Colloidal Magnetic Heterostructured Nanocrystals with Asymmetric Topologies: Seeded-Growth Synthetic Routes and Formation Mechanisms

Colloidal inorganic nanocrystals, free-standing crystalline nanostructures generated and processed in solution phase, represent an important class of advanced nanoscale materials owing to the flexibility with which their physical–chemical properties can be controlled through synthetic tailoring of their compositional, structural and geometric features and the versatility with which they can be integrated in technological fields as diverse as optoelectronics, energy storage/ conversion/production, catalysis and biomedicine. In recent years, building upon mechanistic knowledge acquired on the thermodynamic and kinetic processes that underlie nanocrystal evolution in liquid media, synthetic nanochemistry research has made impressive advances, opening new possibilities for the design, creation and mastering of increasingly complex “colloidal molecules”, in which nanocrystal modules of different materials are clustered together via solid-state bonding interfaces into free-standing, easily processable multifunctional nanocomposite systems. This Review will provide a glimpse into this fast-growing research field by illustrating progress achieved in the wet-chemical development of last-generation breeds of all-inorganic heterostructured nanocrystals (HNCs) in asymmetric non-onionlike geometries, inorganic analogues of polyfunctional organic molecules, in which distinct nanoscale crystalline modules are interconnected in hetero-dimer, hetero-oligomer and anisotropic multidomain architectures via epitaxial heterointerfaces of limited extension. The focus will be on modular HNCs entailing at least one magnetic material component combined with semiconductors and/or metals, which hold potential for generating enhanced or unconventional magnetic properties, while offering diversified or even new chemical-physical properties and functional capabilities. The available toolkit of synthetic strategies, all based on the manipulation of seeded-growth techniques, will be described, revisited and critically interpreted within the framework of the currently understood mechanisms of colloidal heteroepitaxy

Self assembly of highly fluorescent semiconductor nanorods into large scale smectic liquid crystal structures by coffee stain evaporation dynamics

We deposit droplets of nanorods dispersed in solvents on substrate surfaces and let the solvent evaporate. We find that strong contact line pinning leads to dense nanorod deposition inside coffee stain fringes, where we observe large-scale lateral ordering of the nanorods with the long axis of the rods oriented parallel to the contact line. We observe birefringence of these coffee stain fringes by polarized microscopy and we find the direction of the extraordinary refractive index parallel to the long axis of the nanorods.Comment: 11 pages, 6 figures and supporting informatio

Reversible wettability of hybrid organic/inorganic surfaces of systems upon light irradiation/storage cycles

In this work we present hybrid organic/inorganic structures that can exhibit reversible surface wettability, altered in a controllable manner. In particular, we use the method of photo-patterning to produce polymeric SU-8 pillars of specific geometries, onto which we subsequently deposit colloidal TiO2 nanorods. In this way, we combine the microroughness of the polymeric pillars with the nanoroughness of the nanorod-coating to create highly hydrophobic surfaces. The hydrophobicity of these systems can be changed reversibly into hydrophilicity upon irradiation of the hybrid structures with pulsed UV laser light. This behaviour is due to the well-known property of TiO2, that becomes superhydrophilic upon UV light irradiation. This property is reversible and we monitor the recovery of our hybrid polymeric/inorganic-nanorods structures to their initial hydrophobic character upon dark storage and heating. The wetting behaviour has been modelled and analysed according to the surface geometry. The direct implementation of such structures into microfluidics devices is demonstrated. Copyright © 2010 Inderscience Enterprises Ltd

Determination of surface properties of various substrates using TiO2 nanorod coatings with tunable characteristics

We present a novel approach to cover different substrates with thin light-sensitive layers that consist of organic-capped TiO2 nanorods (NRs). Such NR-based coatings exhibit an increasing initial hydrophobicity with increasing NR length, and they demonstrate a surface transition from this highly hydrophobic state to a highly hydrophilic one under selective UV–laser irradiation. This behaviour is reversed under long dark storage. Infrared spectroscopy measurements reveal that light-driven wettability changes are accompanied by a progressive hydroxylation of the TiO2 surface. The surfactant molecules that cover the NRs do not appear to suffer for any significant photocatalytic degradation

