The agrifood industry shows one of the widest ranges of possible end products from crops, such as fruits, legumes, cereals, and tubers. The raw material is generally collected and processed industrially, producing a significant amount of organic waste. The overall picture is made more complex by the wide variety of nature and composition, and by the difficulty identifying the possible uses of the wastes coming from the processing industry. Such wastes are often disposed of in landfills or treated in waste-to-energy plants depending on the area where they are produced. The circular economy approach has suggested numerous possible generic strategies to improve waste management, involving the exploitation of waste to obtain new value-added products. The use of fibers from legume waste from the canning industry in the bioplastics production sector is a promising and relatively little explored line, particularly for the fibers of beans and green beans. With this in mind, in this article, green bean and borlotti bean fibers obtained from the treatment of wastes were used as reinforcing material for polycaprolactone (PCL)-based biocomposites by melt blending. Analyses were carried out about the morphological, spectroscopic, thermal, and mechanical properties of the starting and the obtained materials. Keywords: bean fibers; polycaprolactone; biocomposites

Introduction Nowadays, coastal pollution monitoring consists in study environmental media, such as sediments, water or/and biological samples, as mussels. A new challenge started in 2009 with the International Pellet Watch (IPW), proposing the use of resin pellet as no-living passive samplers, in order to avoid long and high-cost preparation samples of coastal environmental media. Positive correlation (Fig. 1) between POPs concentration in mussels and in resin pellet has been proved during IPW [1]. Fig. 1. Correlation between of ?PCBs in mussels (ng/g-lipid) and in plastic pellets (ng/g-pellet) [1]. Resin pellets are the small virgin plastic particles of different polymeric types from which all plastic objects are made. During plastic production processes, industries and factories disperse resin pellets in the environment and most of them arrive in the ocean standing there for a lot of time. Due to their specific weight almost the same of salt water, many of types of pellets floats in the marine microlayer, and many of them and many of them end up on the beaches. As the main POPs (persistent organic pollutants) and linear hydrocarbons absorption takes place in the microlayer where pollutants are most concentrated than in the water column. In this way pellets can sorb hydrophobic substance [2], [3]. The environmental pollution mapping methods proposed within the IPW is based on Endo et al. (2005) observation regarding a correlation between the degradation state of resin pellets (especially the PE ones) and their POPs content. They sustain that a more pronounced coloring (yellowing) of the pellet should indicate a longer residence time in the sea of such particles, and therefore a greater degradation of their polymeric matrix; the longer time spent in the sea also means a greater probability of having absorbed pollutants dissolved there, from which should follow a correlation between more intense coloration and POPs penetrated. This means that, by selecting the darkest pellets present at different sites, it is possible to get an idea of the degree of pollution in that particular area [4], [5]. As Endo et al. (2005) considerations are supported by a very small number of sampled pellets, we decided to undertake an "Italian pellets survey" in order to investigate, with a greater sample number and so a major statistical accuracy, the structural characteristics of beached pellets, trying to understand if exists a correlation between physical/chemical degradation state, their color (yellowing) and the organic pollutant concentrations. Fig 2. On the left: Discoloration of different polymeric matrix of pellets over time [3]. On the right: Digital photos of the raw pellets of standard of bio-plastic (in black), 6 months-aged in seawater (in blue) and 6-months-aged in sandbox reproducing beach conditions (in orange) [5]. Materials and methods We sampled pellets distributed in all the Italian peninsula during spring/summer of 2019, thanks to the contribution of volunteers of Italian NGO Legambiente. At the moment we have analysed pellets collected from Le Grazie Beach, which is located inside La Spezia Gulf, as shown in Fig.3.

