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PLA/PBAT bioplastic is a commercial biodegradable plastic employed for packaging and several food and agriculture applications. In this regard, properties such as the antioxidant ability to extend food shelf life and light resistance, are of great interest in the production of packaging and mulching films, respectively. These features are obtained by developing blends with pure chemicals and/or natural products as additives. In the present work blend formulations of PLA/ PBAT with a walnut shell extract rich in antioxidants were developed and evaluated for their properties in comparison with classic PLA/PBAT. Specifically, natural additives, and most importantly the production process were purposely selected to i) be green and cost-effective; ii) confer antioxidant properties; and iii) improve material performance. To this aim, a walnut shell extract (EWS) with high antioxidant activity was obtained thanks to a novel green and cost-effective microwave-assisted extraction (MAE) procedure. A response surface methodology was utilized to explore how the total phenolic content (TPC) and antioxidant activity are influenced by varying aqueous ethanol concentration, extraction time, and microwave power. The highest predicted TPC and antioxidant activity were achieved when employing the ideal conditions for Microwave-Assisted Extraction (MAE): using a mixture of 30 % ethanol in water, an irradiation time of 120 s, and a microwave power of 670 W. The optimized EWS was characterized by HPLC-MS determining qualitative and quantitative data with the identification of flavonoids, fatty acids, and anacardic acids among the main components, responsible for antioxidant activity. The resulting EWS powder was melt-mixed at 140Co and 20 RPM with the bio-based PLA/PBAT bioplastic at two different concentrations (0.5 and 1.5 w/w) by forming film specimens. All EWS-based bioplastic films showed increased antioxidant features determined by the DPPH bleaching test, TEAC, and ORAC assays. The films keep the antioxidant capacity even after 7 days of UV-accelerated aging. Remarkably, adding 1.5 % EWS boosted the bioplastic UV light resistance, reducing

This work aims to investigate the morphological and chemical-physical changes induced by adding ZnO nanoparticles to bio-based polymeric materials based on polylactic acid (PLA) and polyamide 11 (PA11). The photo- and water-degradation phenomena of these nanocomposite materials were monitored. For this purpose, the formulation and characterization of novel bio-nanocomposite blends based on PLA and PA11 at a ratio of 70/30 wt.% filled with zinc oxide (ZnO) nanostructures at different percentages were performed. The effect of nanoparticles (<=2 wt.%) within the blends was thoroughly explored by employing thermogravimetry (TGA), size exclusion chromatography (SEC), matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS) and scanning and transmission electron microscopy (SEM and TEM). Adding up to 1% wt. of ZnO resulted in a higher thermal stability of the PA11/PLA blends, with a decrement lower than 8% in terms of molar masses (MMs) values being obtained during blend processing at 200 °C. ZnO promoted trans-ester-amide reactions between the two polymers, leading to the formation of PLA/PA11 copolymers. These species could work as compatibilisers at the polymer interface, improving thermal and mechanical properties. However, the addition of higher quantities of ZnO affected such properties, influencing the photo-oxidative behaviour and thus thwarting the material's application for packaging use. The PLA and blend formulations were subjected to natural aging in seawater for two weeks under natural light exposure. The 0.5% wt. ZnO sample induced polymer degradation with a decrease of 34% in the MMs compared to the neat samples.

As the market uptake of perovskite solar cells (PSCs) is projected to grow rapidly, this clean energy technology will play an increasingly important role in reducing the global carbon footprint. However, one of the major barriers to its full commercialization is the presence of toxic lead (Pb), which enables the current record in photoconversion efficiency but risks being released into the environment when subjected to water or rain. Here we show that Pb leakage can be prevented by applying a transparent titanium dioxide (TiO2) sponge that allows for an efficient Pb sequestration of 58 ng cm(-2) nm(-1). Already an essential material for PSCs, the additional use of TiO2 through a scalable and solvent-free sputtering process promises extra cost benefits and higher sustainability. Further demonstration of the sponge application with desired thickness on ready-to-use devices, glass and polymeric foils enforces the practical value of the current approach. Our study provides a sustainable solution to one of the environmental and health risks of PSCs and would accelerate their practical applications.

The aim of the present progress report is to provide an update on the ongoing research carried out within the PAPILLONS WP1, Task 1.2, focusing on the ageing, transformation, and fragmentation of agricultural plastics (APs). Task 1.2 delves into the degradation and fragmentation processes and rates of MNP generation from APs during usage, ageing, and End-of-Life (EoL). This task comprises four subtasks that collectively contribute to understanding the various AP products degradation and fragmentation behavior and its potential soil pollution by the generation of MNP.

