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The ability of modifying the surface of a given substrate to confer novel “smart” properties only at the surface level is an extremely powerful approach as it allows to introduce specific physical, chemical, or biological characteristics able to favour an increment of the performances compared to the starting substrate. This is particularly true in the case of textiles and fibres, which are largely adopted not only in the textile field, but also in many innovative applications where the surface functionalisation plays a key role [1]. In this context, the first part of the talk will provide an overview over the use of textiles in surgical operations for the hernia care, with a focus on the possibility of using surface treatments to modify non-absorbable synthetic polymeric meshes to confer advanced features. In particular, the introduction of bioresorbable coatings able to exert an in situ antibacterial action is a very promising and widely investigated route to follow as one of the main issues related to the use of fully-absorbable fibres is their poor mechanical properties, which can be overcome by the presence of a bioinert non-absorbable skeletal materials, thus making the combination of both novel absorbable coatings and standard bioinert fibres a better compromise [2-3]. Another (often underestimated) concern related to hernioplasty is the shrinking of the prosthesis after implantation, with consequent collapse of the anchoring sutures through the hernia defect margin. Even here, the possibility of introducing a functional coating able to increase the adhesion ability of the prosthesis to the human tissue is a very promising technological solution alternative to the deposition of biocompatible glue on the meshes during the surgical intervention [4-5]. In the second part of the talk, a brief survey of representative case studies involving the surface modification of textiles for different applications will be discussed, including the modification of natural fibr

Magnetically driven nanosponges with potential application as targeted drug delivery systems were prepared via the addition of magnetite nanoparticles to the synthesis of cyclodextrin and maltodextrin polymers crosslinked with 1,1′-carbonyldiimidazole. The magnetic nanoparticles were obtained separately via a coprecipitation mechanism involving inorganic iron salts in an alkaline environment. Four composite nanosponges were prepared by varying the content of magnetic nanoparticles (5 wt% and 10 wt%) in the cyclodextrin-and maltodextrin-based polymer matrix. The magnetic nanosponges were then characterised by FTIR, TGA, XRD, FESEM, and HRTEM analysis. The magnetic properties of the nanosponges were investigated via magnetisation curves collected at RT. Finally, the magnetic nanosponges were loaded with doxorubicin and tested as a drug delivery system. The nanosponges exhibited a loading capacity of approximately 3 wt%. Doxorubicin was released by the loaded nanosponges with sustained kinetics over a prolonged period of time.

The continuous growing demand of fresh water to fulfil agricultural, industrial, and domestic needs of the global population points out the technological importance of performing smart and efficient wastewater remediation processes. One of the major problems related to water quality is represented by the impact due to emerging pollutants (EPs), a wide class of anthropic chemicals recently recognized (but poorly regulated), hardly removable by traditional treatments.[1] Hence, innovative heterogeneous processes based on the application of hybrid inorganic-organic magnet-responsive nanomaterials (MRNs, e.g., magnetic iron oxides) are receiving great attention as interesting alternative technologies exploitable in light-enhanced advanced oxidation processes (AOPs), and in more traditional sorption routes.[2] In this study, MRNs are functionalized by means of two different bio-based macromolecules, namely: BBS (i.e., humic-like substances isolated from green compost derived from agricultural biowaste), and chitosan (i.e., an amino-polysaccharide derived from shellfish industry biowaste). Both these organic macromolecules are in line with the “Waste Cleaning Waste” approach, very appealing from the green chemistry viewpoint.[3] Eventually, it has been investigated the possibility of converting such organic fractions into carbonaceous phases via pyrolysis, still maintaining the magnetic properties of the inorganic component. Hybrids MRNs are physicochemical, magnetic, and morphological characterized. Finally, in view of showing the potentiality of these hybrid systems, several case studies are discussed, in details: i) Testing BBS-iron oxide systems against caffeine (taken as model EPs) via light-enhanced AOPs at circumneutral conditions.[1] ii) Testing chitosan-derived carbonaceous-iron oxide systems against anthracene and naphthalene via sorption mechanism.[4] iii) Testing all hybrid systems against As(III) and As(V) via sorption mechanism.[5] Results indicate that thes

Magnetic chitosan composite (MCC) made by chitosan matrix embedding magnetite/maghemite were developed for the removal of toxic Cu(II), Pb(II), and Ni(II) from water. Thermogravimetric (TGA) and Zeta potential analyses showed that MCC contains ca. 50 wt % of chitosan and presents a value of isoelectric point (pHIEP) around 8-8.5. The magnetization curve revealed a saturation magnetization of 12 emu g−1, which indicates that MCC can be easily recovered by magnetic separation. Adsorption of the heavy metals to MCC reached equilibrium within 120 min with maximum uptakes of 108.9 mg g−1, 216.8 mg g−1 and 220.9 mg g−1 for Ni(II), Cu(II) and Pb(II), respectively. The results show that the amino and hydroxyl functional groups of chitosan are involved in the adsorption process. The reported adsorption capacity from organic pollutants, such as hydrocarbons, along with the high adsorption capacity shown for heavy metals, point out MCC being a promising versatile adsorbent for wastewater treatments.

