Search

This review sheds light on urgent questions that arise from the need to replace a polymer resin,-poly(ethylene terephthalate), which represents 7.7% market-share in the global plastic demand (Plastics-the Facts 2019), by renewable alternatives. The main question that this review will address is: what are the most promising PET replacements made from biomass? Currently, under debate is naturally its biobased counterpart bio-PET (or even recycle rPET), as well as other aromatic key-players with comparable thermo-mechanical performance and enhanced barrier properties, such as poly(ethylene 2,5-furandicarboxylate) (PEF) and poly(trimethylene 2,5-furandicarboxylate) (PTF). They are most adequate for packaging, but not restricted to. Additional alternatives are the miscellaneous of lignin-based thermoplastic polymers, although the technology involved in this latter case is still premature. (Bio)degradable aliphatic polyesters, despite their typical inferior thermo-mechanical properties, can also play a role e.g., among PET fiber industry applications. Poly(lactic acid) (PLA) is the most developed renewable polyester, already a commercial reality. All biobased polymers reviewed face a major hindrance for their wider deployment their cost-competitiveness. A pertinent question arises then: Are these alternatives, or will they be, economically feasible? Social, political and legal frameworks together with supportive financial schemes are boosting rapid changes. In the future, most probably more than one polymer will come to the market and will be used in some of the panoply of PET applications. This evaluation overviews sustainability issues, including perspectives on their green synthesis. Moreover, this review does also not neglect the accumulation of plastics waste in the environment and the inherent challenges of polymers' end-of-life. Approximately 8 M tons of polymers waste leaks into the environment each year, a fact not disconnected to PET's non-biodegradability and still insufficient collection and recycling rates. This journal is

Using a computer vision approach we have extracted the Haralick's texture features of randomly oriented electrospun nanomaterials in order to predict the proliferative behavior of cells which were subsequently seeded onto the nanosurfaces.

Poly(butylene succinate) (PBS) and poly(butylene/2-butyl,2-ethyl-propylene succinate) (PBSBEPS) membranes are prepared by electrospinning technique. In recent years, interest in biodegradable aliphatic polyesters, including PBS and its copolymers, is increasing as they have potential applications in various sectors such as mulching films, food packaging, tissue engineering, and drug delivery. In this work, the synthesized polymers are dissolved in different solvents, namely acetone, chloroform (CHCl3), methanol, dichloromethane (DCM), and dimethylformamide in order to obtain the best solvent system. These solutions are then electrospun at room temperature to produce micron-sized fibers. The variables examined in determining the optimal solution and electrospinning conditions are the solvent system used, the concentration of PBS and PBS-based random copolymer, applied voltage, flow rate, humidity, and the distance between the needle tip and the collector, all of which have a meaningful effect on the fiber morphology. Among the various solvents used, the DCM and the less toxic CHCl3 result in fewer bead defects among fibers. Besides, an increase in PBS and PBS-based random copolymer concentration determines the reduction of bead defects, which from 12 to 14wt% results in bead-free uniform fibers, when suitable processing parameters are set. Promising results, which can pave the way for the production of membranes loaded with appropriate anticancer molecules for targeted biomedical applications, are obtained.

High-molecular-weight poly(butylene 2,4-furanoate) (2,4-PBF), an isomer of well-known poly(butylene 2,5-furanoate) (2,5-PBF), was synthesized through an eco-friendly solvent-free polycondensation process and processed in the form of an amorphous film by compression molding. Molecular characterization was carried out by NMR spectroscopy and GPC analysis, confirming the chemical structure and high polymerization degree. Thermal analyses evidenced a reduction of both glass-to-rubber transition and melting temperatures, as well as a detriment of crystallization capability, for 2,4-PBF with respect to 2,5-PBF. Nevertheless, it was possible to induce crystal phase formation by annealing treatment. Wide-angle X-ray scattering revealed that the crystal lattices developed in the two isomers are distinct from each other. The different isomerism affects also the thermal stability, being 2,4-PBF more thermally inert than 2,5-PBF. Functional properties, such as wettability, mechanical response, and gas barrier capability, were tested on both amorphous and semicrystalline 2,4-PBF films and compared with those of 2,5-PBF. Reduced hydrophilicity was determined for 2,4-isomer, in line with its lower average dipole moment, suggesting better chemical resistance to hydrolysis. Stress–strain tests have evidenced the higher flexibility and toughness of 2,4-PBF with respect to those of 2,5-PBF and the possibility of improving its mechanical resistance by annealing. Finally, the different isomerism deeply affects the gas barrier performance, being the O2- and CO2-transmission rates of 2,4-PBF 50 and 110 times lower, respectively, than those of 2,5-PBF. The gas barrier properties turned out to be outstanding under a dry atmosphere as well as in humid conditions, suggesting the presence of interchain hydrogen bonds. The gas blocking capability decreases after annealing because of the presence of disclination associated with the formation of crystals., Poly(butylene 2,4-furanoate) was obtained from 2,4-isomer of biobased furandicarboxylic acid, and isomerism further improved the key properties for sustainable packaging applications.