Sonication-Assisted Production of Fosetyl-Al Nanocrystals: Investigation of Human Toxicity and In Vitro Antibacterial Efficacy against Xylella Fastidiosa

none10Recently, there is a growing demand in sustainable phytopathogens control research. Nanotechnology provides several tools such as new pesticides formulations, antibacterial nanomaterials and smart delivery systems. Metal nano-oxides and different biopolymers have been exploited in order to develop nanopesticides which can offer a targeted solution minimizing side effects on environment and human health. This work proposed a nanotechnological approach to obtain a new formulation of systemic fungicide fosetyl-Al employing ultrasonication assisted production of water dispersible nanocrystals. Moreover, chitosan was applicated as a coating agent aiming a synergistic antimicrobial effect between biopolymer and fungicide. Fosetyl-Al nanocrystals have been characterized by morphological and physical-chemical analysis. Nanotoxicological investigation was carried out on human keratinocytes cells through cells viability test and ultrastructural analysis. In vitro planktonic growth, biofilm production and agar dilution assays have been conducted on twoXylella fastidiosasubspecies. Fosetyl-Al nanocrystals resulted very stable over time and less toxic respect to conventional formulation. Finally, chitosan-based fosetyl-Al nanocrystals showed an interesting antibacterial activity againstXylella fastidiosasubsp.paucaandXylella fastidiosasubsp.fastidiosa.Regione Puglia, Deliberazione della Giunta Regionale n. 1410 del 12/06/2015 “Linee guida per il parco della ricerca e sperimentazione finalizzata alla prevenzione e al contenimento del complesso del disseccamento rapido dell’olivo (CODIRO)” Project FATA- “Trattamenti fitoterapici innovativi a base di vettori di chitosano” MIPAAFT, Project Oli.Di.X.I.It-“OLIvicoltura e Difesa da Xylella fastidiosa e da Insetti vettori in Italia”, D.M. 23773 del 6/09/2017.openFrancesca Baldassarre; Giuseppe Tatulli; Viviana Vergaro; Stefania Mariano; Valeria Scala; Concetta Nobile; Nicoletta Pucci; Luciana Dini; Stefania Loreti; Giuseppe CiccarellaBaldassarre, Francesca; Tatulli, Giuseppe; Vergaro, Viviana; Mariano, Stefania; Scala, Valeria; Nobile, Concetta; Pucci, Nicoletta; Dini, Luciana; Loreti, Stefania; Ciccarella, Giusepp

An Insight into Chemistry and Structure of Colloidal 2D-WS2 Nanoflakes: Combined XPS and XRD Study

The surface and structural characterization techniques of three atom-thick bi-dimensional 2D-WS2 colloidal nanocrystals cross the limit of bulk investigation, offering the possibility of simultaneous phase identification, structural-to-morphological evaluation, and surface chemical description. In the present study, we report a rational understanding based on X-ray photoelectron spectroscopy (XPS) and structural inspection of two kinds of dimensionally controllable 2D-WS2 colloidal nanoflakes (NFLs) generated with a surfactant assisted non-hydrolytic route. The qualitative and quantitative determination of 1T’ and 2H phases based on W 4f XPS signal components, together with the presence of two kinds of sulfur ions, S22− and S2−, based on S 2p signal and related to the formation of WS2 and WOxSy in a mixed oxygen-sulfur environment, are carefully reported and discussed for both nanocrystals breeds. The XPS results are used as an input for detailed X-ray Diffraction (XRD) analysis allowing for a clear discrimination of NFLs crystal habit, and an estimation of the exact number of atomic monolayers composing the 2D-WS2 nanocrystalline samples

Reversibly Light-Switchable Wettability of Hybrid Organic/Inorganic Surfaces With Dual Micro-/ Nanoscale Roughness

Here, an approach to realize ''smart'' solid substrates that can convert their wetting behavior between extreme states under selective light irradiation conditions is described. Hybrid organic/inorganic surfaces are engineered by exploiting photolithographically tailored SU-8 polymer patterns as templates for accommodating closely packed arrays of colloidal anatase TiO2 nanorods, which are able to respond to UV light by reversibly changing their surface chemistry. The TiO2-covered SU-8 substrates are characterized by a dual micro-/nanoscale roughness, arising from the overlapping of surfactantcapped inorganic nanorods onto micrometer-sized polymer pillars. Such combined architectural and chemical surface design enables the achievement of UV-driven reversible transitions from a highly hydrophobic to a highly hydrophilic condition, with excursions in water contact angle values larger than 1008. The influence of the geometric and compositional parameters of the hybrid surfaces on their wettability behavior is examined and discussed within the frame of the available theoretical models