Experimental studies in recent years highlight the presence of an increasingly high quantity of microplastics worldwide [1]. The "resin pellets" represent a significant share among the first generation microplastics in the millimeter range (from 1 to 5 mm). They disperse in the environment, even unintentionally, during transport, storage and processing and recent studies show that their content varies from 3% to about 30% of all microplastics surveyed on beaches [2]. A three-years experiment was carried out on a simulated beach and in marine water in Santa Teresa Bay (Gulf of La Spezia, Italy). In detail, special cages have been installed on the underwater observatory, LabMARE coastal station [3], placed at ten meters deep. The submarine station is equipped with a sensor for monitoring environmental parameters, recording data every 10 min. The experiment, aimed at investigating the behavior of plastic items and HDPE, PP, PLA and PBAT pellets, began on March 3, 2020 and is still ongoing. Here, the comparison between the properties of the raw pellets and those placed in the two different environments after six months, is discussed. Through chemical, spectroscopic and thermal analyses (GPC, SEM, FTIR-ATR, DSC, TGA) of granules, variations in color, surface morphology, chemical composition, thermal properties and molecular weight, and polydispersity of materials are analysed to show the different influences of environmental conditions. Acknowledgement: The authors thank the Italian Istituto Zooprofilattico Sperimentale del Piemonte, Liguria e Valle d'Aosta for some of the materials useful for the setup of the experiment, DLTM for the availability of LabMARE coastal underwater platform, Dr. Andrea Bordone and Dr. Giancarlo Raiteri (ENEA) for the temperature data of the seawater, and Dipartimento Polizia di Stato--Centro Nautico Sommozzatori of La Spezia (Italy) for the precious support in sampling activities. The authors also thank the Win on Waste group at Area della Ricerca CNR of Pisa (WoW, https://wow.area.pi.cnr.it/). References: [1] L. Peng, D. Fu, Sci. Total Environ, 698, 134254, 2020. [2] S. Merlino, M. Locritani, G. Bernardi, C. Como, S. Legnaioli, V. Palleschi, M. Abbate, Water, 12, 3389, 2020. [3] https://www.dltm.it/it/news/685-alla-spezia-un-laboratorio-sottomarino-costiero-per-testare-nuove-tecnologie-4.html

Choosing renewable energy from wind, solar, hydro, and biomass sources plays an essential role in reducing emissions and moving the global energy transition forward, as also requested by the European Community. Many national and international projects have been funded and now research activities PNRR-funded are starting to develop materials, components and equipment for the conversion and accumulation, the interoperability of sources, the flexibility and the integration of energy systems. In this direction, various groups belonging to the Institute for Chemical and Physical Processes (IPCF), have based their research activity on both an experimental [1-8] and theoretical [9-10] approach in: synthesis and functionalization of nanostructured materials for electrodes and sensitizers realization of dye-sensitized solar cells development of innovative materials, processes and technologies for the production of hydrogen improvement of reliability, efficiency, flexibility and resilience of the national energy system through a multi-scale computational modeling approach development of machine-learning algorithms and of networks for the construction of smart grids for energy management.

One of the pillars of the circular economy and green chemistry is the recovery and enhancement of waste materials. In the circular economy, a system is established where the products are designed in such a way that the generation of waste is minimal or totally eliminated, implementing a culture in which the product is designed to give it a second useful life, with added value and also the reduction of energy and raw material consumption is maximized [1]. Food industry, in particular, produces huge quantities of these materials that, without a valid reuse process, are destined for waste management with considerable economic and environmental costs. Conversely, reversing the traditional perspective, bio-based waste can become a source of many valuable substances with various applications. The driving force of this type of study is to find more and more uses for those that are basically scraps of industry, the disposal of which would be a considerable expense that would burden production processes. In recent years interest is moving from disposal to waste-valorisation with many advantages, both at the level of innovative products than at the level of waste treatment that at this point become an investment, a potential secondary resource instead of an expense. The valorisation of "the low value residues" for the development of new materials from agri-food waste is one of the many ways to take into consideration. The final stage of a production process becomes the beginning of a new cycle, different and often with unusual outcomes. Here we will show a way to breathe new life into these wastes. Thanks to the fibres and the protein fraction of legumes [2,3], to the cutin extracted from tomatoes [4,5], new materials have been achieved, firstly on a laboratory scale up to the scale-up to make the process industrial. Acknowledgement Marta Project. Sviluppo di una Innovativa MultipiattAforma SmaRt DrifTer - UMV- SAPR Per Indagini MArine. Programma POR CREO FESR TOSCANA 2014-2020. References [1] L. L. del Rio Osorio, E. Flórez-López, C. D. Grande-Tovar, Molecules, 26(2), 515, 2021. [2] L. Ricci, E. Umiltà, M.C. Righetti, T. Messina, C. Zurlini, A. Montanari, S. Bronco, M. Bertoldo, J. Sci. Food Agric., 98, 5368, 2018. [3] S. Bronco, M. C. Righetti, C. De Monte, M. Bertoldo, L. Ricci, P. Cinelli, A. Lazzeri Contributo al "10th Society And Materials International Conference SAM 10", 9-10 Maggio 2016, Roma, con poster dal titolo "Investigation of interfaces polymer/fiber and amorphous/crystal in biocomposite obtained from the valorization of agricultural co-products and by-products". [4] C. De Monte, L. Ricci, Oral communication in Science Colloquia, 11st March 2022 "A new life to industrial biobased wastes: from biopolymers to bioplastics". https://ipcfseminar.wordpress.com/a-new-life-to-industrial-biobased-wastes-from-biopolymers-to-bioplastics/ [5] L. Arrighetti, S. Bronco, C. De Monte, L. Ricci. "È possibile ottenere una bioplastica a partire da scarti agroalimentari?". https://wow.area.pi.cnr.it/bright-2021/