Fully bio-based poly(lactic acid) (PLA) and poly(3-hydroxybutyrate) (PHB) blends plasticized with tributyrin (TB), and their nanocomposite based on chitin nanoparticles (ChNPs) was developed using melt mixing followed by a compression molding process. The combination of PHB and ChNPs had an impact on the crystallinity of the plasticized PLA matrix, thus improving its oxygen and carbon dioxide barrier properties as well as displaying a UV light-blocking effect. The addition of 2 wt% of ChNP induced an improvement on the initial thermal degradation temperature and the overall migration behavior of blends, which had been compromised by the presence of TB. All processed materials were fully disintegrated under composting conditions, suggesting their potential application as fully biodegradable packaging materials.

Considering the current context of research aiming at proposing new bioplastics with low costs and properties similar to fossil-based commodities currently on the market, in the present work, a hybrid blend containing a prevalent amount of cheap inedible cereal flour (70 wt %) and poly(butylene succinate) (PBS) (30 wt %) has been prepared by a simple, eco-friendly, and low-cost processing methodology. In order to improve the interfacial tension and enhance the adhesion between the different phases at the solid state, with consequent improvement in microstructure uniformity and in material mechanical and adhesive performance, the PBS fraction in the blend was replaced with variable amounts (0-25 wt %) of PBS-based green copolymer, which exerted the function of a compatibilizer. The copolymer is characterized by an ad hoc chemical structure, containing six-carbon aliphatic rings, also present in the flour starch structure. The two synthetic polyesters obtained through two-stage melt polycondensation have been deeply characterized from the molecular, thermal, and mechanical points of view. Copolymerization deeply impacts the polymer final properties, the crystallizing ability, and stiffness of the PBS homopolymer being reduced. Also, the prepared ternary blends were deeply investigated in terms of microstructure, thermal, and mechanical properties. Lastly, both pure blend components and ternary blends were subjected to disintegration experiments under composting conditions. The results obtained proved how effective was the compatibilizer action of the copolymer, as evidenced by the investigation conducted on morphology and mechanical properties. Specifically, the mixtures with 15 and 20 wt % Co appeared to be characterized by the best mechanical performance, showing a progressive increase of deformation while preserving good values of elastic modulus and stress. The disintegration rate in compost was found to be higher for the lower amount of copolymer in the ternary blend. However, after 90 days of incubation, the blend richest in copolymer content lost 62% of weight.

This works aims to investigate the effect of the molecular groups found in polyester backbones (type of ring in the acidic subunit and length of the glycolic subunit) on the molecular dynamics. The investigation is done on three furan-based polyesters (PEF, PPF and PBF) as compared to their terephthalic counterparts (PET, PTT, and PBT) after full quenching from the molten state. The segmental molecular dynamics is investigated with MT-DSC, FSC and DRS. It is shown that the cooperativity decreases as the length of the glycolic subunit increases in both furan-based and terephthalic polyesters. No direct correlation between the fragility index and the cooperativity is observed in furan-based polyesters containing glycolic subunits of different lengths. The differences in the isochoric fragilities obtained for the furan-based polyesters and their terephthalic counterparts has been assumed to result from the combination of backbone flexibility and packing efficiency of the macromolecular chains in the amorphous phase.

Highly promising fully biobased random copolyesters, poly(trimethylene 2,5-furandicarboxylate-co-trimethylene sebacate) (PTFcoPTSeb), were synthesized by using bio derived 1,3-propanediol, dimethyl ester of 2,5- furandicarboxylic acid, and sebacic acid, through eco-friendly polycondensation in the melt. Copolymers with high molecular weight containing 5, 15, 25 mol % of PTSeb were obtained, and their chemical structure confirmed by 1H NMR and FTIR spectroscopy. The thermal, tensile and gas barrier properties and composability were studied in relation to the copolymer supramolecular structure. As expected, introduction of PTSeb co-units results in lowering of glass transition temperature of copolymers and improves their flexibility. Besides, all copolymers showed outstanding gas barrier properties to O2 and CO2, with copolymer containing 15 mol % of PTSeb showing exceptional gas barrier properties, better than those of PTF and comparable to those of EVOH, currently used in multilayer packaging films. The same copolymer exhibited temperature induced shape memory behaviour. It was found that low amounts (15-25 mol %) of PTSeb in copolymer significantly modifies PTF thermal, mechanical and barrier properties and renders the final material compostable. Copolyesters containing 15 and 25 mol % of PTSeb can compete in some applications with commercially available compostable Ecoflex® polymer, but with markedly improved barrier properties.

