Triggering of Polymer-Degrading Enzymes from Layered Double Hydroxides for Recycling Strategies.

The use of degrading enzymes in polymer formulation is a very attractive strategy to manage the end-of-life of plastics. However, high temperatures cause the denaturation of enzymes and the loss of their catalytic activity; therefore, protection strategies are necessary. Once protected, the enzyme needs to be released in appropriate media to exert its catalytic activity. A successful protection strategy involves the use of layered double hydroxides: cutinase, selected as a highly degrading polyester hydrolytic enzyme, is thermally protected by immobilization in Mg/Al layered double hydroxide structures. Different triggering media are here evaluated in order to find the best releasing conditions of cutinase from LDH. In detail, phosphate and citrate-phosphate buffers, potassium carbonate, sodium chloride, and sodium sulfate solutions are studied. After the comparison of all media in terms of protein release and activity retained, phosphate buffer is selected as the best candidate for the release of cutinase from LDH, and the effect of pH and concentration is also evaluated. The amount of the enzyme released is determined with the Lowry method. Activity tests are performed via spectrophotometry.

Valorization of Ferulic Acid from Agro-Industrial by-Products for Application in Agriculture.

The use of bioplastic mulch in agriculture has increased dramatically in the last years throughout the world. Nowadays, biodegradable materials for mulching films strive to constitute a reliable and more sustainable alternative to classical materials such as polyethylene (PE). The main challenge is to improve their durability in the soil to meet the required service length for crop farming by using benign and sustainable antioxidant systems. Here, we report the design and fabrication of biodegradable materials based on polybutylene (succinate adipate) (PBSA) for mulching applications, incorporating a fully biobased polymeric antioxidant deriving from ferulic acid, which can be extracted from an industrial by-product. Poly-dihydro (ethylene ferulate) (PHEF) from ferulic acid was synthesized by a two-step polymerization process. It is characterized by improved thermal stability in comparison with ferulic acid monomer and therefore suitable for common industrial processing conditions. Different blends of PBSA and PHEF obtained by melt mixing or by reactive extrusion were prepared and analyzed to understand the effect of the presence of PHEF. The results demonstrate that PHEF, when processed by reactive extrusion, presents a remarkable antioxidant effect, even in comparison with commercial additives, preserving a high level of the mechanical properties of the PBSA matrix without affecting the biodegradable character of the blend.

Enzymatic Degradation of the Most Common Aliphatic Bio-Polyesters and Evaluation of the Mechanisms Involved: An Extended Study.

Commercial hydrolytic enzymes belonging to different subclasses (several lipases, proteinase k, cutinase) were investigated for their ability to degrade different aliphatic polyesters, i.e., poly(butylene succinate) (PBS), poly(butylene succinate-co-adipate) (PBSA), two poly(caprolactone), having two different molecular weights, poly(lactic acid) (PLA) and poly(propylene carbonate) (PPC). The enzyme screening was first carried out by investigating the capacity of fully degrading the target polymers in 24 h, then weight loss measurements of selected polyesters and target enzymes were performed. Solid residues after enzyme degradation were characterized by proton nuclear magnetic resonance (1H NMR), gel permeation chromatography (GPC), infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC) and thermogravimetry (TGA). Liquid fractions were studied via GPC, 1H NMR and high-performance liquid chromatography (HPLC). PCL and PBSA were found to be the most biodegradable polyesters, under the conditions used in this study. PBS was fully degraded only by cutinase, whereas none of the tested enzymes were able to completely degrade PLA and PPC, in the conditions assessed here. Cutinase exhibited the highest hydrolytic activity on PBSA, while lipase from Candida sp. (CALB) on low molecular weight PCL. Chemical analyses on residual solids showed that the enzymatic degradation occurred homogeneously from the surface through an erosion mechanism and did not significantly affect the macromolecular structure and thermal stability. Cleaving action mode for each enzyme (endo- and/or exo-type) on the different polyesters were also proposed based on the evaluation of the degradation products in the liquid fraction.

Current Advances in the Sustainable Conversion of 5-Hydroxymethylfurfural into 2,5-Furandicarboxylic Acid.

