fabricated by covalently binding a blue emitting oligofluorene at the surface of silica beads, that incorporate orange luminescent colloidal CdSe@ZnS quantum dots (QDs). White light was achieved by carefully tuning the size of the QDs to complementarily match the emission color of the blue fluorophore and taking into account the delicate balance between the emission of the QDs in the core of the silica beads and the amount of the organic dye bound to the silica surface. The proposed approach is highly versatile as it can be extended to the fabrication of a variety of luminescent hybrid nano-objects, playing with the complementarity of the emission color of the inorganic and organic fluorophores at the nanoscale.

Plasmon mediated super-absorber flexible nanocomposites for metamaterials

A flexible host has been selected to achieve, for the first time, functional nanocomposites based on CdSe@ZnS core-shell type quantum dots (QDs) and Au nanoparticles (NPs), simultaneously dispersed in a polymer matrix. Coherent interactions between QDs and plasmonic Au NPs embedded in PDMS films have been demonstrated to lead to a relevant enhancement of the absorption cross-section of the QDs, remarkably modifying the optical response of the entire system. Optical and time resolved spectroscopy studies revealed an active gain-plasmon feedback behind the super-absorbing overall effect.