In the present study, 100% bio-based polyesters of 2,5-thiophenedicarboxylic acid were synthesized via two-stage melt polycondensation using glycols containing 3 to 6 methylene groups. The so-prepared samples were characterised from the molecular point of view and processed into free-standing thin films. Afterward, both the purified powders and the films were subjected to structural and thermal characterisation. In the case of thin films, mechanical response and barrier properties to O2 and CO2 were also evaluated. From the results obtained, it emerged that the length of glycolic sub-units is an effective tool to modulate the chain mobility and, in turn, the kind and amount of ordered phases developed in the samples. In addition to the usual amorphous and 3D crystalline phases, in all the samples investigated it was possible to evidence a further phase characterised by a lower degree of order (mesophase) than the crystalline one, whose amount is strictly related to the glycol sub-unit length. The relative fraction of all these phases is responsible for the different mechanical and barrier performances. Last, but not least, a comparison between thiophene-based homopolymers and their furan-based homologues was carried out.

Fully biobased blends of thermoplastic starch and a poly(butylene cyclohexanedicarboxylate)-based random copolyester containing 25 % of adipic acid co-units (PBCEA) are prepared by melt blending and direct extrusion film casting. The obtained films are characterized from the physicochemical and mechanical point of view and their fragmentation under composting conditions is evaluated. The results demonstrate that the introduction of adipic acid co-units in the PBCE macromolecular chains permits to decrease the blending temperature, thus avoiding unwanted starch degradation reactions. Moreover, the presence of small amounts of citric acid as compatibilizer further improves the interfacial adhesion between the two components and promotes the formation of micro-porosities within the films. The synergistic combination of these factors leads to the development of materials showing an elastomeric behavior, i.e. no evident yield and elongation at break higher than 450 %, good moisture resistance and fast fragmentation in compost.

Plastics are perceived as modern and versatile materials, but their use is linked to numerous environmental issues as their production is based on finite raw materials (petroleum or natural gas). Additionally, their low biodegradability results in the accumulation of microplastics. As a result, there is extensive interest in the production of new, environmentally friendly, bio-based and biodegradable polymers. In this context, poly(ethylene vanillate) (PEV) has a great potential as a potentially bio-based alternative to poly(ethylene terephthalate), however, it has not yet been extensively studied. In the present work, the preparation of PEV is reported. The enthalpy and the entropy of fusion of the pure crystalline PEV have been estimated for the first time. Additionally, the equilibrium melting temperature has also been calculated. Furthermore, the isothermal and non-isothermal crystallization behavior are reported in detail, and new insights on the thermal stability and degradation mechanism of PEV are given.

Among the several actions contributing to the development of a sustainable society, there is the eco-design of new plastic materials with zero environmental impact but that are possibly characterized by properties comparable to those of the traditional fossil-based plastics. This action is particularly urgent for food packaging sector, which involves large volumes of plastic products that quickly become waste. This work aims to contribute to the achievement of this important goal, proposing new bio-based cycloaliphatic polymers based on trans-1,4-cyclohexanedicarboxylic acid and containing different amount of camphoric acid (from 0 to 15 mol %), a cheap and bio-based building block. Such chemical modification was conducted in the melt by avoiding the use of solvents. The so-obtained polymers were processed in the form of films by compression molding. Afterwards, the new and successfully synthesized random copolymers were characterized by molecular (NMR spectroscopy and GPC analysis), thermal (DSC and TGA analyses), diffractometric (wide angle X-ray scattering), mechanical (through tensile tests), and O2 and CO2 barrier point of view together with the parent homopolymer. The article aims to relate the results obtained with the amount of camphoric moiety introduced and to present, the different microstructure in the copolymers in more detail, indeed, in these samples, a different crystalline form developed (the so-called β-PBCE). This latter form was the kinetically favored and less packed one, as proven by the lower equilibrium melting temperature determined for the first time by Baur’s equation.

Here, solution-cast blends of polylactic acid (PLA) and a novel bioderived poly(pentamethylene 2,5-furanoate) (PPeF) in variable concentrations (1-50 wt %) are prepared and investigated. The characterization of the thin films (thickness 50 mu m) highlights that PPeF strongly improves the UV-shielding properties of PLA, with a decrease in transmittance at 275 nm from 47.3% of neat PLA to 0.77% with only 1 wt % of PPeF, while the transmittance decrease in the visible region at these PPeF fractions is marginal, allowing the production of optically transparent films. Despite the complete immiscibility of PLA/PPeF blends, PPeF effectively enhances the ductility of PLA as the tensile strain at break increases from 7% of neat PLA to 200% of the blend with 30 wt % of PPeF. This composition is the most promising also from the gas-barrier point of view as the gas transmission rates of CO2 and O-2 drop to one-fourth of those of neat PLA, comparable to those of poly(ethylene terephthalate). These results highlight that PLA/PPeF blends with PPeF fractions of 30 wt % are very promising for food packaging applications, and their properties could be further enhanced by applying suitable compatibilizers.

We report on the molecular origin of poly(pentamethylene 2,5-furanoate) particular physical properties. From the structural point of view we found this polymer can develop crystallinity when stored at room conditions for months. On the other hand, we used broadband dielectric spectroscopy (BDS) measurements, to analyze in very detail the local and segmental molecular dynamics of the material subjected to several thermal treatments. In this way we evidenced that the molecular dynamics are sensitive to thermal history over a broad temperature range. This behavior has been attributed to possible inter-chain interactions detected via infrared spectroscopy and rheology measurements in the non-crystallized polymer.

