Star copolymer films were produced by using spin-coating, drop-casting, and casting deposition techniques, thus obtaining ultrathin and thick films, respectively. The morphology is generally flat, but it becomes substrate-dependent for ultrathin films where the planarization effect of films is not efficient. The indentation hardness of films was investigated by Force Volume Maps in both the air and liquid. In the air, ultrathin films are in the substrate-dominated zone and, thus, the elastic modulus E is overestimated, while E reaches its bulk value for drop-casted ultrathin and thick films. In liquid (water), E follows an exponential decay for all films with a minimum soaked time t0 of 0.37 and 2.65 h for ultrathin and drop-casted ultrathin and thick films, respectively. After this time, E saturates to a value on average 92% smaller than that measured in the air due to film swelling. Such results support the role of film morphology in the antimicrobial activity envisaged in the literature, suggesting also an additional role of film hardness.

Two-dimensional (2D) nanomaterials (e.g., graphene) have attracted growing attention in the (bio)sensing area and, in particular, for biomedical applications because of their unique mechanical and physicochemical properties, such as their high thermal and electrical conductivity, biocompatibility, and large surface area. Graphene (G) and its derivatives represent the most common 2D nanomaterials applied to electrochemical (bio)sensors for healthcare applications. This review will pay particular attention to other 2D nanomaterials, such as transition metal dichalcogenides (TMDs), metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and MXenes, applied to the electrochemical biomedical (bio)sensing area, considering the literature of the last five years (2018-2022). An overview of 2D nanostructures focusing on the synthetic approach, the integration with electrodic materials, including other nanomaterials, and with different biorecognition elements such as antibodies, nucleic acids, enzymes, and aptamers, will be provided. Next, significant examples of applications in the clinical field will be reported and discussed together with the role of nanomaterials, the type of (bio)sensor, and the adopted electrochemical technique. Finally, challenges related to future developments of these nanomaterials to design portable sensing systems will be shortly discussed.

The catalytic and structural changes due to the presence of 0.25 wt% indium on a 3% Ni/CeO2-Al2O3 catalyst prepared by impregnation method were investigated. Catalyst characterizations by XRD, TPR, XPS, TEM and DRIFTS (in presence of CO/CO2/CH4 +CO2) were carried out. In the short (6 h) catalytic methane dry reforming tests at 650 °C both samples were stable, produced essentially no carbon, but indium lowered the activity. In the 4 day longevity tests at 675 °C, stable activity was achieved by the In-promoted catalyst in contrast with the continuous deactivation of the unpromoted Ni sample due to coking and sintering. Indium, partially alloyed with nickel, could better keep nickel in metallic state, and the increased CO2 activation ability, the intimate Ni(In)-CeO2 interface inside the support pores resulted in practically no coking.

This article reports on the synthesis of an innovative smart polymer, P5-QPDMAEMA, opportunely developed with the aim of combining the responsiveness of PDMAEMA polymer and the host-guest properties of covalently linked pillar[5]arenes. Thanks to a traditional Non-Induced Phase Separation (NIPS) process performed at various coagulation pH, the blending of P5-QPDMAEMA with polyethersulfone gave rise to the formation of functional beads for the removal of organic dyes in water. Adsorption tests are carried out on all the produced blend-based beads by employing two representative dyes, the cationic methylene blue (MB), and the anionic methyl orange (MO). In particular, the P5-QPDMAEMA based beads, prepared at acidic pH, featured the best MO removal rate (i. e., 91.3 % after 150 minutes starting from a 20 mg ? L-1 solution) and a high selectivity towards the removal of the selected anionic dye. Based on the adsorption kinetics and isotherm calculations, the pseudo-first order and Freundlich models were shown to be the most suitable to describe the MO adsorption behavior, achieving a maximum adsorption capacity of 21.54 mg ? g-1. Furthermore, zwitterionic beads are obtained by a post-functionalization of the PDMAEMA and the P5-QPDMAEMA based beads, to test their removal capability towards both anionic and cationic dyes, as shown.