The present work is aimed at the scale up of CrioPurA, a chelating material that is used in water treatment for the removal of toxic metals such as chromium, boron, and arsenic, with higher efficiencies than current competitors. The advancement of the TRL (Technology Readiness Level) of the proof-of-concept material to levels 5-6 concerns the study of environmental sustainability in relation to the economy of production, and the possible alternative methods of use. The scaling up was carried out on the synthesis of 4-vinyl-benzyl chloride with N-methyl-D-glucamine, a reaction that leads to the formation of the monomer 4-vinyl-benzyl-N-methyl-D-glucamine (VbNMDG). The synthesis of the monomer, used for the cryo-polymerization of the filtering material, has been modified to allow greater environmental sustainability and cost-effectiveness of the process. Specifically, methanol, used as a solvent for monomer synthesis, was recycled with a 10% loss. Furthermore, on a laboratory scale1,2, the purification of the monomer takes place by crystallization from CHCl3. During the scale-up, this step was advantageously eliminated. The subsequent polymerization process was therefore reviewed in terms of stoichiometric ratios of the reactants, to achieve reaction yields and chemical-physical properties like those tested for the proof of concept 1, 2. The scale-up process was carried out gradually, going through three intermediate steps, up to 1 kg of production, obtaining an 80% yield. Finally, CrioPurA was tested in a demonstrator purposely made to allow flow tests up to a flow rate of 300 liters/hour by varying the load of polluted water. The product obtained by applying the new protocol was also analyzed at different pH values, comparing the data obtained with those of the main competitors on the market. The advancement of the TRL of the CrioPurA material has allowed the design of alternative and more sustainable synthetic roads both in economic and environmental terms. The material has been successfully tested both in batch and flow, at different pH values and using polluting loads of organic nature.

N-methyl-D-glucamine (NMG) is a chelating molecule used for environmental purposes for its high efficiency and selectivity versus metal ions species. The technology namely CrioPurA regards the realization of NMG-based hydrogels, produced by cryo-polymerization in water. The synthesis of ad-hoc functionalized polymeric materials with chelating groups is a sustainable and low-cost strategy to obtain adsorbent materials. In particular, the technique adopted for the realization of material allows to obtain different structures as well as shapes of different sizes, with high porosity, permeability and excellent sequestering action towards boron, arsenic, chromium and other metals ions from the water. CrioPurA can be regenerated, reused and adapted to existing water treatment plants

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In this study, antibacterial polymer blends based on Polyvinyl Chloride (PVC) and Polystyrene-Ethylene-Butylene-Styrene (SEBS), loaded with the ionic liquid (IL) 1-hexadecyl-3-methyl imidazolium 1,3-dimethyl 5-sulfoisophthalate (HdmimDMSIP) at three different concentrations (1%, 5%, and 10%), were produced. The IL/blends were characterized by their thermo-mechanical properties, surface morphology, and wettability. IL release from the blends was also evaluated. The agar diffusion method was used to test the antibacterial activity of the blends against Staphylococcus epidermidis and Escherichia coli. Results from thermal analyses showed compatibility between the IL and the PVC matrix, while phase separation in the SEBS/IL blends was observed. These results were confirmed using PY-GC MS data. SEM analyses highlighted abundant IL deposition on PVC blend film surfaces containing the IL at 5-10% concentrations, whereas the SEBS blend film surfaces showed irregular structures similar to islands of different sizes. Data on water contact angle proved that the loading of the IL into both polymer matrices induced higher wettability of the blends' surfaces, mostly in the SEBS films. The mechanical analyses evidenced a lowering of Young's Modulus, Tensile Stress, and Strain at Break in the SEBS blends, according to IL concentration. The PVC/IL blends showed a similar trend, but with an increase in the Strain at Break as IL concentration in the blends increased. Both PVC/IL and SEBS/IL blends displayed the best performance against Staphylococcus epidermidis, being active at low concentration (1%), whereas the antimicrobial activity against Escherichia coli was lower than that of S. epidermidis. Release data highlighted an IL dose-dependent release. These results are promising for a versatile use of these antimicrobial polymers in a variety of fields.

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It is well known that skin wound healing could be severely impaired in space. In particular, the skin is the tissue at risk of injury, especially during human-crewed space missions. Here, we propose a hybrid system based on the biocompatible poly 2-hydroxyethyl methacrylate (pHEMA) to actively support a nanocontainer filled with the drug. Specifically, during the cryo-polymerization of HEMA, halloysite nanotubes (HNTs) embedded with thymol (Thy) were added as a component. Thy is a natural pharmaceutical ingredient used to confer wound healing properties to the material, whereas HNTs were used to entrap the Thy into the lumen to ensure a sustained release of the drug. The as-obtained material was characterized by chemical-physical methods, and tests were performed to assess its ability for a prolonged drug release. The results showed that the adopted synthetic procedure allows the formation of a super absorbent system with good swelling ability that can contain up to 5.5 mg of Thy in about 90 mg of dried sponge. Releasing tests demonstrated the excellent material's ability to perform a slow controlled delivery of 62% of charged Thy within a week. As humans venture deeper into space, with more extended missions, limited medical capabilities, and a higher risk of skin wounds, the proposed device would be a versatile miniaturized device for skin repair in space.