International audience; A Bacillus amyloliquefaciens strain was isolated from composted plastics and identified using microbial identification system BIOLOG and 16S rDNA sequences. The capability to attack virgin and ɣ-irradiation/high temperature-pretreated LLDPE films was investigated for comparison to evaluate the effect of pretreatment. A biodeteriorating effect characterized by low weight reductions of 1.1 ± 0.3 to 3.2 ± 1.3% was observed with the pretreated LLDPE within 40–60 days. The precision of the gravimetric method was sometimes negatively affected by the fragmentation of plastic films during the biological treatment or by traces of microbial biofilm firmly adhering to the plastic material. FTIR spectra before and after 60-day treatment indicated a decrease of carbonyl band and flattening of the 1300-1100 cm−1 zone due to bacterial action. GPC showed an increase of Mn and Mw of 2300–3700 and 32 200–35 500 g mol−1, respectively, and a decrease of polydispersity index suggesting presence of low molar weight LLDPE oligomers in pretreated LLDPE. The analysis of crystallinity and melting enthalpy detected the removal of oligomers during biodeterioration. ESI-MS analysis of the medium after 60-day biotreatment of pretreated LLDPE showed a presence of 3-hydroxybutyrate oligomers linked to the disappearance of low molar weight LLDPE oligomers that was not observed with virgin LLDPE. Coincidence of the removal of LLDPE oligomers and the appearance of 3-hydroxybutyrate oligomers suggested metabolization of low molecular LLDPE fractions present in the pretreated LLDPE by B. amyloliquefaciens. The experiments with virgin LLDPE demonstrated a positive effect of the pretreatment.

A class of eco-friendly copolyesters based on poly(butylene 2,5-thiophenedicarboxylate) (PBTF) is presented. The main goal of the study was to enhance the biodegradation rate of PBTF homopolymer. To this purpose, aliphatic sequences based on adipic acid have been introduced in the macromolecular backbone. The synthesized polymers have been characterized from thermal and structural point of view and their properties have been compared to those of the two homopolymers, i.e. PBTF and poly(butylene adipate).The peculiar microstructure of PBTF, due to the presence of an uninduced 2D-ordered phase, i.e. meso-phase, impacted also the copolymers' behavior, e.g. causing an increase of the materials' stiffness. Biodegradation rate in compost increased with the increase of mobile aliphatic sequences that allowed for an easier access to the ester bonds by the enzymes responsible for chain depolymerization. Lastly, gas permeability resulted strictly dependent on copolymer composition. Copolymers rich in thiophenedicarboxylate co-units displayed a gas barrier behavior comparable to poly(ethylene furanoate), while with the increase of adipate content the permeability increased, remaining however competitive with respect to that of polyolefines and polylactic acid. (C) 2018 Elsevier Ltd. All rights reserved.

In the present work, the effect of ether oxygen atom introduction in a furan ring-containing polymer has been evaluated. Solvent-free polycondensation process permitted the preparation of high molecular weight poly(diethylene 2,5-furandicarboxylate) (PDEF), by reacting the dimethyl ester of 2,5-furandicarboxylic acid with diethylene glycol. After molecular and thermal characterization, PDEF mechanical response and gas barrier properties to O2 and CO2, measured at different temperatures and humidity, were studied and compared with those of poly(butylene 2,5-furandicarboxylate) (PBF) and poly(pentamethylene 2,5-furanoate) (PPeF) previously determined. Both PDEF and PPeF films were amorphous, differently from PBF one. Glass transition temperature of PDEF (24 °C) is between those of PBF (39 °C) and PPeF (13 °C). As concerns mechanical response, PDEF is more flexible (elastic modulus [E] = 673 MPa) than PBF (E = 1290 MPa) but stiffer than PPeF (E = 9 MPa). Moreover, PDEF is the most thermally stable (temperature of maximum degradation rate being 418 for PDEF, 407 for PBF and 414 °C for PPeF) and hydrophilic (water contact angle being 74° for PDEF, 90° for PBF and 93° for PPeF), with gas barrier performances very similar to those of PPeF (O2 and CO2 transmission rate being 0.0022 and 0.0018 for PDEF and, 0.0016 and 0.0014 cm3 cm/m2 d atm for PPeF). Lab scale composting experiments indicated that PDEF and PPeF were compostable, the former degrading faster, in just one day. The results obtained are explained on the basis of the high electronegativity of ether oxygen atom with respect to the carbon one, and the consequent increase of dipoles along the macromolecule.