2,5-Furandicarboxylic acid (FDCA) is currently considered one of the most relevant bio-sourced building blocks, representing a fully sustainable competitor for terephthalic acid as well as the main component in green polymers such as poly(ethylene 2,5-furandicarboxylate) (PEF). The oxidation of biobased 5-hydroxymethylfurfural (HMF) represents the most straightforward approach to obtain FDCA, thus attracting the attention of both academia and industries, as testified by Avantium with the creation of a new plant expected to produce 5000 tons per year. Several approaches allow the oxidation of HMF to FDCA. Metal-mediated homogeneous and heterogeneous catalysis, metal-free catalysis, electrochemical approaches, light-mediated procedures, as well as biocatalytic processes share the target to achieve FDCA in high yield and mild conditions. This Review aims to give an up-to-date overview of the current developments in the main synthetic pathways to obtain FDCA from HMF, with a specific focus on process sustainability.

End of Life of Biodegradable Plastics: Composting versus Re/Upcycling.

Nowadays the issues related to the end of life of traditional plastics are very urgent due to the important pollution problems that plastics have caused. Biodegradable plastics can help to try to mitigate these problems, but even bioplastics need much attention to carefully evaluate the different options for plastic waste disposal. In this Minireview, three different end-of-life scenarios (composting, recycling, and upcycling) were evaluated in terms of literature review. As a result, the ability of bioplastics to be biodegraded by composting has been related to physical variables and materials characteristics. Hence, it is possible to deduce that the process is mature enough to be a good way to minimize bioplastic waste and valorize it for the production of a fertilizer. Recycling and upcycling options, which could open up many interesting new scenarios for the production of high-value materials, are less studied. Research in this area can be strongly encouraged.

Recent advances in the production of biomedical systems based on polyhydroxyalkanoates and exopolysaccharides.

In recent years, growing attention has been devoted to naturally occurring biological macromolecules and their ensuing application in agriculture, cosmetics, food and pharmaceutical industries. They inherently have antigenicity, low immunogenicity, excellent biocompatibility and cytocompatibility, which are ideal properties for the design of biomedical devices, especially for the controlled delivery of active ingredients in the most diverse contexts. Furthermore, these properties can be modulated by chemical modification via the incorporation of other (macro)molecules in a random or controlled way, aiming at improving their functionality for each specific application. Among the wide variety of natural polymers, microbial polyhydroxyalkanoates (PHAs) and exopolysaccharides (EPS) are often considered for the development of original biomaterials due to their unique physicochemical and biological features. Here, we aim to fullfil a gap on the present associated literature, bringing an up-to-date overview of ongoing research strategies that make use of PHAs (poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate), poly (3-hydroxyoctanoate), poly(3-hydroxypropionate), poly (3-hydroxyhexanoate-co-3-hydroxyoctanoate), and poly (3-hydroxybutyrate-co-3-hydroxyhexanoate)) and EPS (bacterial cellulose, alginates, curdlan, pullulan, xanthan gum, dextran, hyaluronan, and schizophyllan) as sources of interesting and versatile biomaterials. For the first time, a monograph addressing the properties, pros and cons, status, challenges, and recent progresses regarding the application of these two important classes of biopolymers in biomedicine is presented.

Bio-Based Furan-Polyesters/Graphene Nanocomposites Prepared by In Situ Polymerization.

In situ intercalative polymerization has been investigated as a strategic way to obtain poly(propylene 2,5-furandicarboxylate) (PPF) and poly(hexamethylene 2,5-furandicarboxylate) (PHF) nanocomposites with different graphene types and amounts. Graphene (G) has been dispersed in surfactant stabilized water suspensions. The loading range in composites was 0.25-0.75 wt %. For the highest composition, a different type of graphene (XT500) dispersed in 1,3 propanediol, containing a 6% of oxidized graphene and without surfactant has been also tested. The results showed that the amorphous PPF is able to crystallize during heating scan in DSC and graphene seems to affect such capability: G hinders the polymer chains in reaching an ordered state, showing even more depressed cold crystallization and melting. On the contrary, such hindering effect is absent with XT500, which rather induces the opposite. Concerning the thermal stability, no improvement has been induced by graphene, even if the onset degradation temperatures remain high for all the materials. A moderate enhancement in mechanical properties is observed in PPF composite with XT500, and especially in PHF composite, where a significative increase of 10-20% in storage modulus E' is maintained in almost all the temperature range. Such an increase is also reflected in a slightly higher heat distortion temperature. These preliminary results can be useful in order to further address the field of application of furan-based polyesters; in particular, they could be promising as packaging materials.

Integrated Efforts for the Valorization of Sweet Potato By-Products within a Circular Economy Concept: Biocomposites for Packaging Applications Close the Loop.

