Smart pillar[5]arene-based PDMAEMA/PES beads for selective dye pollutants removal: design, synthesis, chemical-physical characterization, and adsorption kinetic studies.

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.

Sustainable Secondary-Raw Materials, Natural Substances and Eco-Friendly Nanomaterial-Based Approaches for Improved Surface Performances: An Overview of What They Are and How They Work.

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.

Super-Hydrophobicity of Polyester Fabrics Driven by Functional Sustainable Fluorine-Free Silane-Based Coatings.

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.

Waterborne Eco-Sustainable Sol-Gel Coatings Based on Phytic Acid Intercalated Graphene Oxide for Corrosion Protection of Metallic Surfaces.

In the past few years, corrosion protection of metal materials has become a global challenge, due to its great economic importance. For this reason, various methods have been developed to inhibit the corrosion process, such as surface treatment approaches, by employing corrosion inhibitors through the deposition of opportunely designed functional coatings, employed to preserve from corrosion damages metallic substrates. Recently, among these techniques and in order to avoid the toxic chromate-based pre-treatment coatings, silane-based coatings and films loaded with organic and inorganic corrosion inhibitors have been widely used in corrosion mitigation water-based surface treatment. In this study, the synthetic approach was devoted to create an embedded, hosted, waterborne, and eco-friendly matrix, obtained by use of the sol-gel technique, through the reaction of functional alkoxysilane cross-linking precursors, namely (3-glycidyloxypropyl)trimethoxysilane (GPTMS) and (3-aminopropyl)triethoxysilane (APTES), in the presence of graphene oxide (GO) intercalated with natural and non-toxic phytic acid (PA) molecules. As a matter of fact, all experimental results from FT-IR spectroscopy, UV-Vis analysis, and SEM confirmed that PA molecules were successfully decorated on GO. Furthermore, polarization measurements and a neutral salt spray test were used to evaluate the anticorrosive performance on aluminum and steel substrates, thus showing that the GO-PA nanofiller improved the barrier and corrosion protection properties of the developed functional silane-based coatings.

Functional Silane-Based Nanohybrid Materials for the Development of Hydrophobic and Water-Based Stain Resistant Cotton Fabrics Coatings.

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.

A Review of Stimuli-Responsive Smart Materials for Wearable Technology in Healthcare: Retrospective, Perspective, and Prospective.

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.

Development of Eco-Friendly Hydrophobic and Fouling-Release Coatings for Blue-Growth Environmental Applications: Synthesis, Mechanical Characterization and Biological Activity.

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.

Design and Development of Fluorinated and Biocide-Free Sol-Gel Based Hybrid Functional Coatings for Anti-Biofouling/Foul-Release Activity.

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).

Functional Nanohybrids and Nanocomposites Development for the Removal of Environmental Pollutants and Bioremediation.

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.

Development of Functional Hybrid Polymers and Gel Materials for Sustainable Membrane-Based Water Treatment Technology: How to Combine Greener and Cleaner Approaches.

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.

Synthesis, Chemical-Physical Characterization, and Biomedical Applications of Functional Gold Nanoparticles: A Review.

Relevant properties of gold nanoparticles, such as stability and biocompatibility, together with their peculiar optical and electronic behavior, make them excellent candidates for medical and biological applications. This review describes the different approaches to the synthesis, surface modification, and characterization of gold nanoparticles (AuNPs) related to increasing their stability and available features useful for employment as drug delivery systems or in hyperthermia and photothermal therapy. The synthetic methods reported span from the well-known Turkevich synthesis, reduction with NaBH4 with or without citrate, seeding growth, ascorbic acid-based, green synthesis, and Brust-Schiffrin methods. Furthermore, the nanosized functionalization of the AuNP surface brought about the formation of self-assembled monolayers through the employment of polymer coatings as capping agents covalently bonded to the nanoparticles. The most common chemical-physical characterization techniques to determine the size, shape and surface coverage of AuNPs are described underlining the structure-activity correlation in the frame of their applications in the biomedical and biotechnology sectors.

Nanostructured Surface Finishing and Coatings: Functional Properties and Applications.

This review presents current literature on different nanocomposite coatings and surface finishing for textiles, and in particular this study has focused on smart materials, drug-delivery systems, industrial, antifouling and nano/ultrafiltration membrane coatings. Each of these nanostructured coatings shows interesting properties for different fields of application. In this review, particular attention is paid to the synthesis and the consequent physico-chemical characteristics of each coating and, therefore, to the different parameters that influence the substrate deposition process. Several techniques used in the characterization of these surface finishing coatings were also described. In this review the sol-gel method for preparing stimuli-responsive coatings as smart sensor materials is described; polymers and nanoparticles sensitive to pH, temperature, phase, light and biomolecules are also treated; nanomaterials based on phosphorus, borates, hydroxy carbonates and silicones are used and described as flame-retardant coatings; organic/inorganic hybrid sol-gel coatings for industrial applications are illustrated; carbon nanotubes, metallic oxides and polymers are employed for nano/ultrafiltration membranes and antifouling coatings. Research institutes and industries have collaborated in the advancement of nanotechnology by optimizing conversion processes of conventional materials into coatings with new functionalities for intelligent applications.

Development of Antibacterial and Antifouling Innovative and Eco-Sustainable Sol-Gel Based Materials: From Marine Areas Protection to Healthcare Applications.

Bacterial colonization of surfaces is the leading cause of deterioration and contaminations. Fouling and bacterial settlement led to damaged coatings, allowing microorganisms to fracture and reach the inner section. Therefore, effective treatment of surface damaged material is helpful to detach bio-settlement from the surface and prevent deterioration. Moreover, surface coatings can withdraw biofouling and bacterial colonization due to inherent biomaterial characteristics, such as superhydrophobicity, avoiding bacterial resistance. Fouling was a past problem, yet its untargeted toxicity led to critical environmental concerns, and its use became forbidden. As a response, research shifted focus approaching a biocompatible alternative such as exciting developments in antifouling and antibacterial solutions and assessing their antifouling and antibacterial performance and practical feasibility. This review introduces state-of-the-art antifouling and antibacterial materials and solutions for several applications. In particular, this paper focuses on antibacterial and antifouling agents for concrete and cultural heritage conservation, antifouling sol-gel-based coatings for filtration membrane technology, and marine protection and textile materials for biomedicine. In addition, this review discusses the innovative synthesis technologies of antibacterial and antifouling solutions and the consequent socio-economic implications. The synthesis and the related physico-chemical characteristics of each solution are discussed. In addition, several characterization techniques and different parameters that influence the surface finishing coatings deposition were also described.