Innovative nanofibrous scaffolds have attracted considerable attention in bone tissue engineering, due to their ability to mimic the hierarchical architecture of an extracellular matrix. Aiming at investigating how the polymer chemistry and fiber orientation of electrospun scaffolds (ES) based on poly(butylene succinate) (PBS) and poly(butylene succinate/diglycolate) (P(BS80BDG20)) affect human osteoblast differentiation, uniaxially aligned (a-) and randomly (r-) distributed nanofibers were produced. Although human osteoblastic SAOS-2 cells were shown to be viable and adherent onto all ES materials, a-P(BS80BDG20) exhibited the best performance both in terms of cellular phosphorylated focal adhesion kinase expression and in terms of alkaline phosphatase activity, calcified bone matrix deposition and quantitative gene expression of bone specific markers during differentiation. It has been hypothesized that the presence of ether linkages may lead to an increased density of hydrogen bond acceptors along the P(BS80BDG20) backbone, which, by interacting with cell membrane components, can in turn promote a better cell attachment on the copolymer mats with respect to the PBS homopolymer. Furthermore, although displaying the same chemical structure, r-P(BS80BDG20) scaffolds showed a reduced cell attachment and osteogenic differentiation in comparison with a-P(BS80BDG20), evidencing the importance of nanofiber alignment. Thus, the coupled action of polymer chemical structure and nanofiber alignment played a significant role in promoting the biological interaction.

Furanoate polyesters are emerging as promising bioderived polymers that could replace petrochemical-derived polyesters in several applications, for example, the textile field. Here, sustainable and fully bioderived fibers are wet-spun by blending poly(lactic acid) (PLA) and poly(pentamethylene 2,5-furanoate) (PPeF), with up to 50 wt% of PPeF. PLA/PPeF blends result as immiscible, with PPeF domains homogeneously distributed within the PLA matrix, as shown by scanning electron micrographs. The immiscibility is confirmed by differential scanning calorimetry, as the glass transition temperature of PLA is unaffected by PPeF. The immiscibility and poor adhesion between PLA and PPeF are responsible for the decrease in stress at break and elongation at break from 30.1MPa and 127%, of PLA fibers, to 3.5MPa and 1.9%, at high PPeF amounts. However, the addition of PPeF strongly decreases the PLA's tendency to absorb water and retain the processing solvents, showing a mass loss decrease from 3.1% for PLA fibers to 1% for fibers containing 50 wt% PPeF, thereby addressing one of the main drawbacks of PLA. These results, although preliminary, offer new directions for future works on innovative and sustainable fibers based on furanoate polyesters.

Novel poly(lactic acid)-based chain extended triblock copolymers have been successfully synthesized in melt. The new polymers are characterized by a triblock ABA architecture, where A, is poly(lactic acid) and B is an ad hoc synthesized random biobased aliphatic copolyester poly(propylene/neopentyl glycol succinate). PLLA homopolymer has been also prepared for the sake of comparison. The samples under study were deeply characterized from the molecular, thermal and structural point of view. Mechanical and barrier properties and compostability were also investigated, in order to assess the potentiality of these materials in food packaging applications. The results obtained show that copolymerization leads to better mechanical response and barrier properties with respect to poly(lactic) acid homopolymer. Moreover, the presence of the central B block in the main polymer chain facilitates the process of compostability.

Polymer nanostructures were developed on fully bio-based poly(trimethylene furanoate) (PTF) films, by using the technique of Laser Induced Periodic Surface Structures (LIPSS). We found that irradiation times between 1 and 8 min allowed the formation of periodic and nanometric ripples, when using an UV pulsed laser source at a fluence of 8 mJ/cm2. The wrinkled surfaces were studied by a combined macro- and nanoscale approach. We evaluated possible physicochemical changes taking place on the polymer surface after irradiation by infrared spectroscopy, contact angle measurements and atomic force microscopy. The macroscopic properties of PTF showed almost no changes after nanostructure formation, differently from the results previously found for the terephthalic counterparts, as poly(ethylene terephthalate), PET, and poly(trimethylene terephthalate), PTT. At the nanoscale, the surface mechanical properties of the nanostructured PTF were found to be improved, as evidenced by force spectroscopy measurements. In particular, stiffer surfaces characterized by an increased Young's modulus were measured for the nanostructured sample., This work has been supported by Ministry of Science, Innovation and Universities (MCIU, Spain) under the project CTQ2016-75880-P. D.E.M. acknowledges the financial support obtained through the Post-Doctoral fellowship “Juan de la Cierva – Incorporación” (IJCI-2017-31600, MCIU, Spain). E.R. thanks MCIU for the tenure of a Ramón y Cajal contract (No. RYC-2011-08069).

Dye-sensitized photooxygenation reaction of bio-based double bond-containing substrates is proposed as sustainable functionalization of terpenes and terpenoids to transform them into polyoxygenated compounds to be employed for the synthesis of new bio-based polyesters. As proof of concept, citronellol 1 has been regioselectively converted into diol 4 using singlet oxygen (O-1(2)), a traceless reagent that can be generated from air, visible light and zeolite supported-photosensitizer (Thionine-NaY). With our synthetic approach, diol 4 has been obtained in two-steps, with good regioselectivity, using green reagents such as light and air, and finally a solvent-free oxidation step. From this compound, a citronellol-based copolyester of poly(butylene succinate) (PBS) has been synthesized and fully characterized. The results obtained evidence that the proposed copolymerization of PBS with the citronellol-based building blocks allows to obtain a more flexible and functionalizable material, by exploiting a largely available natural molecule modified through a green synthetic path.

