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.

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 document is structured in six chapters. The first chapter describes, from a theoretical point of view, the topics that will form the essential basis for a clearer and more complete understanding of the following sections. In the subsequent four chapters (Chapters 2-4) the overall results obtained in this thesis will be presented. In the fifth chapter, however, the thesis's conclusions will be presented, analyzing the results and discussing possible future prospects of applications in both the industrial and basic research fields. Finally, in the sixth and last chapter, the materials used in this work, the methodology of the various syntheses, the deposition and characterization techniques will be described.

High performance textiles are one of the most recent advance of the textile and clothing industry. With input from imenient reearchers in the field, this book contributes a critical overview of key advancement in the field. Chapters binding the utilization of high performance textiles in such areas as medicine, protective clothing, heat and fire protection, industrial filtration, geotextiles, civil engineering and sustainable energy applications. Also, included evaluation of novel surface modification using nano particles, supercritical fluid, laser, irradiation with electron beam and plasma technologies for a wide scope of high performance textiles.

In the field of stimuli-responsive materials, introducing a pH-sensitive dyestuff onto textile fabrics is a promising approach for the development of wearable sensors. In this paper, the alizarin red S dyestuff bonded with a sol-gel precursor, namely trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane, was used to functionalize polyethylene terephthalate fabrics, a semi-crystalline thermoplastic polyester largely used in the healthcare sector mainly due to its advantages, including mechanical strength, biocompatibility and resistance against abrasion and chemicals. The obtained hybrid halochromic silane-based coating on polyester fabrics was investigated with several chemical characterization techniques. Fourier transform infrared spectroscopy and X-ray Photoelectron Spectroscopy confirmed the immobilization of the dyestuff-based silane matrix onto polyethylene terephthalate samples through self-condensation of hydrolyzed silanols under the curing process. The reversibility and repeatability of pH-sensing properties of treated polyester fabrics in the pH range 2.0-8.0 were confirmed with diffuse reflectance and CIELAB color space characterizations. Polyester fabric functionalized with halochromic silane-based coating shows the durability of halochromic properties conversely to fabric treated with plain alizarin red S, thus highlighting the potentiality of the sol-gel approach in developing durable halochromic coating on synthetic substrates. The developed wearable pH-meter device could find applications as a non-invasive pH sensor for wellness and healthcare fields.

World population growth, with the consequent consumption of primary resources and production of waste, is progressively and seriously increasing the impact of anthropic activities on the environment and ecosystems. Environmental pollution deriving from anthropogenic activities is nowadays a serious problem that afflicts our planet and that cannot be neglected. In this regard, one of the most challenging tasks of the 21st century is to develop new eco-friendly, sustainable and economically-sound technologies to remediate the environment from pollutants. Nanotechnologies and new performing nanomaterials, thanks to their unique features, such as high surface area (surface/volume ratio), catalytic capacity, reactivity and easy functionalization to chemically modulate their properties, represent potential for the development of sustainable, advanced and innovative products/techniques for environmental (bio)remediation. This review discusses the most recent innovations of environmental recovery strategies of polluted areas based on different nanocomposites and nanohybrids with some examples of their use in combination with bioremediation techniques. In particular, attention is focused on eco-friendly and regenerable nano-solutions and their safe-by-design properties to support the latest research and innovation on sustainable strategies in the field of environmental (bio)remediation.

The need to ensure adequate antifouling protection of the hull in the naval sector led to the development of real painting cycles, which involve the spreading of three layers of polymeric material on the hull surface exposed to the marine environment, specifically defined as primer, tie coat and final topcoat. It is already well known that coatings based on suitable silanes provide an efficient and non-toxic approach for the hydrophobic and antifouling/fouling release treatment of surfaces. In the present work, functional hydrophobic hybrid silica-based coatings (topcoats) were developed by using sol-gel technology and deposited on surfaces with the "doctor blade" method. In particular, those organic silanes, featuring opportune functional groups such as long (either fluorinated) alkyl chains, have a notable influence on surface wettability as showed in this study. Furthermore, the hydrophobic behavior of this functionalized coating was improved by introducing an intermediate commercial tie-coat layer between the primer and the topcoat, in order to decrease the wettability (i.e., decreasing the surface energy with a matching increase in the contact angle, CA) and to therefore make such coatings ideal for the design and development of fouling release paints. The hereby synthesized coatings were characterized by optical microscopy, contact angle analysis and a mechanical pull-off test to measure the adhesive power of the coating against a metal substrate typically used in the nautical sector. Analysis to evaluate the bacterial adhesion and the formation of microbial biofilm were related in laboratory and simulation (microcosm) scales, and assessed by SEM analysis.