With the aim to fully exploit the by-products obtained after the industrial extraction of starch from sweet potatoes, a cascading approach was developed to extract high-value molecules, such as proteins and pectins, and to valorize the solid fraction, rich in starch and fibrous components. This fraction was used to prepare new biocomposites designed for food packaging applications. The sweet potato residue was added to poly(3-hydroxybutyrate-co-3-hydroxyvalerate) in various amounts up to 40 wt % by melt mixing, without any previous treatment. The composites are semicrystalline materials, characterized by thermal stability up to 260 °C. For the composites containing up to 10 wt % of residue, the tensile strength remains over 30 MPa and the strain stays over 3.2%. A homogeneous dispersion of the sweet potato waste into the bio-polymeric matrix was achieved but, despite the presence of hydrogen bond interactions between the components, a poor interfacial adhesion was detected. Considering the significant percentage of sweet potato waste used, the biocomposites obtained show a low economic and environmental impact, resulting in an interesting bio-alternative to the materials commonly used in the packaging industry. Thus, according to the principles of a circular economy, the preparation of the biocomposites closes the loop of the complete valorization of sweet potato products and by-products.

Water Vapor Sorption and Diffusivity in Bio-Based Poly(Ethylene Vanillate)-PEV.

The dynamic and equilibrium water vapor sorption properties of amorphous and highly crystalline poly(ethylene vanillate) (PEV) films were determined via gravimetric analysis, at 20 °C, over a wide range of relative humidity (0-95% RH). At low RH%, the dynamic of the sorption process obeys Fick's law while at higher relative humidity it is characterized by a drift ascribable to non-Fickian relaxations. The non-Fickian relaxations, which are responsible for the incorporation of additional water, are correlated with the upturn of the sorption isotherms and simultaneously the hysteresis recorded between sorption and desorption cycles. The sorption isotherms of amorphous and highly crystalline PEV are arranged in the same concentration range of that of PET proving the similarity of the two polyesters. Water diffusion coefficients, whose determination from individual kinetic sorption/desorption curves required treatment with the Barens-Hopfenberg model, were demonstrated to be ≈ 10× higher for amorphous PEV compared to amorphous PET. Such a difference originates from the enhanced segmental flexibility of PEV chains.

Cascade strategies for the full valorisation of Garganega white grape pomace towards bioactive extracts and bio-based materials.

Agro-waste reduction and reuse are among the current main social challenges. In this perspective, the present research was aimed at the complete valorisation of Garganega grape pomace by recovering bioactive phenol extracts and by testing the solid fibre extract residues in composite formulation for packaging applications. The pomace was derived from white wine production, therefore, respect to red pomace, it was promptly removed from must after pressing, and its exploitation can be particularly interesting and valuable as still rich in active compounds. Phenol extracts were obtained both via solvent-based and pressurised liquid extractions and their phytochemical compositions were compared in terms of total amount of phenols, flavonoids, flavanols, anthocyanins, hydroxycinnamic acids, and reducing sugars. Antioxidant activity and detailed phenol profiles were also achieved. The highest phenol yield was obtained via solvent-based extraction with 75% acetone (v/v), solid/liquid ratio 1:5, 2h incubation at 50°C (77.9 gGAeq/kgDW). The fibrous solid residue of the extraction was characterized via thermogravimetric analysis and used for composite preparation by melt mixing with the renewable and biodegradable PHBV polymer through a green approach (solvent-less process). The composites resulted thermally stable at high temperatures, showing initial degradation processes only at temperatures higher than 250°C. Differential scanning calorimetry analyses were carried out to study melting and crystallization phenomena, while mechanical properties were investigated by tensile tests. The materials finally showed properties similar to those of the matrix. The bio-composites can be considered as an alternative to plain PHBV, since they are less expensive and eco-friendlier thanks to a reduced polymeric content, and they could represent a suitable way for full agro-waste exploitation.

Eco-Conversion of Two Winery Lignocellulosic Wastes into Fillers for Biocomposites: Vine Shoots and Wine Pomaces.