This work reports on the light-induced heterogeneous photodegradation of four micro-contaminants (MCs): Carbamazepine (C), Flumequine (F), Ibuprofen (I), and Sulfamethoxazole (S), using two different heterogeneous advanced oxidation processes. The first one is the semiconductor photocatalysis, run in the presence of the suspension of a home prepared TiO 2 (TiO 2 HP); the second one is an heterogeneous photo-Fenton process run in the presence of a hybrid magnetic nanomaterial (MB3) with an iron oxides core and an organic shell made of bio-based substances (BBS) isolated from urban biowaste. The two materials work upon two different mechanisms and were already tested (and the action mechanism hypothesized) at the lab scale under model conditions: TiO 2 acts as photocatalyst through the photo-generation of hole/electron pairs able to give rise to oxidation and reduction reactions, whereas hybrid magnetic nanomaterial acts in the presence of H 2 O 2 by a photo-Fenton like mechanism. The results evidenced the better performances of TiO 2 HP (also better than the well-known reference TiO 2 P25). Preliminary photodegradation experiments carried out in a pilot plant under natural solar radiation confirmed the good results obtained with TiO 2 HP. Moreover, in the adopted experimental conditions, the Fe(II) leached from MB3 can be considered as responsible of the MCs degradation through a homogeneous photo-Fenton reaction, where MB3 act as iron reservoir.

The Lab4treat experience has been developed to demonstrate the use of magnetic materials in environmental applications. It was projected in the frame of the European project Mat4Treat, and it was tested several times in front of different audiences ranging from school students to the general public in training and/or divulgation events. The experience lends itself to discuss several aspects of actuality, physics and chemistry, which can be explained by modulating the discussion depth level, in order to meet the interests of younger or more experienced people and expand their knowledge. The topic is relevant, dealing with the recycling of urban waste and water depollution. The paper is placed within the field of water treatment for contaminant removal; therefore, a rich collection of recent (and less recent) papers dealing with magnetic materials and environmental issues is described in the Introduction section. In addition, the paper contains a detailed description of the experiment and a list of the possible topics which can be developed during the activity. The experimental approach makes the comprehension of scientific phenomena effective, and, from this perspective, the paper can be considered to be an example of interactive teaching.

Biowaste-derived substances isolated from green compost (BBS-GC) are environmentally friendly reactants similar to humic substances, which contain multiple functionalities, that are suitable for adsorbing different kinds of pollutants in wastewater. Herein, sodium alginate (derived from brown algae) cross-linked with both Ca2+ ions and BBS-GC in the form of hydrogels and dried films are proposed as green, easy-to-form, and handleable materials for tertiary water treatments. The results show that both hydrogels and films are mechanically stable and can effectively remove differently charged dyes through an adsorption mechanism that can be described by the Freundlich model. BBS-GC-containing gels always performed better than samples prepared without BBS-GC, revealing that such unconventional materials can integrate waste valorization and water decontamination, potentially providing social and environmental benefits.

Thermoresponsive poly(N-isopropylacrylamide)-grafted silica nanoparticles (SiNPs) have been synthesized and fully characterized by ATR-FTIR, TGA, HRTEM, BET and DLS analysis. Hybrid solid phase extraction (SPE) beds with tuneable pore size and switchable surface chemistry were prepared by packing the polymergrafted nanoparticles inside SPE cartridges. The cartridges were tested by checking the thermoregulated elution of model compounds, namely methylene blue, caffeine and amoxicillin. Extraction of the analytes and regeneration of the interaction sites on the sorbent surface was carried out entirely in water solution by changing the external temperature below and above the lower critical solution temperature (LCST) of the polymer. The results demonstrate that the elution of model compounds depends on the temperature-regulated size of the inter-particle voids and on the change of surface properties of the PNIPAM-grafted nanoparticles from hydrophilic to hydrophobic.

