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Poly(lactide) (PLA) and poly(ethylene glycol) (PEG)-based hydrogels were prepared by mixing phosphate buffer saline (PBS, pH 7.4) solutions of four-arm (PEG-PLA)2-R-(PLA-PEG)2 enantiomerically pure copolymers having the opposite chirality of the poly(lactide) blocks. Dynamic Light Scattering, rheology measurements, and fluorescence spectroscopy suggested that, depending on the nature of the linker R, the gelation process followed rather different mechanisms. In all cases, mixing of equimolar amounts of the enantiomeric copolymers led to micellar aggregates with a stereocomplexed PLA core and a hydrophilic PEG corona. Yet, when R was an aliphatic heptamethylene unit, temperature-dependent reversible gelation was mainly induced by entanglements of PEG chains at concentrations higher than 5 wt.%. When R was a linker containing cationic amine groups, thermo-irreversible hydrogels were promptly generated at concentrations higher than 20 wt.%. In the latter case, stereocomplexation of the PLA blocks randomly distributed in micellar aggregates is proposed as the major determinant of the gelation process. [ABSTRACT FROM AUTHOR]

Immobilizing natural antioxidant and biologically active molecules in layered double hydroxides (LDHs) is an excellent method to retain and release these substances in a controlled manner, as well as protect them from thermal and photochemical degradation. Herein, we describe the preparation of host–guest systems based on LDHs and rosmarinic and glycyrrhetinic acids, two molecules obtained from the extraction of herbs and licorice root, respectively, with antioxidant, antimicrobial, and anti-inflammatory properties. Intercalation between the lamellae of the mono-deprotonated anions of rosmarinic and glycyrrhetinic acid (RA and GA), alone or in the presence of an alkyl surfactant, allows for readily dispersible systems in biobased polymer matrices such as poly(lactic acid) (PLA), poly(butylene succinate) (PBS), and a 60/40 wt./wt. PLA/PBS blend. The composites based on the PLA/PBS blend showed better interphase compatibility than the neat blend, correlated with increased adhesion at the interface and a decreased dispersed phase size. In addition, we proved that the active species migrate slowly from thin films of the composite materials in a hydroalcoholic solvent, confirming the optimization of the release process. Finally, both host–guest systems and polymeric composites showed antioxidant capacity and, in the case of the PLA composite containing LDH-RA, excellent inhibitory capacity against E. coli and S. aureus. [ABSTRACT FROM AUTHOR]

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is among the most attracting low environmental impact polymeric materials. Coffee Silverskin (CS), an agro-food residue, has been compounded in variable amounts into a PHBV matrix in the presence of acetyl tributyl citrate (ATBC) as plasticizer, and calcium carbonate (CaCO3) as filler, to produce biocomposites through a pre-industrial scale melt extrusion technique. Thermal, morphological and mechanical properties have been investigated in order to validate whether these PHBV/CS based biocomposites could be used to manufacture moulded items, e.g. coffee capsules body. The increasing concentration of CS in PHBV improves the stiffness and the heat deflection temperature properties of the biocomposites. Coffee capsules body have been produced by injection moulding starting from the optimized formulations, based on the PHBV/CS system, and were characterized in terms of migration properties in contact with simulants. Notably, the overall migration at 100 °C was below the limit (10 mg/dm²) required for plastic materials in food contact applications. [ABSTRACT FROM AUTHOR]

Aiming at the tuning of thermo-mechanical features by chemical cross-linking, a biopolyester commercial blend based on poly(lactic acid) (PLA) with poly(butylene adipate-co-terephthalate)(PBAT) (ecovio®T2280, BASF) was processed in Brabender in the presence of dicumyl peroxide (DCP, 0-0.2 wt.-%). The effect of DCP addition was investigated and rationalized by means of solubility tests and gel content evaluation, as well as rheological, mechanical, and molecular weight analysis of the prepared compounds. Moreover, detailed DSC and TMDSC investigations provided a deep insight into the structural modifications occurred at the macromolecular level. We found that chain branching as well as cross-linking occurred in the samples processed in the presence of DCP, thus returning compounds having increased toughness and modulated crystalline content and thermal behavior. Noteworthy, the presence of specific, undisclosed additives, triggers the occurrence of peculiar behaviors in the ecovio® commercial blend, not previously observed in model PLA/PBAT blends of similar composition. Despite only partially soluble in chloroform, the new ecovio® DCP-modified compounds still remained workable in the melt, thus providing a suitable, simple and economically affordable strategy to finely modulate the thermo-mechanical properties starting from a commercially available, compostable compound. [ABSTRACT FROM AUTHOR]

Molecularly designed materials based on macromolecules and organic dyes offer unique opportunities in connection with the possibility of preparing optically responsive 'smart' materials. Indeed macromolecules are able to transmit and amplify small signals reaching sites at interacting distance through the involvement of the whole chain. The corresponding materials can then acquire stimuli-responsive properties in relation to specific features connected to primary structure and conformation. As a first approach to benefit from the above features for preparing eco-compatible smart materials, bio-related polypeptides, polysaccharides and polyesters can be used as the macromolecular partner in combination with a selected dye following different interaction methodologies. Two distinct routes were used to prepare optically responsive products from the above bio-related polymers, respectively based either on the covalent bonding to the original macromolecules of photochromic molecular species, such as azobenzene and spiropyran, or on the morphology-modulated dispersion of highly conjugated dyes in the polymer bulk. Examples related to the two different routes have been investigated in our laboratory and are presented and discussed also with reference to selected recent cases from the literature. Copyright © 2012 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