Two winery residues, namely vine shoots (ViSh) and wine pomace (WiPo), were up-cycled as fillers in PHBV-based biocomposites. Answering a biorefinery approach, the impact of a preliminary polyphenols extraction step using an acetone/water mixture on the reinforcing effect of fillers was assessed. Biocomposites (filler content up to 20 wt%) were prepared by melt-mixing and compared in terms of final performance (thermal, mechanical and barrier). It was shown that the reinforcing effect was slightly better in the case of vine shoots, while it was not significantly affected by the pre-treatment, demonstrating that these two winery residues could be perfectly used as fillers in composite materials even after an extraction process to maximize their potential of valorization.

Polymorphism and Multiple Melting Behavior of Bio-Based Poly(propylene 2,5-furandicarboxylate).

Furandicarboxylate-based polyesters are considered an interesting class of bio-based polymers due to their improved properties with respect to the petrol-based terephthalate homologs. An in-depth analysis of the crystal structure of poly(propylene 2,5-furandicarboxylate) (PPF), after maximum possible removal of the catalyst, was carried out. The study disclosed that purified PPF presents two different crystalline phases after crystallization from the melt. Crystallizations at temperatures lower than 120 °C lead to growth of a single crystal form (ß-form), whereas two different crystal forms (α and ß) were found to coexist at higher Tcs. This behavior is opposite to that previously observed for unpurified PPF. The possibility that the catalyst nucleates the α-phase, which therefore becomes the kinetically favored modification at low crystallization temperatures in the presence of a higher amount of catalyst residue, has been considered as a feasible explanation. Two concomitantly different spherulitic morphologies were observed and connected to the ß- and α-phase, respectively. The association between polymorphism and melting behavior was studied. The origin of the peaks that compose the multiple melting endotherm recorded at conventional heating rates was determined by combined wide-angle X-ray scattering, differential scanning calorimetry, fast scanning chip calorimetry, and polarized light optical microscopy measurements. The higher thermal stability of the α-crystals in comparison with the ß-form was thus demonstrated.

From winery waste to bioactive compounds and new polymeric biocomposites: A contribution to the circular economy concept.

The paper aims at optimising and validating possible routes toward the full valorisation of grape agrowaste to produce bioactive molecules and new materials. Starting from Merlot red pomace, phenol complex mixtures were successfully extracted by using two different approaches. Extracts obtained by solvent-based (SE) technique contained up to 46.9 gGAeq/kgDW of total phenols. Depending on the used solvent, the prevalence of compounds belonging to different phenol families was achieved. Pressurized liquid extraction (PLE) gave higher total phenol yields (up to 79 gGAeq/kgDW) but a lower range of extracted compounds. All liquid extracts exerted strong antioxidant properties. Moreover, both SE and PLE extraction solid residues were directly exploited (between 5 and 20% w/w) to prepare biocomposite materials by direct mixing via an eco-friendly approach with PHBV polymer. The final composites showed mechanical characteristics similar to PHVB matrix. The use of pomace residues in biocomposites could therefore bring both to the reduction of the cost of the final material, as a lower amount of costly PHBV is used. The present research demonstrated the full valorisation of grape pomace, an agrowaste produced every year in large amounts and having a significant environmental impact.

State-of-the-Art Production Chains for Peas, Beans and Chickpeas-Valorization of Agro-Industrial Residues and Applications of Derived Extracts.

The world is confronted with the depletion of natural resources due to their unsustainable use and the increasing size of populations. In this context, the efficient use of by-products, residues and wastes generated from agro-industrial and food processing opens the perspective for a wide range of benefits. In particular, legume residues are produced yearly in very large amounts and may represent an interesting source of plant proteins that contribute to satisfying the steadily increasing global protein demand. Innovative biorefinery extraction cascades may also enable the recovery of further bioactive molecules and fibers from these insufficiently tapped biomass streams. This review article gives a summary of the potential for the valorization of legume residual streams resulting from agro-industrial processing and more particularly for pea, green bean and chickpea by-products/wastes. Valuable information on the annual production volumes, geographical origin and state-of-the-art technologies for the extraction of proteins, fibers and other bioactive molecules from this source of biomass, is exhaustively listed and discussed. Finally, promising applications, already using the recovered fractions from pea, bean and chickpea residues for the formulation of feed, food, cosmetic and packaging products, are listed and discussed.

Olive Mill Wastewater Valorization in Multifunctional Biopolymer Composites for Antibacterial Packaging Application.