The growing utilization of renewable and residual biomasses for environmental preservation and remediation are important goals to be pursued to minimize the environmental impact of human activities. In this paper, sodium alginate (derived from brown algae) was crosslinked using chitosan (mainly derived from the exoskeleton of crustaceans) in the presence of biowaste-derived substances isolated from green compost (BBS-GC), to produce hydrogels and dried films. The obtained materials were tested as adsorbents for wastewater remediation. To this purpose, gels were characterized using a multi-analytical approach and used as active substrates for the removal of three differently-charged molecules, chosen as model pollutants: crystal violet, rhodamine B, and orange II. The effectiveness of the gel formulations was demonstrated and attributed to the variety of active functionalities introduced by the different precursors, the structural factors and the peculiar physicochemical properties of the resulting materials.

N-rich biochars were obtained via pyrolysis treatment of chitosan (a low-cost biopolymer from natural biomasses) at mild conditions (in the 284 °C–540 °C range), thus offering an energy efficient and low carbon footprint synthesis. These low surface area N-doped biochars were morphologically and physicochemically characterized, and tested as hosting material in lithium-sulfur (Li-S) batteries. Sulfur/biochars cathodes thus obtained showed good capacity retention and improved Coulombic efficiency compared to a standard N-rich high surface area carbon and multiwalled carbon nanotubes (MWCNT) reference substrates. Such enhanced electrochemical properties are attributable to the better retention of Li polysulfides by means of the residual functionalities still present in the biochars, thus making the valorization of chitosan potentially appealing even in the industrial sector related to the development of energy storage devices.

The valorization of low-cost biobased resources (such as biomasses and their derivatives) as alternative feedstock for the preparation of innovative sustainable materials allows both economic and environmental benefits, for instance when these materials enhance the photodegradation of organic pollutants in water remediation processes. This chapter presents the physicochemical features of biobased substances (BBS) isolated from urban organic residues, and it reports on their performances as chemical auxiliaries in advanced oxidation processes (AOPs). In the homogeneous phase, BBS can indeed promote the direct oxidation of organic pollutants through the formation of many reactive species, and it can also allow running Fenton and photo-Fenton processes at circumneutral pH. Additionally, BBS can be used in heterogeneous phase. In addition, the preparation, characterization, and pollutant photodegradation efficiency of novel heterogeneous systems based on hybrid magnet-responsive materials functionalized with biobased substances is discussed, whereas the functionalization with oxidative enzymes is presented as well.

Pyrolysis is the simplest method to convert bio-based materials into carbonaceous chars. In this study, Na alginate (an aquatic-derived substance isolated from brown algae) is thermally treated under very mild condition (onset temperature). The effectiveness of the conversion has been determined via physicochemical characterizations, showing the possibility of modifying the (bio)polymeric chemical structure just at the beginning of its thermal degradation, guaranteeing an overall energetic beneficial effect.

The photodegradation of an aqueous solution of diclofenac (DCF) has been attempted in the presence of hydrogen peroxide and organic/inorganic hybrid magnetic materials under simulated and real solar light. The hybrid magnetic materials have been prepared via coprecipitation synthesis starting from iron(II) and iron(III) inorganic salts in the presence of bioderived organic products (i.e., chitosan or bio-based substances isolated from commercially available composted urban biowastes) acting as stabilizers of the iron-containing phase. In addition to the as prepared hybrid materials, the corresponding materials obtained after a pyrolytic step at low temperature (550 °C) have been tested. The obtained results evidenced the capability of the materials to activate hydrogen peroxide at mild pH promoting DCF (photo) degradation. All the materials feature also as adsorbents since a decrease of DCF is observed also when working in the dark and in the absence of hydrogen peroxide.

The municipal biowaste anaerobic digestate of a typical waste treatment plant is pyrolyzed under a mild condition (i.e., 540 °C) to directly yield N-doped biochar without performing any subsequent functionalization process. The results confirmed the integration of nitrogen heteroatoms within the carbonaceous framework. The morphological characterization, instead, evidenced the formation of a rather dense biochar with a very low surface area.