Two novel hexacoordinated Co(II)-based single-ion magnets were prepared and characterised. Both neutral complexes feature metal-centred coordination with one terminal and one bidentate nitrate anions along with tridentate derivatives of a 2,6-bis(1H-benzimidazole-2-yl)pyridine ligand containing either n-octyl (complex 1) or n-dodecyl (complex 2) chains. The presence of long aliphatic chains ensures their solubility in low polarity and volatile solvents frequently used for lithography patterning. This enabled the preparation of microstructural layers and patterns on technologically relevant substrates by easy-to-handle and low-cost wet lithographic techniques. On the other hand, attempts at surface deposition via sublimation were not successful due to thermal instability. The electronic structure of complexes typically features an orbitally non-degenerate ground state well-separated from the lowest excited state, which allows one to analyse magnetic anisotropy by the spin Hamiltonian approach. Zero-field splitting parameters obtained from CASSCF-NEVPT2 calculations and from the analysis of magnetic data suggest that both compounds display positive axial D parameters within a range of 17-25 cm(-1). Combined results from high-field electron paramagnetic resonance (X-band and HF-EPR) and Fourier-transform infrared magnetic spectroscopy (FIRMS) simulated with the spin Hamiltonian provided the axial and rhombic zerofield splitting terms D = +23.7 cm(-1) for complex 1 and D = +24.2 cm(-1) for complex 2, together with pronounced rhombicity in the range of E/D approximate to 0.15-0.19 for both compounds. Dynamic magnetic investigations have revealed the field-induced slow relaxation of magnetisation, with maximal relaxation times (tau) of 7.6 ms for 1 and 0.8 ms for 2. This relaxation is governed via a combination of several relaxation mechanisms, among which the quantum tunnelling was efficiently suppressed by the applied static magnetic field. The effective barriers of spin reversal U-eff = 77(4) K for 1 and U-eff = 70(2) K for 2 are consistent with the expected values calculated using the ZFS parameters.

Nowadays the need for hybrid multifunctional nanostructured materials or nanocomposite has increased and become essential as nanotechnology and nanomaterial engineering is advancing with more accurate, sophisticated and either sustainable applications. [1] In particular, new (multi)functional hybrid organic-inorganic materials (HOIM) can be developed and used in different potential application fields like opto-electronic, mechanical, sensing, energy conversion and storage, environmental technologies, bio-medical, textiles, blue growth, building, and cultural heritage sectors, thanks to their unique and improved features and surface properties. [2] In this regard, (waste)water treatment and remediation methods represent an important subject of investigation for the abatement not only of the common classes of environmental pollutants, but also of various classes of emerging substances, constantly released into the environment by the anthropogenic activities. As a matter of facts, a variety of chemical synthesis and methods are actually used to develop hybrid materials and filtration membranes for water purification. [3-4] Furthermore, for the sake of sustainability and environmental protection, also the design and development of (multi)functional nanohybrids, nanocomposites and functional polymeric blends through a multidisciplinary feedback could considerably contribute to the improvement of human daily life and well-being. Herein, the development and application of innovative (multi)functional hybrid materials or nanocomposites, as well as membranes for the selective removal of contaminants from water, will be described and discussed in order to undertake the correlation between the designed functionalities and the properties of the obtained materials to assess the importance of a rational safe-by-design of more sustainable and innovative solutions for water remediation. These materials are based on the use of an appropriate multicomponent polymeric matrix based on opportune functional polymeric precursors, natural fillers or molecules, or either blended polymers. Further efforts are being made in this regard to create synthetic protocols and advanced technologies [4] that are fully green and eco-friendly, beginning with bio-based natural primary or secondary raw materials, in order to produce more sustainable, recyclable and re-usable materials, paying attention to their life cycle from cradle to grave in accordance with the circular economy principles.