The goal of this work was to investigate the morphological and chemical-physical changes induced by adding ZnO nanoparticles to bio-based polymeric materials based on polylactic acid (PLA) and polyamide 11 (PA11). Precisely, the photo- and water-degradation phenomena of nanocomposite materials were monitored. For this purpose, the formulation and characterization of novel bio- nanocomposite blends based on PLA and PA11 at a ratio of 70/30 wt.% filled with zinc oxide (ZnO) nanostructures at different percentages were performed. The effect of ZnO nanoparticles (<=2 wt.%) within the blends was thoroughly explored by employing thermogravimetry (TGA), size exclusion chromatography (SEC), matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS) and scanning and transmission electron microscopy (SEM and TEM). Adding up to 1% wt. of ZnO resulted in a higher thermal stability of the PA11/PLA blends, with a decrement lower than 8% in terms of molar masses (MMs) values being obtained during blend processing at 200 oC. ZnO promoted trans-ester-amide reactions between the two polymers, leading to the formation of PLA/PA11 copolymers. These species could work as compatibilisers at the polymer interface, improving thermal and mechanical properties. However, the addition of higher quantities of ZnO affected such properties, influencing the photo-oxidative behaviour and thus thwarting the material's application for packaging use. The PLA and blend formulations were subjected to natural aging in seawater for two weeks under natural light exposure. The 0.5% wt. ZnO sample induced polymer degradation with a decrease of 34% in the MMs compared to the neat samples.

A series of poly(ether sulfone) random copolymers at various loading of diphenolic acid (DPA) units were synthesized and subjected to a comprehensive kinetics degradation study to assess their thermal behaviour. Poly(ether sulfones) were synthesized from different amounts of 4,4?dihydroxydiphenylsulfone, DPA and stoichiometric quantity of 4,4?-dichlorodiphenyl sulfone by nucleophilic aromatic displacement. The apparent activation energy (E) of degradation for the prepared compounds was determined by using a kinetics literature method, discussed and compared with each other and with those obtained in the past for similar polymers. The comprehensive thermal stability evaluation was completed with the assessment of the initial decomposition temperature of the prepared copolymer, showing a good thermal performance but, in the meantime, suggesting caution as regards the percentage of functionalization setting the limit beyond which a deterioration of the physical properties of the copolymers at 30% of pendant carboxylic acid groups was observed.

EnjoiPol comprises several interesting research activities in the framework of the development and characterization of hybrid polymeric nanomaterials. The mission is to develop concrete solutions to the modern environmental challenges such as the pollution of natural water supplies, marine environment, and soil due to the presence of emerging contaminants such as microplastics, pesticides and fertilizers, heavy metals and drugs. Specifically, EnjoiPol research activities concern: a)chemical and structural characterization of plastics and microplastics present in marine environment and soil; in particular, the study of their interaction with organic and inorganic contaminants and their adsorption/release behaviour in the media.1 Part of the work is devoted to the valorisation of plastic debris collected from the sea, obtaining biofuel by means of pyrolysis treatment; b)formulation and study of innovative nano-systems coated with chitosan or alginate, for the realization of safe nano-fertilisers with low environmental impact;2 c)synthesis of acrylic and vinyl hydrogels/cryogels, properly functionalised for the selective removal of organic and inorganic contaminants from water. Specifically, we focused our attention on the sequestration of heavy metals3, drugs and pesticides4, by using chelation and molecular imprinting strategies. Hybrid organic/inorganic nanomaterials have been designed and synthesised, by combining the polyacrylates with organic photoactive units. The final hybrid nano-systems can perform selective removal and photodegradation of the contaminants at the polymer/water interface until mineralization.5 The patented polymer materials are currently involved in the industrial scale up activities, as well as the technology transfer process, including business study and marketing analysis; d)formulation and characterization of new bio-based polymer nanocomposites for the realization of rigid and sustainable packaging. Study of the degradation induced by UV light irradiation and by exposure to marine environment.6 Acknowledgements: the authors really thank all the people and institution involved in the projects Papillion, Clean, Antìbio, Samothrace, CrioPura References [1]. Submitted: Chemosphere [2]. Leonardi M., Caruso M.G., Carroccio S.C., Boninelli S., Curcuruto G., Zimbone M., Allegra M., Torrisi B., Ferlito F., Miritello M.; Smart nanocomposites of chitosan/alginate nanoparticles loaded with copper oxide as alternative nanofertilizers; Environ. Sci.: Nano, 2021, 8, 174187. [3]. Brevetto e CEJ 2020 [4]. Zagni C., Dattilo S., Mecca T., Gugliuzzo C., Scamporrino A. A., Privitera V., Puglisi R., Carroccio S. C.; Single and dual polymeric sponges for emerging pollutants removal, European Polymer Journal, 2022, 179, 111556

