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Within bioplastics, natural poly(3-hydroxybutyrate) (PHB) stands out as fully biocompatible and biodegradable, even in marine environments; however, its high isotacticity and crystallinity limits its mechanical properties and hence its applications. PHB can also be synthesized with different tacticities via a catalytic ring-opening polymerization (ROP) of rac-β-butyrolactone (BBL), paving the way to PHB with better thermomechanical and processability properties. In this work, the catalyst family is extended based on aluminum phenoxy-imine methyl catalyst [AlMeL 2 ], that reveals efficient in the ROP of BBL, to the halogeno analogous complex [AlClL 2 ]. As well, the impact on the ROP mechanism of different initiators is further explored with a particular focus in dimethylaminopyridine (DMAP), a hardly studied initiator for the ROP of BBL. A thorough mechanistic study is performed that evidences the presence of two concomitant DMAP-mediated mechanisms, that lead to either a DMAP or a crotonate end-capping group. Besides, in order to increase the possibilities of PHB post-polymerization functionalization, the introduction of a side-chain functionality is explored, establishing the copolymerization of BBL with β-allyloxymethylene propiolactone (BPL OAll ), resulting in well-defined P(BBL-co-BPL OAll ) copolymers., (© 2024 The Authors. Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)

Functional packaging represents a new frontier for research on food packaging materials. In this context, adding antioxidant properties to packaging films is of interest. In this study, poly(butylene adipate-co-terephthalate) (PBAT) and olive leaf extract (OLE) have been melt-compounded to obtain novel biomaterials suitable for applications which would benefit from the antioxidant activity. The effect of cellulose nanocrystals (CNC) on the PBAT/OLE system was investigated, considering the interface interactions between PBAT/OLE and OLE/CNC. The biomaterials' physical and antioxidant properties were characterized. Morphological analysis corroborates the full miscibility between OLE and PBAT and that OLE favours CNC dispersion into the polymer matrix. Tensile tests show a stable plasticizer effect of OLE for a month in line with good interface PBAT/OLE interactions. Simulant food tests indicate a delay of OLE release from the 20 wt% OLE-based materials. Antioxidant activity tests prove the antioxidant effect of OLE depending on the released polyphenols, prolonged in the system at 20 wt% of OLE. Fluorescence spectroscopy demonstrates the nature of the non-covalent PBAT/OLE interphase interactions in π-π stacking bonds. The presence of CNC in the biomaterials leads to strong hydrogen bonding interactions between CNC and OLE, accelerating OLE released from the PBAT matrix., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper titled “Interface interactions driven antioxidant properties in olive leaf extract/cellulose nanocrystals/poly(butylene adipate-co-terephthalate) biomaterials”., (Copyright © 2024 The Author(s). Published by Elsevier B.V. All rights reserved.)

Biodegradable blends based on plasticized poly(lactic acid) PLA and thermoplastic starch (TPS) have been obtained. The influence of the PLA plasticizer as a compatibility agent has been studied by using two different plasticizers such as neat oligomeric lactic acid (OLA) and functionalized with maleic acid (mOLA). In particular, the morphological, thermal, and mechanical properties have been studied as well as the shape memory ability of the melt-processed materials. Therefore, the influence of the interaction between different plasticizers and the PLA matrix as well as the compatibility between the two polymeric phases on the thermally-activated shape memory properties have been studied. It is very interesting to use the same additive able to act as both plasticizer and compatibilizer, decreasing the glass transition temperature of PLA to a temperature close to the physiological one, obtaining a material suitable for potential biomedical applications. In particular, we obtain that OLA-plasticized blend (oPLA/TPS) show very good thermally-activated capability at 45 °C and 50% deformation, while the blend obtained by using maleic OLA (moPLA/TPS) did not show shape memory behavior at 45 °C and 50% deformation. This fact is due to their morphological changes and the loss of two well-distinguished phases, one acting as fixed phase and the other one acting as switching phase to typically obtain shape memory response. Therefore, the thermally-activated shape memory results show that it is very important to make a balance between plasticizer and compatibilizer, considering the need of two well-established phases to obtain shape memory response.