Recently, nanotechnologies have shifted toward the development of hybrid nanomaterials and functional nanocomposites, which are distinguished by the presence of functional nanometric components or nanofillers dispersed in a polymeric matrix, resulting in increased properties compared to those of either starting component. The original concept is to create an enhanced nanohybrid or nanocomposite material that is appropriate as a surface coating or for other sustainable applications due to increased qualities such as: 1) antifouling or antibacterial; 2) flame-retardant; 3) drug release; 4) sensing; 5) mechanical resistance; and 6) pollutant absorption and degradation [1]. In particular, the incorporation of sensing functions into fabric textiles is a powerful approach toward the development of so-called "smart textiles", enabling the development of wearable sensors, i.e. novel systems characterized by main textile characteristics such as flexibility, biocompatibility, comfort, and mechanical resistance, capable of reacting and adapting to specific external stimuli from their surroundings [2]. This work will show in details the design, synthesis, and characterization of hybrid nanomaterials and multifunctional, innovative and smart nanocomposites based on functional nanoparticles and nanofillers dispersed in polymeric matrices and/or in combination with suitable dopants, used as-is or as coatings of various substrates, for uses in opto-electronic devices, sensors, catalytic processes, cultural heritage, environmental remediation, construction, blue growth, biomedicine and textiles. The setting up of totally green and eco-friendly synthesis procedures based on natural components or wastes to produce functional products that can also be recycled, will be underlined as a crucial step toward sustainability.

A multifunctional hybrid material based on sepiolite for environmental recovery and bio-remediation is described. In particular, the invention describes the design and development of suitably functionalized hybrid nanomaterials starting from sepiolite and the subsequent study of the absorbent and degrading properties in relation to aromatic hydrocarbons, by activating hydrocarbon-clastic bacteria. These nanomaterials have been prepared in order to remove hydrocarbon pollutants (e.g. oil) in natural matrices (marine environment), with potential applications in the field of environmental remediation.

A multi-functional hybrid material based on natural clays for environmental bio-remediation and recover), is disclosed. In particular, the invention discloses the design and development of appropriately functionalized nanohybrid materials starting from nanostructured clays and the subsequent study of the absorbent properties in relation to hydrocarbons, heavy metals, chemical pollutants, oils, particulate, and microplastics. These nanomaterials were prepared in order to remove the hydrocarbon pollutants (for example oil) and metal pollutants in natural matrices (marine environment), with potential applications in the field of environmental remediation.

Chemical treatments are extensively used in textile finishing procedures to improve different properties of natural and synthetic fibers. Sol-gel chemistry is based on hydrolysis and condensation of metal alkoxides or between hydrated metal species. Indeed, many silicon alkoxides are insoluble in water and the alkoxide ratio/ water is often adjusted to limit hydrolysis. The development of innovative technologies can introduce new functionalities to textiles without modifying their appearance, thus introducing barrier properties for many application fields such as antibacterial and mosquito-repellent textiles. The economic impact that mosquitos cause is really high, so much so that the development of efficient repellents is of huge importance, especially if they are of natural origin and harmless to human health. The high volatility and uncontrollable delivery of these oils can be solved through the sol-gel technique, which can control their release.

Alkoxysilanes represent a class of molecules widely employed to achieve the preparation of plenty of functional surfaces by easy, cost-effective and eco-friendly sol-gel methods. In this regard, the advancements of research activities include the proper design of film/patterns/brushes, by starting from opportune alkoxysilane and/or other metal/metalloid precursors, in order to obtain efficient innovative and homogenous functional surfaces showing implemented properties by means of the simple and eco-friendly sol-gel method. Therefore, in light of these aspects, the employment of opportune functional alkoxysilanes, either in combination with other nanofillers or molecules, is a key step for the design, and development of sol-gel based nanohybrid or nanocomposite coatings suitable for different surface properties implementation and applications, spanning from blue-growth sector to smart and technical textiles, from biomedicine to building and cultural heritages, from environmental remediation to catalysis. Some of the most relevant and explicative examples of these innovative and sustainable sol-gel based coatings will be described in this chapter.

Over the past decade, inorganic fillers and sol-gel-based flame-retardant technologies for textile treatments have gained increasing research interest as useful alternatives to hazardous chemicals previously employed in textile coating and finishing. This review presents the current state of the art of inorganic flame-retardant technology for cotton fabrics to scientists and researchers. Combustion mechanism and flammability, as well as the thermal behavior of neat cotton samples, are first introduced. The main section is focused on assessing the effect of inorganic and sol-gel-based systems on the final flame-retardant properties of cotton fabrics, emphasizing their fire safety characteristics. When compared to organic flame-retardant solutions, inorganic functional fillers have been shown to be more environmentally friendly and pollution-free since they do not emit compounds that are hazardous to ecosystems and humans when burned. Finally, some perspectives and recent advanced research addressing the potential synergism derived from the use of inorganic flame retardants with other environmentally suitable molecules toward a sustainable flame-retardant technological approach are reviewed.

