Alessandro Di Mauro

Novel synthesis of ZnO/PMMA nanocomposites for photocatalytic applications

The incorporation of nanostructured photocatalysts in polymers is a strategic way to obtain novel water purification systems. This approach takes the advantages of: (1) the presence of nanostructured photocatalyst; (2) the flexibility of polymer; (3) the immobilization of photocatalyst, that avoids the recovery of the nanoparticles after the water treatment. Here we present ZnO-polymer nanocomposites with high photocatalytic performance and stability. Poly (methyl methacrylate) (PMMA) powders were coated with a thin layer of ZnO (80 nm thick) by atomic layer deposition at low temperature (80 °C). Then the method of sonication and solution casting was performed so to obtain the ZnO/PMMA nanocomposites. A complete morphological, structural, and chemical characterization was made by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analyses. The remarkable photocatalytic efficiency of the nanocomposites was demonstrated by the degradation of methylene blue (MB) dye and phenol in aqueous solution under UV light irradiation. The composites also resulted reusable and stable, since they maintained an unmodified photo-activity after several MB discoloration runs. Thus, these results demonstrate that the proposed ZnO/PMMA nanocomposite is a promising candidate for photocatalytic applications and, in particular, for novel water treatment.

Hierarchical Effect behind the Supramolecular Chirality of Silver(I)–Cysteine Coordination Polymers

Cysteine is a sulfur-containing amino acid that easily coordinates to soft metal ions and grafts to noble metal surfaces. Recently, chiroptical activity of Ag(+)/cysteine coordination polymers has been widely studied, while, on the other hand, the appearance of a plasmon-enhanced circular dichroic signal (PECD) at the plasmonic spectral region (λ > 400 nm) has been observed for AgNPs capped with chiral sulfur-containing amino acids. These two events are both potentially exploited for sensing applications. However, the presence of Ag(+) ions in AgNP colloidal solution deals with the competition of cysteine grafting at the metal NP surface and/or metal ion coordination. Herein we demonstrate that the chiroptical activity observed by adding cysteine to AgNP colloids prepared by pulsed laser ablation in liquids (PLAL) is mainly related to the formation of CD-active Ag(+)/cysteine supramolecular polymers. The strict correlation between supramolecular chirality and hierarchical effects, driven by different chemical environments experienced by cysteine when different titration modalities are used, is pivotal to validate cysteine as a fast and reliable probe to characterize the surface oxidation of AgNPs prepared by pulsed laser ablation in liquids by varying the laser wavelengths.

Controlled large-scale fabrication of sea sponge-like ZnO nanoarchitectures on textured silicon

A simple and effective approach to fabricate extensive 3D ZnO nanoarchitectures on alkaline etched (100) Si substrates is presented. Textured silicon micropattern drives ZnO 1D growth on all the {111} exposed faces, resulting in sea sponge-likeZnO nanoarchitectures. The obtained 3D nanostructured ZnO is the result of a perfectly ordered array of continuous and crystalline ZnO nanorods, grown on the silicon pyramid {111} faces. The substrate orientation and the relative roughness, intrinsically derived by the alkaline silicon texturization, drive the preferential growth of one-dimensional ZnO nanorods. The ZnO nanorods photoluminescence spectra show, at room temperature, a narrow ultraviolet (UV) emission peak at 3.28 eV and a broad unstructured green band emission at 2.57 eV. These luminescence emissions are attributed to the near band-edge exciton transitions and to the defect emission, respectively. This original approach to fabricate high surface area ZnO nanoarchitectures presents the advantages of well established and reproducible methodologies of semiconductors industrial manufacturing (silicon micromachining and chemical vapor deposition), thus representing an easy scaling up solution to fabricate new ZnO-based nanomaterials.

Spontaneous deposition of polylysine on surfaces: Role of the secondary structure to optimize noncovalent coating strategies

Understanding the factors that governs spontaneous molecular transfer from solution to solid surface is fundamental to control noncovalent surface functionalization strategies, both in term of robustness and reproducibility. The comprehension of the nature of interaction involved in the mechanism of spontaneous adsorption will allow for a fine modulation of the deposition process. Herein, we provide experimental evidences to demonstrate that poly-lysine secondary structure represents a crucial factor profoundly influencing the outcome of its spontaneous deposition on quartz surfaces. In particular, random coil to α-helix transition is required to drive an effective transfer of the poly-l-lysine at the liquid-solid interface. β-sheet deposition requires longer times to be accomplished, while random-coil deposition is highly unfavored. Accordingly, polylysine deposition on quartz and silicon is effective when α-helix is formed in solution (pH>10). This surface noncovalent functionalization represents a simple strategy to fabricate hybrid organic-inorganic or biocompatible materials. In fact, the proposed methodology is proven robust and repeatable and compatible for combination with solution or vapor phases (i.e. MOCVD) nanomaterial deposition approaches.