Biofouling has destructive effects on shipping and leisure vessels, thus producing severe problems for marine and naval sectors due to corrosion with consequent elevated fuel consumption and higher maintenance costs. The development of anti-fouling or fouling release coatings creates deterrent surfaces that prevent the initial settlement of microorganisms. In this regard, new silica-based materials were prepared using two alkoxysilane cross-linkers containing epoxy and amine groups (i.e., 3-Glycidyloxypropyltrimethoxysilane and 3-aminopropyltriethoxysilane, respectively), in combination with two functional fluoro-silane (i.e., 3,3,3-trifluoropropyl-trimethoxysilane and glycidyl-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononylether) featuring well-known hydro repellent and anti-corrosion properties. As a matter of fact, the co-condensation of alkoxysilane featuring epoxide and amine ends, also mixed with two opportune long chain and short chain perfluorosilane precursors, allows getting stable amphiphilic, non-toxic, fouling release coatings. The sol-gel mixtures on coated glass slides were fully characterized by FT-IR spectroscopy, while the morphology was studied by scanning electron microscopy (SEM), and atomic force microscopy (AFM). The fouling release properties were evaluated through tests on treated glass slides in different microbial suspensions in seawater-based mediums and in seawater natural microcosms. The developed fluorinated coatings show suitable antimicrobial activities and low adhesive properties; no biocidal effects were observed for the microorganisms (bacteria).

In recent years thanks to the Internet of Things (IoT), the demand for the development of miniaturized and wearable sensors has skyrocketed. Among them, novel sensors for wearable medical devices are mostly needed. The aim of this review is to summarize the advancements in this field from current points of view, focusing on sensors embedded into textile fabrics. Indeed, they are portable, lightweight, and the best candidates for monitoring biometric parameters. The possibility of integrating chemical sensors into textiles has opened new markets in smart clothing. Many examples of these systems are represented by color-changing materials due to their capability of altering optical properties, including absorption, reflectance, and scattering, in response to different external stimuli (temperature, humidity, pH, or chemicals). With the goal of smart health monitoring, nanosized sol-gel precursors, bringing coupling agents into their chemical structure, were used to modify halochromic dyestuffs, both minimizing leaching from the treated surfaces and increasing photostability for the development of stimuli-responsive sensors. The literature about the sensing properties of functionalized halochromic azo dyestuffs applied to textile fabrics is reviewed to understand their potential for achieving remote monitoring of health parameters. Finally, challenges and future perspectives are discussed to envisage the developed strategies for the next generation of functionalized halochromic dyestuffs with biocompatible and real-time stimuli-responsive capabilities.

The textile-finishing industry, is one of the main sources of persistent organic pollutants in water; in this regard, it is necessary to develop and employ new sustainable approaches for fabric finishing and treatment. This research study shows the development of an efficient and eco-friendly procedure to form highly hydrophobic surfaces on cotton fabrics using different modified silica sols. In particular, the formation of highly hydrophobic surfaces on cotton fabrics was studied by using a two-step treatment procedure, i.e., first applying a hybrid silica sol obtained by hydrolysis and subsequent condensation of (3-Glycidyloxypropyl)trimethoxy silane with different alkyl(trialkoxy)silane under acid conditions, and then applying hydrolyzed hexadecyltrimethoxysilane on the treated fabrics to further improve the fabrics' hydrophobicity. The treated cotton fabrics showed excellent water repellency with a water contact angle above 150° under optimum treatment conditions. The cooperative action of rough surface structure due to the silica sol nanoparticles and the low surface energy caused by long-chain alkyl(trialkoxy)silane in the nanocomposite coating, combined with the expected roughness on microscale due to the fabrics and fiber structure, provided the treated cotton fabrics with excellent, almost super, hydrophobicity and water-based stain resistance in an eco-sustainable way.