Heat-shrinkable films are widely used as disposable secondary packaging but are conventionally made from fossil-based and nonbiodegradable polyvinyl chloride or polyethylene. To lower the environmental impact of such products, this work reports the development of recyclable, biodegradable, and partially biosourced heat-shrinkable biocomposites that are cost-competitive with existing shrink wraps. Poly(butylene adipate- co -terephthalate), a growing biodegradable thermoplastic, was simultaneously reinforced with pulp fibers and partially cross-linked in a single-step reactive melt processing. The designed peroxide-initiated reaction led to a 55 wt % cocontinuous insoluble gel incorporating all the pulp fibers into a cross-linked polymer network. In the solid state, the cross-linked biocomposite shows 60% elongation at break with a 200% increase in Young's modulus, while the only addition of pulp fibers stiffens and embrittles the matrix. Creep tests in the melt state indicated that the cross-linked network induces homogeneous shrinking even during the loading phase, demonstrating the potential use of the biocomposites as heat-shrinkable films. The shrinking also promotes the shape-memory of the biocomposite, which retains its dimensions after four cycles. The circularity of the materials was assessed by mechanical recycling and industrial composting, which have proven feasible end-of-life options for heat-shrinkable biocomposites., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

In this work, using supramolecular polyurethanes theories, two polycaprolactone-based polyurethanes with 2-ureido-4-[1H]-pyrimidinone (UPy) motifs capable of forming quadruple hydrogen bonds were synthetized and characterized, focusing our attention on their capability to show thermally activated shape-memory response. In particular, 1 H NMR analyses confirmed the chemical structure of the supramolecular polyurethanes, while DSC showed their totally amorphous morphology. DMTA in tensile mode was used to study their thermally activated shape-memory properties. In our case, the UPy units are the switching domains while the network formed by the segregated hard segments is the permanent domain obtained materials with excellent shape-memory response at both 100 and 85 °C. These materials are promising for multi-responsive materials where bio-based and potentially recyclable polymers with excellent shape-memory properties are needed.

Two non-toxic potassium compounds, 1 and 2 , with a commercial oximate ligand have been prepared and fully spectroscopically characterized. Their activity as catalysts for the ring-opening polymerization (ROP) process of LLA has been studied, showing that they are extremely active and able to polymerize the monomer in a few minutes. For derivative 2 , the presence of a crown ether in the potassium coordination sphere affects the nuclearity of the compound and consequently its solubility, with both aspects having an influence in the polymerization process. Detailed studies of the polymerization mechanism have been performed, and an unusual anionic mechanism was observed in absence of a co-initiator. Indeed, the monomer deprotonation generates a lactide enolate, which initiates the polymerization propagation. On the contrary, when a 1:1 ratio of cat:BnOH is used, a mixture of mechanisms is observed, the anionic mechanism and the activated monomer one, while from a cat:BnOH ratio of 1:2 and over, only the activated monomer mechanism is observed.