To meet modern society's requirements for sustainability and environmental protection, innovative and smart surface coatings are continually being developed to improve or impart surface functional qualities and protective features. These needs regard numerous different sectors, such as cultural heritage, building, naval, automotive, environmental remediation and textiles. In this regard, researchers and nanotechnology are therefore mostly devoted to the development of new and smart nanostructured finishings and coatings featuring different implemented properties, such as anti-vegetative or antibacterial, hydrophobic, anti-stain, fire retardant, controlled release of drugs, detection of molecules and mechanical resistance. A variety of chemical synthesis techniques are usually employed to obtain novel nanostructured materials based on the use of an appropriate polymeric matrix in combination with either functional doping molecules or blended polymers, as well as multicomponent functional precursors and nanofillers. Further efforts are being made, as described in this review, to carry out green and eco-friendly synthetic protocols, such as sol-gel synthesis, starting from bio-based, natural or waste substances, in order to produce more sustainable (multi)functional hybrid or nanocomposite coatings, with a focus on their life cycle in accordance with the circular economy principles.

Polyester fibers are widely employed in a multitude of sectors and applications from the technical textiles to everyday life thanks to their durability, strength, and flexibility. Despite these advantages, polyester lacks in dyeability, adhesion of coating, hydrophilicity, and it is characterized by a low wettability respect to natural fibers. On this regard, beyond the harmful hydrophobic textile finishings of polyester fabrics containing fluorine-compounds, and in order to avoid pre-treatments, such as laser irradiation to improve their surface properties, research is moving towards the development of fluorine-free and safer coatings. In this work, the (3-glycidyloxypropyl)trimethoxysilane (GPTMS) and various long alkyl-chain alkoxysilanes were employed for the fabrication in the presence of a catalyst of a water-based superhydrophobic finishing for polyester fabrics with a simple sol-gel, non-fluorinated, sustainable approach and the dip-pad-dry-cure method. The finished polyester fabrics surface properties were investigated by static and dynamic water repellency tests. Additionally, the resistance to common water-based liquids, abrasion resistance, moisture adsorption, and air permeability measurements were performed. Scanning electron microscopy was employed to examine the micro- and nano-morphology of the functionalized polyester fabrics surfaces. The obtained superhydrophobic finishings displayed high water-based stain resistance as well as good hydrophobicity after different cycles of abrasion.

The surface modification of textile fabrics and therefore, the development of advanced textile materials featuring specific implemented and new properties, such as improved durability and resistance, is increasingly in demand from modern society and end-users. In this regard, the sol-gel technique has shown to be an innovative and convenient synthetic route for developing functional sol-gel coatings useful for the protection of textile materials. Compared with the conventional textile finishing process, this technique is characterized by several advantages, such as the environmentally friendly approaches based on one-step applications and low concentration of non-hazardous chemicals. The sol-gel method, starting from inorganic metal alkoxides or metal salts, leads to inorganic sols containing particles that enable a chemical or physical modification of fiber surfaces, giving rise to final multifunctional properties of treated textile fabrics. This review considered the recent developments in the synthesis of inorganic nanoparticles and nanosols by sol-gel approach for improving wear and UV resistance, as well as antibacterial or antimicrobial effects for textile applications.

Water quality and disposability are among the main challenges that governments and societies will outside during the next years due to their close relationship to population growth and urbanization and their direct influence on the environment and socio-economic development. Potable water suitable for human consumption is a key resource that, unfortunately, is strongly limited by anthropogenic pollution and climate change. In this regard, new groups of compounds, referred to as emerging contaminants, represent a risk to human health and living species; they have already been identified in water bodies as a result of increased industrialization. Pesticides, cosmetics, personal care products, pharmaceuticals, organic dyes, and other man-made chemicals indispensable for modern society are among the emerging pollutants of difficult remediation by traditional methods of wastewater treatment. However, the majority of the currently used waste management and remediation techniques require significant amounts of energy and chemicals, which can themselves be sources of secondary pollution. Therefore, this review reported newly advanced, efficient, and sustainable techniques and approaches for water purification. In particular, new advancements in sustainable membrane-based filtration technologies are discussed, together with their modification through a rational safe-by-design to modulate their hydrophilicity, porosity, surface characteristics, and adsorption performances. Thus, their preparation by the use of biopolymer-based gels is described, as well as their blending with functional cross-linkers or nanofillers or by advanced and innovative approaches, such as electrospinning.