Thanks to the continuous progress of tissue engineering, the opportunity to overcome the main limits of traditional medicine is becoming more and more concrete. By a targeted study of biomaterials and their properties, it is possible to find ad hoc solutions for the fabrication of tissue engineered scaffolds. More in details, poly(butylene succinate) PBS is a biocompatible synthetic polymer already investigated for biomedical applications, but characterized by a high degree of crystallinity, which leads to long degradation times and mechanical properties often not suitable in the field of soft tissue engineering. In the present study, a PBS-based copolymer containing 30 mol% of dithiodipropionic co-units, P(BSBDTDP), was synthesized by two-step melt polycondensation. The comonomeric unit is characterized by the presence of -S-S- bond, potentially capable of improving both biocompatibility and biodegradability with respect to the homopolymer. After synthesis, 3D-mats and films were obtained by electrospinning and compression moulding, respectively, and then subjected to molecular, thermal and mechanical characterization. In addition, in view of a possible application in soft tissue engineering, enzymatic biodegradation studies and in vitro biocompatibility tests, using NIH-3T3 cell line, were also carried out. The results obtained show that through copolymerization solid-state properties could be nicely tailored. More in details, compared to PBS, P(BSBDTDP) is characterized by a lower crystallinity degree and mechanical properties typical of soft tissues, maintaining at the same time the good thermal stability of the parent homopolymer. In addition, copolymeric scaffold better supports cell adhesion and proliferation, undergoing degradation in biological environment slightly faster than its PBS homologous. (C) 2020 Elsevier Ltd. All rights reserved.

Herein, we present poly(butylene 1,4-cyclohexanedicarboxylate) (PBCE) films characterized by an unpatterned microstructure and a specific hydrophobicity, capable of boosting a drastic cytoskeleton architecture remodeling, culminating with the neuronal-like differentiation of human bone marrow-mesenchymal stem cells (hBM-MSCs). We have used two different filming procedures to prepare the films, solvent casting (PBCE) and compression-moulding (PBCE*). PBCE film had a rough and porous surface with spherulite-like aggregations (&Oslash, = 10&ndash, 20 &mu, m) and was characterized by a water contact angle = 100&deg, PBCE* showed a smooth and continuous surface without voids and visible spherulite-like aggregations and was more hydrophobic (WCA = 110&deg, ). Both surface characteristics were modulated through the copolymerization of different amounts of ether-oxygen-containing co-units into PBCE chemical structure. We showed that only the surface characteristics of PBCE-solvent-casted films steered hBM-MSCs toward a neuronal-like differentiation. hBM-MSCs lost their canonical mesenchymal morphology, acquired a neuronal polarized shape with a long cell protrusion (&ge, 150 &mu, m), expressed neuron-specific class III &beta, tubulin and microtubule-associated protein 2 neuronal markers, while nestin, a marker of uncommitted stem cells, was drastically silenced. These events were observed as early as 2-days after cell seeding. Of note, the phenomenon was totally absent on PBCE* film, as hBM-MSCs maintained the mesenchymal shape and behavior and did not express neuronal/glial markers.

11 pags., 7 figs., 4 tabs., In the present paper, four fully biobased homopolyesters of 2,5-furandicarboxylic acid (2,5-FDCA) with a high molecular weight have been successfully synthesized by two-stage melt polycondensation, starting from the dimethyl ester of 2,5-FDCA and glycols of different lengths (the number of methylene groups ranged from 3 to 6). The synthesized polyesters have been first subjected to an accurate molecular characterization by NMR and gel-permeation chromatography. Afterward, the samples have been successfully processed into free-standing thin films (thickness comprised between 150 to 180 μm) by compression molding. Such films have been characterized from the structural (by wide-angle X-ray scattering and small-angle X-ray scattering), thermal (by differential scanning calorimetry and thermogravimetric analysis), mechanical (by tensile test), and gas barrier (by permeability measurements) point of view. The glycol subunit length was revealed to be the key parameter in determining the kind and fraction of ordered phases developed by the sample during compression molding and subsequent cooling. After storage at room temperature for one month, only the homopolymers containing the glycol subunit with an even number of-CH2-groups (poly(butylene 2,5-furanoate) (PBF) and poly(hexamethylene 2,5-furanoate) (PHF)) were able to develop a three-dimensional ordered crystalline phase in addition to the amorphous one, the other two appearing completely amorphous (poly(propylene 2,5-furanoate (PPF) and poly(pentamethylene 2,5-furanoate) (PPeF)). From X-ray scattering experiments using synchrotron radiation, it was possible to evidence a third phase characterized by a lower degree of order (one-or two-dimensional), called a mesophase, in all the samples under study, its fraction being strictly related to the glycol subunit length: PPeF was found to be the sample with the highest fraction of mesophase followed by PHF. Such a mesophase, together with the amorphous and the eventually present crystalline phase, significantly impacted the mechanical and barrier properties, these last being particularly outstanding for PPeF, the polyester with the highest fraction of mesophase among those synthesized in the present work., G.G., M.S., N.L., and A.M. acknowledge the Italian Ministry of University and Research. This publication is based upon work from COST Action FUR4Sustain, CA18220, supported by COST (European Cooperation in Science and Technology).