Surface modification by vanadium pentoxide turns oxide nanocrystals into powerful adsorbents of methylene blue

HYPOTHESIS If nanocrystals of such semiconductor as SnO2 and TiO2, which are not known as powerful adsorbents, have their surface modified by layer of V2O5, how will the adsorption properties be affected? Answering this question would provide a new set of surface properties to be designed by surface engineering of oxide nanocrystals. EXPERIMENTS SnO2 and TiO2 colloidal nanocrystals were prepared by coupling sol-gel and solvothermal synthesis. By co-processing with V chloroalkoxide and subsequent heat-treatment at 400-500 °C, surface deposition of V2O5 layers was obtained. The methylene blue adsorption onto the prepared materials was tested and compared with the pure oxide supports. Cycling of the materials and analysis of the adsorption process was also investigated. FINDINGS The V-modified nanocrystals extracted ∼80% methylene blue from 1.5 × 10-5 M aqueous solution after 15 min only, contrarily to pure materials, which took up only 30% of the dye even after 120 min. Comparison with pure commercial V2O5 showed that the peculiar adsorption properties were imparted by the surface deposition of the V2O5-like layers. This report demonstrates that new classes of adsorbing materials can be conceived by suitably coupling different metal oxides.

A novel patient-oriented numerical procedure for glaucoma drainage devices

The present work analyses the performance of four glaucoma drainage devices, by means of a novel patient-oriented numerical procedure. The procedure is based on the three-dimensional geometry reconstruction from the stacks of tomographic images of a human eye, at different angles, on meshing and on thermo-fluid dynamics modelling activities, carried out on the reconstructed computational domain. The current three-dimensional eye model considers anterior chamber (AC), trabecular meshwork, Schlemms canal, and collector channels, making use of generalised porous medium approach for modelling ocular porous tissue and cavities. The intraocular pressure (IOP) management inside AC of human eye is analysed, by comparing the results obtained for four drainage devices implanted in a human eye for glaucoma treatment, ie, ExPRESS shunt, iStent inject, SOLX gold micro shunt, and the novel silicon shunt device. The numerical results allow predicting the effects of the installation of these implants on human eyes, in terms of IOP decrease, aqueous humour velocity, pressure, friction coefficient, and local Nusselt number, pointing out the clear distinction between pre-operative and post-operative eye conditions for different glaucoma surgical techniques.

ZnO-pHEMA Nanocomposites: an Eco-friendly and Reusable Material for Water Remediation

The design of new hybrid nanocomposites based on poly(2-hydroxyethylmethacrylate) (pHEMA) graphene oxide (GO) cryosponges, wherein ZnO nanolayers have been deposited to induce photocatalytic properties, is reported here. Atomic layer deposition at low temperature is specifically selected as the deposition technique to stably anchor ZnO molecules to the pendant polymer OH groups. Furthermore, to boost the pHEMA cryogel adsorption capability versus organic dyes, GO is added during the synthetic procedure. The morphology, the crystallinity, and the chemical composition of the samples are deeply investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction analyses, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Swelling properties, mechanical performance, and adsorption kinetics models of the hybrid materials are also evaluated. Finally, the adsorption and photocatalytic performance are tested and compared for all of the samples using methylene blue as a dye. Particularly, the adsorption efficiency of ZnO/pHEMA and ZnO/pHEMA-GO nanocomposites, as well as their in situ regeneration via photocatalysis, renders such devices very appealing for advanced wastewater treatment technology.

Temperature Effect on Rheological Behavior of Silicone Oils. a Model for the Viscous Heating

The rheological behavior of silicone oils, (CH3)3SiO-[Si(CH3)2O]n-Si(CH3)3, and their mixtures is studied. Shear-stress measurements, in the temperature range of 293-313 K, reveal that this polymer family is a group of shear-thinning liquids with a yield stress below which no flow occurs. Experimental diagrams, i.e., shear stress versus shear rate, are satisfactorily described by the Casson fluid model over a wide range of shear rates. In order to monitor the effect of temperature on fluid properties, Cassons rheological model is reformulated using the fictitious shear rate, γ̇f, and the infinite-shear viscosity, η∞, as constitutive parameters. Due to low intermolecular forces and high chain flexibility, γ̇f varies very little when the temperature increases. For this reason, the apparent material viscosity depends on temperature only through η∞, which exponentially decreases until high shear rates are reached, and there is more alignment possible. Interestingly, the temperature sensitivity of this pseudoplastic behavior is the same for all of the silicone oils investigated; therefore, they can be classified according to their tendency to emulsify. Experimental results are then used to model the flow of silicone oils in a cylindrical pipe and estimate the temperature increase due to viscous heating. Numerical results show that the normalized temperature, i.e., ratio of fluid temperature to wall temperature, increases approximately 23%, and the apparent viscosity decreases drastically, going toward the center of the tube. The non-Newtonian nature of fluid is reflected in the presence of a critical region. In this region, the velocity and temperature gradients vanish. Since silicon oil is a surgical tool, we hope that the acquired physicochemical information can provide help to facilitate the removal of this material during surgical procedures.