In this work, a new thermal stimuli sensitive multiphase polymer system consisting of a bio-related mixture of poly(lactic acid) (PLA, 85 wt%) and poly(1,4-butylene succinate) (PBS, 15 wt%) was prepared by the controlled incorporation of moderate amounts (60 to 70 °C) leading to a clear change of the emission properties due to the occurrence of dye aggregation. Thermal analysis by DSC showed an evident connection between blend morphology features and luminescence response. The results are here discussed with reference to the transition temperatures of the two polymer phases and their effect on aggregation/disaggregation of dispersed BBS. [ABSTRACT FROM AUTHOR]

A series of task-specific ionic liquids (TSILs) based on glycerylimidazolium cations have been prepared by reaction of 1-chloropropanediol, a compound obtainable from glycerol (a widely available and in-expensive waste product), with the appropriate base (1-H-imidazole, 1,2-dimethylimidazole and 1-methyl-1-H-imidazole). The reaction of 3-(1H-imidazol-1-yl)propane-1,2-diol with chloroalkanes, bromoalkanes and alkyl mesylates gave the corresponding salts which were characterized. The possibility to use these ILs in palladium catalyzed reactions was evaluated, evidencing good catalyst stability and a high recyclability. [ABSTRACT FROM AUTHOR]

The article examines the modulation of poly(lactic acid) (PLA) properties as a consequence of poly(butylene adipate-co-terepthalate) (PBAT) blending and acetyl tributyl citrate (ATBC) plasticization. The researchers evaluated the effect of the concentration of either the plasticizer or copolyester on the final material flexibility of the PLA. The study analyzed the preferential solubilization of ATBC in the PBAT phase and assessed the possible use of PLA in food packaging applications.

In recent years, the circular economy and sustainability have gained attention in the food industry aimed at recycling food industrial waste and residues. For example, several plant-based materials are nowadays used in packaging and biofuel production. Among them, by-products and waste from coffee processing constitute a largely available, low cost, good quality resource. Coffee production includes many steps, in which by-products are generated including coffee pulp, coffee husks, silver skin and spent coffee. This review aims to analyze the reasons why coffee waste can be considered as a valuable source in recycling strategies for the sustainable production of bio-based chemicals, materials and fuels. It addresses the most recent advances in monomer, polymer and plastic filler productions and applications based on the development of viable biorefinery technologies. The exploration of strategies to unlock the potential of this biomass for fuel productions is also revised. Coffee by-products valorization is a clear example of waste biorefinery. Future applications in areas such as biomedicine, food packaging and material technology should be taken into consideration. However, further efforts in techno-economic analysis and the assessment of the feasibility of valorization processes on an industrial scale are needed. [ABSTRACT FROM AUTHOR]

In the perspective of producing a rigid renewable and environmentally friendly rigid packaging material, two comb-like copolymers of cellulose acetate (AC) and oligo(lactic acid) OLA, feeding different percentages of oligo(lactic acid) segments, were prepared by chemical synthesis in solvent or reactive extrusion in the melt, using a diepoxide as the coupling agent and were used as compatibilizers for poly(lactic acid)/plasticized cellulose acetate PLA/pAC blends. The blends were extruded at 230 °C or 197 °C and a similar compatibilizing behavior was observed for the different compatibilizers. The compatibilizer C1 containing 80 wt% of AC and 14 wt% of OLA resulted effective in compatibilization and it was easily obtained by reactive extrusion. Considering these results, different PLAX/pAC(100-X) compounds containing C1 as the compatibilizer were prepared by extrusion at 197 °C and tested in terms of their tensile and impact properties. Reference materials were the uncompatibilized corresponding blend (PLAX/pAC(100-X)) and the blend of PLA, at the same wt%, with C1. Significant increase in Young's modulus and tensile strength were observed in the compatibilized blends, in dependence of their morphologic features, suggesting the achievement of an improved interfacial adhesion thanks to the occurred compatibilization. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Front Cover: Processing of PLA/PBAT compostable blends with dicumyl peroxide gives chain‐branching and crosslinking, thus providing a simple and economically affordable strategy to finely modulate the thermo‐mechanical properties of the commercial material. Further details can be found in the article by F. Signori,* A. Boggioni, M. C. Righetti, C. E. Rondán, S. Bronco, and F. Ciardelli on page 153. [ABSTRACT FROM AUTHOR]

In this work we present controlled, low-damage nanotopographic surface modification of poly(ethylene terephthalate) (PET). High-resolution nanopatterning over macroscopic areas was performed by " low-temperature" hot embossing lithography (HEL). While for standard HEL the temperature is typically raised up to many tens of Celsius degrees above the polymer glass transition temperature (Tg), we demonstrate optimal results at a temperature very close to the bulk Tg of PET (72 degrees C). Nanopits and nanobarcodes were transferred onto the surface of PET commercial sheets, demonstrating reliable sub-100 nm resolution over macroscopic areas. Sample optical, mechanical, and thermal characteristics were systematically analyzed before and after embossing at low (75 degrees C) and high (150 degrees C) temperature by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, tensile tests, and differential scanning calorimetry (DSC). We show that, while conventional high-temperature HEL can lead to dramatic degradation of the polymer in terms of transparency, flexibility, and crystallinity content, our low-temperature process fully maintains original surface and bulk substrate properties.