Descrizione di un esperimento di lungo periodo, volto alla comprensione degli effetti indotti su oggetti di plastica di uso comune ed in particolare sui resin pellets, dalla lunga immersione in ambiente marino reale. Si tratta di un esperimento in situ con un nuovo approccio per studiare l'invecchiamento dei pellets di plastica commerciali (definiti dimensionalmente come microplastiche) in ambiente marino utilizzando configurazioni sperimentali specificamente progettate per il monitoraggio a lungo termine del comportamento dei granuli di plastica (HDPE, PP, PLA e PBAT ). In particolare sono discussi i risultati dei primi sei mesi di una campagna di monitoraggio triennale. Cambiamenti di colore, morfologia superficiale, composizione chimica, proprietà termiche, peso molecolare e polidispersione, hanno mostrato le diverse influenze delle condizioni ambientali (acqua di mare o in condizioni costiere sabbiose). I risultati suggeriscono l'inizio di fenomeni di invecchiamento ma con un'evoluzione nel tempo ancora lunga e da stabilire. I risultati suggeriscono che qualsiasi presenza accidentale di MPs in PLA e/o PBAT in ambiente marino deve essere evitata perché dopo sei mesi il loro degrado è piuttosto limitato.

A new approach for studying the aging and degradation of commercial plastics in marine environments through an in-situ experiment is presented. Two experimental setups specifically designed for long-term monitoring of the behaviour of plastic granules (HDPE, PP, PLA and PBAT) are used. The results of the first six months of a three-year monitoring campaign are presented. The physico-chemical modifications that eventually occur in marine conditions (both in seawater and in sandy coastal conditions) on the granules before and after exposure to natural elements are described. Changes in colour, surface morphology, chemical composition, thermal properties, molecular weight and polydispersity, showed the diferences in influences of environmental conditions.

In this paper, we present two novel experimental setups specifically designed to perform in situ long-term monitoring of the aging behaviour of commercial plastic granules (HDPE, PP, PLA and PBAT). The results of the first six months of a three year monitoring campaign are presented. The two experimental setups consist of: (i) special cages positioned close to the sea floor at a depth of about 10 m, and (ii) a box containing sand exposed to atmospheric agents to simulate the surface of a beach. Starting from March 2020, plastic granules were put into the cages and plunged in seawater and in a sandboxe. Chemical spectroscopic and thermal analyses (GPC, SEM, FTIR-ATR, DSC, TGA) were performed on the granules before and after exposure to natural elements for six months, in order to identify the physical-chemical modifications occurring in marine environmental conditions (both in seawater and in sandy coastal conditions). Changes in colour, surface morphology, chemical composition, thermal properties, molecular weight and polydispersity, showed the different influences of the environmental conditions. Photooxidative reaction pathways were prevalent in the sandbox. Abrasive phenomena acted specially in the sea environment. PLA and PBAT did not show significant degradation after six months, making the possible reduction of marine pollution due to this process negligible.

A green, effective methodology for the preparation of water-based dispersions of poly(lactic acid) (PLA) for coating purposes is herein presented. The procedure consists of two steps: in the first one, an oil-in-water emulsion is obtained by mixing a solution of PLA in ethyl acetate with a water phase containing surfactant and stabilizer. Different homogenization methods as well as oil/water phase ratio, surfactant and stabilizer combinations were screened. In the second step, the quantitative evaporation of the organic provides water dispersions of PLA that are stable, at least, over several weeks at room temperature or at 4 degrees C. Particle size was in the 200-500 nm range, depending on the preparation conditions, as confirmed by scanning electron microscope (SEM) analysis. PLA was found not to suffer significant molecular weight degradation by gel permeation chromatography (GPC) analysis. Furthermore, two selected formulations with glass transition temperature (Tg) of 51 degrees C and 34 degrees C were tested for the preparation of PLA films by drying in PTFE capsules. In both cases, continuous films that are homogeneous by Fourier-transform infrared spectroscopy (FT-IR) and SEM observation were obtained only when drying was performed above 60 degrees C. The formulation with lower Tg results in films which are more flexible and transparent.