Olive mill wastewater (OMW) is the aqueous waste derived from the production of virgin olive oil. OMW typically contains a wide range of phenol-type molecules, which are natural antioxidants and/or antibacterials. In order to exploit the bioactive molecules and simultaneously decrease the environmental impact of such a food waste stream, OMW has been intercalated into the host structure of ZnAl layered double hydroxide (LDH) and employed as an integrative filler for the preparation of poly(butylene succinate) (PBS) composites by in situ polymerization. From the view point of the polymer continuous phase as well as from the side of the hybrid filler, an investigation was performed in terms of molecular and morphological characteristics by gel permeation chromatography (GPC) and X-ray diffraction (XRD); also, the thermal and mechanical properties were evaluated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic thermomechanical analysis (DMTA). Antibacterial properties have been assessed against a Gram-positive and a Gram-negative bacterium, Staphylococcus aureus and Escherichia coli, respectively, as representatives of potential agents of foodborne illnesses.

Outstanding chain-extension effect and high UV resistance of polybutylene succinate containing amino-acid-modified layered double hydroxides.

Polybutylene succinate (PBS) nanocomposite materials were prepared using a melt compounding process. The Mg2Al-based PBS nanocomposites, dispersed with inorganic-organic hybrid materials (layered double hydroxides, LDHs), were functionalized with the amino acids L-histidine (HIS) and L-phenylalanine (PHE). The rheological and anti-ultraviolet (anti-UV) properties were investigated and compared to filler-free PBS as well as LDH Mg2Al/nitrate as references. Both organo-modified LDHs exhibited a remarkable chain-extension effect for PBS with an outstanding increase in the zero-shear viscosity η0 for PBS-Mg2Al/PHE (two order of magnitude increase as compared to filler-free PBS). These results were compared to data found in the literature. Moreover, HIS and PHE anions embedded into the LDH structure can successfully prevent the chain scission reactions that usually occur during photo-ageing of PBS under UV radiation exposure. This highlights the outstanding performance of the LDH hybrid materials, and in particular, their application as a polymer chain extender and UV stabilizer for PBS, which can likely be extended to other biodegradable polymers.

Bio-Based PA11/Graphene Nanocomposites Prepared by In Situ Polymerization.

Bio-based polyamide 11 (PA11)-graphene nanocomposites with different filler concentrations (0.25, 0.5, 0.75, 1.5 and 3 wt%) were prepared by In Situ polymerization starting from a water dispersed suspension of graphene nanoplatelets. The effects of the incorporation of the filler were studied in terms of molecular, morphological, thermal and dynamic mechanical properties of the final materials. During the crystallization process from the melt, the filler induces a notable nucleating effect even if the crystal growth rate tends to decrease. The glass transition temperature tends to shift to higher temperatures indicating a decrement of the molecular mobility. Thermal stability is enhanced confirming a good filler dispersion into the matrix. Mechanical reinforcement, investigated by means of a dynamic mechanical thermal analyzer was also highlighted. It was observed that a graphene concentration of 0.75 wt% induces the highest final performances.

Dual chain extension effect and antibacterial properties of biomolecules interleaved within LDH dispersed into PBS by in situ polymerization.

Nanocomposites based on poly(butylene succinate) (PBS) and hydrotalcite-type anionic clays (HTs) organo-modified with biomolecules characterized by antibacterial and/or antioxidant activities, such as l-ascorbic acid (ASA), phloretic acid (HPP), l-tyrosine (TYR) and l-tryptophan (TRP), have been prepared by in situ polymerization. From XRD analysis and rheology experiments in a molten polymer state, intercalated HT hybrid platelets acting here as a hybrid filler are found to be well dispersed into polymers while providing a chain extension effect on PBS. Moreover, the molecules, when hosted within a HT interlayer gap, do preserve their pristine antibacterial activity, both in HT and in the resulting PBS composites. In particular, under the experimental conditions tested, HT/ASA and HT/TYR present the best combination of both properties (chain extension effect and antibacterial), especially versus E. coli as high as 90 and 97% of inhibition, respectively, using 2.5 wt% hybrid filler only. These findings open future applications for PBS associated with the hybrid HT filler as multifunctional materials in active packaging applications.

A Sustainable Route to a Terephthalic Acid Precursor.

A new synthetic pathway for the production of p-toluic acid has been developed starting from reagents derived from renewable resources. A Diels-Alder reaction between sorbic and acrylic acids is followed by a combined dehydrogenation/ decarboxylation process, providing p-toluic acid in high yields. This route permits to use milder conditions compared to other Diels-Alder approaches reported in the literature, and therefore can contribute to a more sustainable terephthalic acid production.