Single-screw extrusion allows obtaining composite films containing poly(ethylene-co-vinyl alcohol), hereinafter EVOH, and water-soluble lignin-like biopolymers (SLP) isolated from the alkaline hydrolysate of two materials sampled from an urban waste treatment plant. During extrusion, a condensation reaction occurs between the EVOH and SLP. The products are heterogeneous. They contain a mix of EVOH-SLP copolymers with different composition and solubility properties. The films were characterized for tensile strength and water sorption properties. Young modulus and strain at break, respectively, were 2.8 GPa and 14% for neat EVOH vs. 2.1-0.9 GPa and 17–4% for the blends containing 2–15% SLP, with values decreasing upon increasing the % SLP. The blends were more hydrophilic than neat EVOH; their water sorption capacity was found to increase upon increasing the SLP content. Compared to previously reported similar blends obtained by twin-screw extrusion and solvent casting, the data for the single-screw extruded films allows discussing several aspects connected to the valorisation of blends obtained from fossil and biowaste sourced polymers.

Chitin (a biopolymer obtained from shellfish industry) was used as precursor for the production of biochars obtained via pyrolysis treatments performed at mild conditions (in the 290–540 °C range). Biochars were physicochemical characterized in order to evaluate the pyrolysis-induced effects in terms of both functional groups and material structure. Moreover, such carbonaceous materials were tested as adsorbent substrates for the removal of target molecules from aqueous environment as well as in solid-gas experiments, to measure the adsorption capacities and selectivity toward CO2. Lastly, biochars were also investigated as possible cathode materials in sustainable and low-cost electrochemical energy storage devices, such as lithium-sulphur (Li-S) batteries. Interestingly, experimental results evidenced that such chitin-derived biochars obtained via pyrolysis at mild conditions are sustainable, low-cost and easy scalable alternative materials suitable for both environmental and energetic applications.

In this study, chitosan and bio-based substances (BBS) obtained from composted biowaste were used as stabilizers for the synthesis of magnet-sensitive nanoparticles (NPs) via coprecipitation method. A pyrolysis treatment was carried out on both biopolymers at 550 °C, and their consequent conversion into a carbon matrix was followed by means of different physicochemical characterization techniques (mainly FTIR spectroscopy and XRD), whereas magnetic properties were evaluated by magnetization curves. The prepared materials were tested in water remediation processes from arsenic (As) species (both inorganic and organic forms). These tests, explained by means of the most common adsorption models, evidenced that the best performances were reached by both materials obtained after pyrolysis treatments, pointing out the promising application of such magnet-sensitive materials as easy-recoverable tools for water purification treatments.

Composted urban biowaste-derived substances (BBS-GC) are used as carbon sources for the preparation of carbon-coated magnet-sensitive nanoparticles obtained via co-precipitation method and the subsequent thermal treatment at 550 °C under nitrogen atmosphere. A multitechnique approach has been applied to investigate the morphology, magnetic properties, phase composition, thermal stability of the obtained magnet-sensitive materials. In particular, pyrolysis-induced modifications affecting the BBS-GC/carbon shell were highlighted. The adsorption capacity of such bio-derivative magnetic materials for the removal of hydrophobic contaminants such as polycyclic aromatic hydrocarbons was evaluated in order to verify their potential application in wastewater remediation process. The promising results suggest their use as a new generation of magnet-responsive easily-recoverable adsorbents for water purification treatments.

Sustainable alternative substrates for advanced applications represent an increasing field of research that attracts the attention of worldwide experts (in accordance with green chemistry principles). In this context, bio-based substances (BBS) isolated from urban composted biowaste were purified and characterized. Additionally, these materials were tested as auxiliaries in advanced oxidizing photocatalytic processes for the abatement of organic contaminants in aqueous medium. Results highlighted the capability of these substances to enhance efficiency in water remediation treatments under mild conditions, favoring the entire light-driven photocatalytic process.

The exploitation of organic waste as a source of bio-based substances to be used in environmental applications is gaining increasing interest. In the present research, compost-derived bio-based substances (BBS-Cs) were used to prepare hybrid magnetic nanoparticles (HMNPs) to be tested as an auxiliary in advanced oxidation processes. Hybrid magnetic nanoparticles can be indeed recovered at the end of the treatment and re-used in further water purification cycles. The research aimed to give new insights on the photodegradation of caffeine, chosen as marker of anthropogenic pollution in natural waters, and representative of the contaminants of emerging concern (CECs). Hybrid magnetic nanoparticles were synthetized starting from Fe(II) and Fe(III) salts and BBS-C aqueous solution, in alkali medium, via co-precipitation. Hybrid magnetic nanoparticles were characterized via X-ray diffraction (XRD), thermo-gravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy. The effect of pH, added hydrogen peroxide, and dissolved oxygen on caffeine photodegradation in the presence of HMNPs was assessed. The results allow for the hypothesis that caffeine abatement can be obtained in the presence of HMNPs and hydrogen peroxide through a heterogeneous photo-Fenton mechanism. The role of hydroxyl radicals in the process was assessed examining the effect of a selective hydroxyl radical scavenger on the caffeine degradation kinetic.