Polyvinyl butyral (PVB) is an amorphous polymer employed in many technological applications. In order to highlight the relationships between macroscopic properties and dynamics at a microscopic level, motions of the main-chain and of the propyl side-chains were investigated between Tg - 288o C and Tg + 55o C, with Tg indicating the glass transition temperature. To this aim, a combination of solid state Nuclear Magnetic Resonance (NMR) methods was applied to two purposely synthesized PVB isotopomers: one fully protonated and the other perdeuterated on the side-chains.1 H time domain NMR and1 H field cycling NMR relaxometry experiments, performed across and above Tg, revealed that the dynamics of the main-chain corresponds to the ?-relaxation associated to the glass transition, which was previously characterized by dielectric spectroscopy. A faster secondary relaxation was observed for the first time and ascribed to side-chains. The geometry and rate of motions of the different groups in the side-chains were characterized below Tg by2 H NMR spectroscopy.

Polyvinyl alcohol (PVA) hydrogels were prepared by a cyclic freezing-thawing technique without any cross-linker agent, using PVA and Maghnite water dispersion with different ratios. The obtained results have shown a higher thermal stability of samples with sodium than with alkylammonium Maghnite. Furthermore, thermal stability was maximum at the lowest investigated Maghnite/PVA ratio, but higher than for the pure PVA at all the investigated compositions. DSC analysis has shown both a low crystal degree and a low heat capacity jump at the glass transition temperature for samples with high Maghnite content. This phase does not seem to depend on the kind of cations, sodium or alkylammonium into the gallery of the clay.

BACKGROUNDPea, lentil, faba bean, chickpea and bean proteins are potentially renewable raw materials for bioplastic production that can be obtained from agricultural waste. Plastics are usually processed under heating, and thus thermal stability is a mandatory requirement for the application. In this study, the thermal behavior of several legume protein isolates at different purity degrees was investigated.

In this work, we demonstrate - in two different settings - the potential of the recognition motif made by tetraphosphonate cavitand/N-methyl ammonium salt for the development of supramolecular polymer chemistry. In the first part a novel pH sensitive supramolecular homopolymer was assembled by proper design of the corresponding monomer, and monitoring the self-assembling process by several analytical tools, including NMR spectroscopy and light scattering techniques. These measurements provided the evidence for the formation of the homopolymer and its pH responsiveness. In the second study, the two recognition groups - tetraphosphonate cavitand (Host) and sarcosine hydrochloride (Sarc) - introduced in polystyrene (PS-Host) and poly(butyl methacrylate) (PBMA-Sarc) respectively, led to the mixing of the two otherwise immiscible polymers thanks to the energetically favourable host-guest interactions between the polymer chains. The polymer blending was verified by the presence of a single glass transition temperature (T-g) and showed its homogeneous morphology by atomic force microscopy (AFM).

Nitroxyl radicals were used as functionalizing agents during the free radical postreactor modification process of polyolefins carried out in the melt. The 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (HO-TEMPO) and the 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (BzO-TEMPO) free radicals were successfully grafted onto a polyethylene-based material (ethylene-co-1-octene copolymer) by coupling reaction with polymer macroradicals; these last were formed by H-abstraction through peroxide addition. The macromolecular structure of the functionalized polyolefins was assessed by 1H-NMR, FTIR spectroscopy, and SEC measurements which were used to evidence the grafting site, to evaluate the grafting level and to highlight the occurrence of chain extension through crosslinking side reactions. Indeed the use of proper model compounds allowed the preparation of accurate FTIR calibration curves for the quantitative determination of the functionalization degree. Besides the high temperature SEC analysis highlighted that this fast and simple coupling reaction between macroradicals and nitroxyl free radicals grants the grafting of functionalities onto the polyolefin backbone by contemporarily preventing the side reactions liable of the structure and MW modification of the pristine polymer.