This article belongs to the Special Issue Synthesis, Characterization and Simulation of Soft Matter with EUSMI., Poly(2,5-alkylene furanoate)s are bio-based, smart, and innovative polymers that are considered the most promising materials to replace oil-based plastics. These polymers can be synthesized using ecofriendly approaches, starting from renewable sources, and result into final products with properties comparable and even better than those presented by their terephthalic counterparts. In this work, we present the molecular dynamics of four 100% bio-based poly(alkylene 2,5-furanoate)s, using broadband dielectric spectroscopy measurements that covered a wide temperature and frequency range. We unveiled complex local relaxations, characterized by the simultaneous presence of two components, which were dependent on thermal treatment. The segmental relaxation showed relaxation times and strengths depending on the glycolic subunit length, which were furthermore confirmed by high-frequency experiments in the molten region of the polymers. Our results allowed determining structure–property relations that are able to provide further understanding about the excellent barrier properties of poly(alkylene 2,5-furanoate)s. In addition, we provide results of high industrial interest during polymer processing for possible industrial applications of poly(alkylene furanoate)s., This research was funded by the European Union: EUSMI, H2020-INFRAIA-2016-1, PROJECT 731019, via proposals E171100043 and E171100040. The APC was funded by EUSMI. B.R.-H. and A.A. acknowledge funding from Basque Government (IT-1175-19). D.E.M.-T. acknowledges financial support via the postdoctoral fellowship “Juan de la Cierva–Incorporación” grant (IJCI-2017-31600, MCIU–Spain). G.G., M.S. and N.L. and A.M. acknowledge financial support via the framework COST Action FUR4Sustain, CA18220, supported by COST (European Cooperation in Science and Technology).

Novel A-B-A triblock copolymers based on poly(L-lactic acid) (PLLA) were designed with an ad hoc chemical structure to prepare micro- and nanoparticles for controlled drug delivery. A block is formed by PLLA, while central B block is a copolymeric system based on poly(butylene succinate) and poly(triethylene succinate): more specifically, two copolymers with fix composition (50:50 mol:mol) and different molecular architecture were synthesized. One of them is characterized by a block architecture, i.e. long butylene succinate and triethylene succinate sequences form the macromolecular chains, the other being on the contrary a random copolymer with short sequences. The so-obtained materials were characterized from the molecular and thermal point of view. Moreover, to investigate the effect of both chemical structure and molecular architecture of the polymers synthesized on drug release kinetics, Dexamethasone-encapsulated micro- and nanoparticles were prepared by oil-in-water miniemulsion technique. These particles were subjected to thermal and morphological characterization. After that, drug release studies were carried out, and the effect of chemical composition, sequence distribution and particle size on release profile was evaluated. (C) 2020 Elsevier Ltd. All rights reserved.

The crystallization behavior of fully biobased poly(butylene isophthalate) (PBI) has been investigated using calorimetric and microscopic techniques. PBI is an extremely slow crystallizing polymer that leads, after melt-crystallization, to the formation of lamellar crystals and rather large spherulites, due to the low nuclei density. Based upon quantitative analysis of the crystal-nucleation behavior at low temperatures near the glass transition, using Tammann&rsquo, s two-stage nuclei development method, a nucleation pathway for an acceleration of the crystallization process and for tailoring the semicrystalline morphology is provided. Low-temperature annealing close to the glass transition temperature (Tg) leads to the formation of crystal nuclei, which grow to crystals at higher temperatures, and yield a much finer spherulitic superstructure, as obtained after direct melt-crystallization. Similarly to other slowly crystallizing polymers like poly(ethylene terephthalate) or poly(l-lactic acid), low-temperature crystal-nuclei formation at a timescale of hours/days is still too slow to allow non-spherulitic crystallization. The interplay between glass relaxation and crystal nucleation at temperatures slightly below Tg is discussed.