Esposizione dell'evoluzione della tecnologia "CrioPurA

A platform of polymeric cryogels based on methacrylic acid (C-mA) meglumine (C-megl), lysine (C-lys), and 2- hydroxy ethyl methacrylate (C-ph), as well as a combination thereof having both negatively and positively charged moieties, have been synthesized and used to efficiently remove emerging contaminants from water. Their peculiar properties in sequestering antibiotics (Levofloxacin, Ampicillin, Doxycycline), anti-inflammatory (Piroxicam), antifungal (Fluconazole), anti-parasite (Moxidectin), pesticides (2,4D) and dyes (Thymol blue, Methylene Violet) were tested taking into account their ionic nature in solution. The adsorption experiments performed in batches at different pH and pollutant concentrations have demonstrated the outstanding ability of these macroporous soft systems in complexing molecules by the instauration of various binding forces, also in the presence of inorganic species such as arsenic (as arseniate). In addition, it was demonstrated as the novel dual- material, ad-hoc synthesized by using opposite charge cryogels, can simultaneously remove antagonist dyes in a single and fast cycle. Besides, a quasi-total release of the target molecules was achieved by changing pH, allowing the regeneration of the macroporous sponges for multiple re-uses without losing their performance. The latter peculiar feature may be adopted for drug delivery applications since the release can be modulated and pro- grammed by a specific pH stimulus.

L'obiettivo di questo lavoro riguarda lo scale up di un materiale chelante che trova impiego nella trattamento acque per la rimozione metalli tossici quali arsenico, boro e cromo. L'attività svolta ha mirato ad uno sviluppo sostenibile della produzionesia del monomero che del polimero. La sintesi del monomero e la sua successiva polimerizzazione sono state scalate arrivando alla produzione e al design di 1 Kg di materiale filtrante testato sia in bach che sotto un flusso di 300l/h.

Aromatic poly(ether sulfone)s (PESs) are engineering thermoplastic materials with excellent chemical and thermal stability. Despite this, PESs have some limitations. Lack of hydrophilic groups and the closing arrangement of macromolecular chains lead to the high hydrophobicity of PES, causing the accumulation phenomena on the surface of membranes (biofouling). With the aim to obtain materials well balanced in terms of hydrophobic and hydrophilic character, the insertion of carboxyl and sulfonic groups and their effects on the behaviors of the polymers was verified and applied to the engineering of different kind of membranes for several applications. New functionalized Poly(ether sulfone)s having different molar ratio of 4,4-bis phenoxy pentanoic acid (diphenolic acid; DPA) units were synthesized and structurally characterized by (1H and 13C)-NMR, MALDI-TOF MS, FT-IR, DSC, and Contact Angle analyses. Thermal degradation processes were also studied by direct-pyrolysis/MS (DPMS), stepwise pyrolysis-gas chromatography/MS and thermogravimetric techniques. The presence of different amount of DPA units along the polymer chains affects the chemical and physical properties of the copolymers. The Tg and the contact angle values decrease as the molar fraction of DPA units increases, whereas the hydrophilicity increases. NMR and MALDI-TOF MS analyses show that all polymer chains are, as expected, randomic and almost terminated with hydroxyl and chlorine as end groups. The thermal stabilities, the pyrolysis products and the thermal degradation mechanisms of the copolymer samples have been identified through the combination of DPMS, Py-GC/MS and TGA data. Their thermal behavior was compared with that of a well-known commercial PES (referred to as PESES) sample.

Benzofulvene derivatives bearing complexed and un-complexed pyridine rings are designed and synthesized to assess the effects on the spontaneous solid-state polymerization of the presence in position 6 of the 3-phenylbenzofulvene moiety of bulky substituents capable of establishing metallophilic interactions. Both the benzofulvene monomers are found to polymerize spontaneously upon solvent removal under reduced pressure in the apparent absence of catalysts or initiators. The resulting polybenzofulvene derivatives are characterized by NMR spectroscopy, MALDI-TOF mass spectrometry, and in photophysical studies.

Materiale informativo/didattico sulla storia, gli aspetti tecnici, il corretto utilizzo e le possibili vie di smaltimento dei materiali plastici. Riferimenti ai manufatti plastici ritrovati in mare ed al possibile recupero energetico tramite tecniche pirolitiche.