Increasing energy autonomy and lowering dependence on lithium-based batteries are more and more appealing to meet our current and future needs of energy-demanding applications such as data acquisition, storage, and communication. In this respect, energy harvesting solutions from ambient sources represent a relevant solution by unravelling these challenges and giving access to an unlimited source of portable/renewable energy. Despite more than five decades of intensive study, most of these energy harvesting solutions are exclusively designed from ferroelectric ceramics such as Pb(Zr,Ti)O 3 and/or ferroelectric polymers such as polyvinylidene fluoride and its related copolymers, but the large implementation of these piezoelectric materials into these technologies is environmentally problematic, related with elevated toxicity and poor recyclability. In this work, we reveal that fully biobased non-isocyanate polyurethane-based materials could afford a sustainable platform to produce piezoelectric materials of high interest. Interestingly, these non-isocyanate polyurethanes (NIPUs) with ferroelectric properties could be successfully synthesized using a solvent-free reactive extrusion process on the basis of an aminolysis reaction between resorcinol bis-carbonate and different diamine extension agents. Structure-property relationships were established, indicating that the ferroelectric behavior of these NIPUs depends on the nanophase separation inside these materials. These promising results indicate a significant potential for fulfilling the requirements of basic connected sensors equipped with low-power communication technologies., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Modern society's growing demands for accountable high-performance and more environmentally friendly materials is leading to increased interest and fast development of sustainable polymeric composite materials. New generations of "greener" products originating from renewable resources fulfil emerging requirements of low environmental and health & safety impacts and contribute to diminishing global dependence on fossil feedstock. The preparation of sustainable polymeric composites via reliable and reproducible melt-compounding methods is still challenging but has the potential to yield applicable and market competitive products. This literature survey reviews the current state of research involving the use of cellulosic materials, as bio-sourced and sustainable reinforcement in melt-processed polyamides and focuses on the main hurdles that prevent their successful large-scale melt-compounding. Particular emphasis is dedicated to emerging bio-sourced polyamides fitting the performance of engineering materials and at the same time offering additional interesting properties for advanced applications such as piezoelectricity for transducers, sensors, actuators and energy harvesters., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Starch nanocrystals (SNCs) were successfully synthesized by acid hydrolysis of waxy barley starch and were characterized by X-ray diffraction, scanning and transmission electron microscopy. Nanocomposites based on ethylene-co-vinyl acetate (EVA) and SNCs were produced by melt-processing using a microextruder. Interesting is to note that SNCs do not lose their crystalline nature during melt-processing. Moreover, the mechanical and thermal properties of the neat matrix were improved by the addition of SNCs thanks to the strong hydrogen bonding between the nanofillers surface and the acetate groups of the matrix. The introduction of 2 wt.% and 5 wt.% of SNCs into the matrix, lead to an increase of its elastic modulus of about 50% and 100%, respectively. Moreover, the addition of SNCs provoked an increase of the thermal stability of about 10 °C respect to the neat matrix. These results clearly revealed the possibility to introduce SNCs in a polymeric matrix by extrusion enabling to reach materials with enhanced mechanical and thermal properties due to beneficial hydrogen bonding between SNCs and EVA., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Humidity-activated shape memory behavior of plasticized starch-based films reinforced with the innovative combination of starch nanocrystals (SNCs) and catechin as antioxidant were studied. In a previous work, we reported the processing of gelatinized starch-based films filled with SNCs and catechin as antioxidant agent, and we observed that this novel combination leads to starch-based film with enhanced thermal and mechanical performance. In this work, the humidity-activated shape memory behavior of the previous developed starch-based films was characterized. The moisture loss as well as the moisture absorption were studied since they are essential parameters in humidity-activated shape memory polymers to fix the temporary shape and to recover the original shape, respectively. Therefore, the effect of the incorporation of SNCs and catechin on the humidity-activated shape memory properties of plasticized starch was also studied. Moreover, the effectiveness of catechin to increase the polymer stability under oxidative atmosphere and the thermo-mechanical relaxation of all the starch-based materials were studied. The combination of plasticized starch matrix loaded with both, SNCs and catechin, leads to a multifunctional starch-based films with increased hydrophilicity and with excellent humidity-activated shape memory behavior with interest for potential biomedical applications., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Smart multiresponsive bionanocomposites with both humidity- and thermally activated shape-memory effects, based on blends of ethylene-vinyl acetate (EVA) and thermoplastic starch (TPS) are designed. Thermo- and humidity-mechanical cyclic experiments are performed in order to demonstrate the humidity- as well as thermally activated shape memory properties of the starch-based materials. In particular, the induced-crystallization is used in order to thermally activate the EVA shape memory response. The shape memory results of both blends and their nanocomposites reflect the excellent ability to both humidity- and thermally activated recover of the initial shape with values higher than 80 and 90%, respectively.