The production and maintenance of road pavements consume resources and produce wastes that are disposed of in landfills. To make more sustainable this activity, we have envisioned a method based on a circular use of residues (oil and char) from municipal solid waste pyrolysis as useful additives for producing improved asphalts and for recycling old asphalts to generate new ones, reducing at the same time the consumption of resources for the production of new road pavements and the disposal of wastes to landfills. This work aims to show the feasibility of the integration of two processes (thermal treatment of municipal solid waste on one side, and that of road pavement production on the other side) where the products deriving from waste pyrolysis become added-value materials to improve the quality of road pavements. In this contribution, we presented the effect of pyrolysis product addition on asphalt binder (bitumen) preparation and aging. Solid and liquid products, deriving from the pyrolysis of two kinds of wastes (refused derived fuel (RDF) and granulated rubber tyre waste), have been used for the preparation of asphalt binder samples. Rheological tests have been performed to determine the mechanical properties of neat asphalt binder (bitumen) and those enriched with pyrolysis derived products. Measurements to evaluate possible anti-aging effects have been also performed. The collected results indicate that char addition strengthens the overall bitumen intermolecular structure while bio-oil addition exerts a rejuvenating activity.

In this paper, we demonstrate the capability to establish spin-polarized currents in doped SrTiO3 (STO). The results are based on the study of charge and spin transport in STO layers doped by the reversible electromigration of oxygen atoms in resistive-switching La0.7Sr0.3MnO3/STO/Co vertical stacks. The formation of oxygen vacancies inside STO results in a metallic conductivity at temperatures <200-250 K, above which a transition to an insulatinglike behavior is detected. A detailed theoretical analysis shows that the behavior of the metallic phase in our samples corresponds to the well-known state of the thermodynamically doped STO featuring the so-called bad metal behavior. Thus, our findings introduce this class of unconventional materials as valuable candidates for innovative spintronic devices.

Abstract A growth mode of pentacene thin films deposited by high vacuum sublimation where the morphology versus thickness h "rings" back and forth between rough 3D films with pyramid islands and smooth 2D films with ziqqurat islands is discovered. The roughness ? versus h exhibits seamless coherent oscillations whose amplitude and wavelength increase as integer multiples of 1.5 ML thickness. The quantized oscillations are reconducted to dynamic wetting/dewetting transitions involving the upper layers of pentacene film. Importantly, the transconductance of organic field effect transistors, either in solid state or electrolyte-gated, exhibits antiphase oscillations with one-decade swing. Charge mobilities in the wetting regime reach 0.1 cm2 V-1 s-1, in line with high-end values reported for thin-film pentacene transistors. Controlling this growth mode enables the limitations of charge transport imposed by the roughening transition to be overcome, a universal feature of high vacuum growth to date.

Starting from the late 1980s, scanning probe microscopy has progressively diffused in Italy until today. In this paper, we provide a brief account of the main historical events and a current picture of the distribution of the active groups. A survey was prepared by LimeSurvey, made of six sections asking for personal and institutional data, human resources, equipment available, fields of interest, research projects, educational/dissemination activities, and two relevant publications in the last six years. It turns out that the Italian community includes more than seventy groups and two companies. It is widely diffused, although mostly concentrated near large academic and research institutions, often in locations where prominent Italian researchers have operated. This community is active in many scientific fields and can produce research of high international quality. It shows a wide competence, as proven by the list of research works published in journals ranked within the top 20% class. The diffusion of SPM microscopes in industry is still sporadic, possibly due to extensive collaborations between the research institutions and industries themselves. The authors hope that this work might be useful to the community and beyond, and that it might stimulate the formation of a more structured network.