Although the importance of Fe (hydr)oxides for soil organic matter (OM) stabilization and C retention by surface adsorption is well known, only recently has coprecipitation been recognized as an important process responsible for C storage in hydromorphic soils, such as rice paddy soils. Under periodic fluctuations in redox conditions the interaction between dissolved organic carbon (DOC) and Fe (hydr)oxides may not only involve organic coatings on mineral surfaces, but also Fe-DOC coprecipitates that form during the oxidation of soil solutions containing important amounts of DOC and Fe2+. The aim of this work was to provide new insights into the mechanisms involved, and the amount and selectivity of C retained during the coprecipitation process. A series of Fe-OM associations with increasing C loading was synthesized at pH 6 by surface adsorption or coprecipitation (oxidation of ferrous iron) utilizing rice-straw derived dissolved organic matter. The kinetics of Fe2+ oxidation and complexation, and the total and selective retention of DOC during the coprecipitation process were evaluated. Moreover, synthesized associations, as well as a field coprecipitate collected in situ from a paddy soil, were studied by X-ray diffraction, N2 gas adsorption-desorption isotherms, electrophoretic mobility measurements and thermogravimetric analyses. Coprecipitation resulted in higher organic C contents (49-213 mg g-1) with respect to adsorbed systems (18-47 mg g-1), and favoured the inclusion of OM within highly aggregated associations having particularly low BET specific surface areas. Coprecipitates sampled in situ also showed a similar retention of organic C confirming that this process may contribute significantly to the OM stabilization in paddy topsoils. The mechanisms involved in the retention of straw-derived DOM during coprecipitation were shown to be strongly dependent on C/Fe ratio of the solution. Although the overall coprecipitation process was highly selective for ar

Un approccio supramolecolare per la fabbricazione di membrane polimeriche nano e isoporose a base di copolimeri a blocchi.

[EN] Caffeine-photosensitized degradation has been studied in the presence of bio-based materials derived from urban biowaste after aerobic aging. A peculiar fraction (namely bio-based substances (BBSs)), soluble in all the pH range, has been used as photosensitizing agent. Several caffeine photodegradation tests have been performed, and positive results have been obtained in the presence of BBSs and H2O2, without and with additional Fe(II) (photo-Fenton-like process). Moreover, hybrid magnetite-BBS nanoparticles have been synthesized and characterized, in order to improve the sensitizer recovery and reuse after the caffeine degradation. In the presence of such nanoparticles and H2O2 and Fe(II), the complete caffeine degradation has been attained in very short time. Both homogeneous and heterogeneous processes were run at pH = 5, milder condition compared to the classic photo-Fenton process.

In this study, bio-based substances (BBS) obtained from composted urban biowaste are used as stabilizers for the synthesis of magnet-sensitive nanoparticles (NPs). The BBS-stabilized NPs are characterized by means of different techniques (FTIR, XRD, SEM, BET analysis, magnetization curves). Additionally, TGA coupled on-line with FTIR and GC/MS analysis of the exhausted gas are performed in order to simultaneously identify all the degradation products and evaluate the exact composition of such BBS-stabilized materials. Moreover, Fenton-like or photo-Fenton-like experiments carried out at circumneutral pH are performed in order to evaluate the BBS-functionalized NPs photo-activity towards the degradation of caffeine (taken as model emerging pollutant). The obtained promising results encourage the use of BBS as a green alternative tool for the preparation of smart materials with enhanced magnet-sensitive properties, also suitable for applications in wastewater purification treatments.

Herein, porous photoactive nanocomposites are prepared by a simple one-pot synthesis approach using a salt and aqueous media. Within this reactive hypersaline route, the salt not only serves in the structuring of the composite but also becomes an integral active part of it. Here, the addition of sodium thiocyanate to a titania precursor guides, on the one hand, the formation of needleshaped nanoparticles and, on the other hand, forms yellow compound isoperthiocyanic acid, which is homogeneously incorporated into the porous nanocomposite. Compared to a pure titania reference, this material reveals a 7-fold-increased photodegradation rate of Rhodamine B as a model compound. This reveals the reactive hypersaline route to be a promising and facile synthesis route toward photoactive porous materials.