Poly(butylene 2,6-naphthalate) (PBN) is a crystallizable linear polyester containing a rigid naphthalene unit and flexible methylene spacer in the chemical repeat unit. Polymeric materials made of PBN exhibit excellent anti-abrasion and low friction properties, superior chemical resistance, and outstanding gas barrier characteristics. Many of the properties rely on the presence of crystals and the formation of a semicrystalline morphology. To develop specific crystal structures and morphologies during cooling the melt, precise information about the melt-crystallization process is required. This review article summarizes the current knowledge about the temperature-controlled crystal polymorphism of PBN. At rather low supercooling of the melt, with decreasing crystallization temperature, β’- and α-crystals grow directly from the melt and organize in largely different spherulitic superstructures. Formation of α-crystals at high supercooling may also proceed via intermediate formation of a transient monotropic liquid crystalline structure, then yielding a non-spherulitic semicrystalline morphology. Crystallization of PBN is rather fast since its suppression requires cooling the melt at a rate higher than 6000 K·s−1. For this reason, investigation of the two-step crystallization process at low temperatures requires application of sophisticated experimental tools. These include temperature-resolved X-ray scattering techniques using fast detectors and synchrotron-based X-rays and fast scanning chip calorimetry. Fast scanning chip calorimetry allows freezing the transient liquid-crystalline structure before its conversion into α-crystals, by fast cooling to below its glass transition temperature. Subsequent analysis using polarized-light optical microscopy reveals its texture and X-ray scattering confirms the smectic arrangement of the mesogens. The combination of a large variety of experimental techniques allows obtaining a complete picture about crystallization of PBN in the entire range of melt-supercoolings down to the glass transition, including quantitative data about the crystallization kinetics, semicrystalline morphologies at the micrometer length scale, as well as nanoscale X-ray structure information.

The peculiar reactivity of catechol carbonate (CC) with amines and polyamines in both solvent and catalyst free conditions is herein described. In all the tests performed at room temperature, CC conversion reached 100% in few seconds leading to the selective formation of the corresponding 2-hydroxyphenylcarbamate. This compound is furtherly rapidly converted to the di-substituted urea by the consecutive nucleophilic attack of another amine. Noteworthy, the application of this approach can be successfully extended to the one-pot bio-amine based synthesis of polyurea as herein proposed for the first time in literature. The reaction is of general purpose for primary amines and catechol can be easily recovered by sublimation as pure crystals ready to be recycled for the synthesis of new CC. An exception is related to the reactivity of secondary amine, which leads anyway to the selective formation of substituted phenolic carbamates (e.g. 2-hydroxyphenyl diethylcarbamate), suitable as intermediates in medicinal chemistry.

Plastics remarkably contribute to marine litter, which is raising serious concerns. Currently, little is known about the fate of most plastics entering the marine environment and their potential biodegradation rate and extent under anoxic conditions. In this work, biodegradation of polyvinyl chloride (PVC) films by consortia enriched from marine samples (litter and water) was evaluated in anaerobic microcosms. After 7 months, three microcosms showed dense biofilms on plastic surfaces, gravimetric weight losses up to 11.7 ± 0.6%, marked decreases in thermal stability and average molecular weight of the polymer, suggesting microbial attack towards polymer chains. After 24 months, further three consortia showed the same abilities. Microbial communities analyzed at month 24 included taxa closely related to those previously reported as halogenated organic compounds degraders. The study is the first report on PVC biodegradation by marine anaerobic microbes and provides insights on potential biodegradation of the plastic film introduced into the sea by native microbes.

Biopolymers are gaining increasing importance as substitutes for plastics derived from fossil fuels, especially for packaging applications. In particular, furanoate-based polyesters appear as the most credible alternative due to their intriguing physic/mechanical and gas barrier properties. In this study, block copolyesters containing 2,5-furan and trans-1,4-cyclohexane moieties were synthesized by reactive blending, starting from the two parent homopolymers: poly(propylene furanoate) (PPF) and poly(propylene cyclohexanedicarboxylate) (PPCE). The whole range of molecular architectures, from long block to random copolymer with a fixed molar composition (1:1 of the two repeating units) was considered. Molecular, thermal, tensile, and gas barrier properties of the prepared materials were investigated and correlated to the copolymer structure. A strict dependence of the functional properties on the copolymers&rsquo, block length was found. In particular, short block copolymers, thanks to the introduction of more flexible cyclohexane-containing co-units, displayed high elongation at break and low elastic modulus, thus overcoming PPF&rsquo, s intrinsic rigidity. Furthermore, the exceptionally low gas permeabilities of PPF were further improved due to the concomitant action of the two rings, both capable of acting as mesogenic groups in the presence of flexible aliphatic units, and thus responsible for the formation of 1D/2D ordered domains, which in turn impart outstanding barrier properties.

The overall migration behavior and the disintegration under composting conditions of films based on plasticized poly(lactic acid)/poly(3-hydroxybutyrate) (PLA-PHB) blends were studied, with the main aim of determining the feasibility of their application as biodegradable food packaging materials. The role of composition in the disintegration process was evaluated by monitoring the changes in physical and thermal properties that originated during the degradation process. PLA and PHB were blended in two weight ratios with 15 wt% of tributyrin, using a Haake mixer and then compression molded into ~150 μm films. We found that the migration level of all of the studied blends was below check intended meaning retained in non-polar simulants, while only plasticized blends could withstand the contact with polar solvents. The disintegration of all of the materials in compost at 58 °C was completed within 42 days, the plasticized PHB underwent the fastest degradation, taking only 14 days. The presence of the TB plasticizer speeded up the degradation process. Different degradation mechanisms were identified for PLA and PHB. To evaluate the annealing effect separately from bacteria degradation, the influence of temperature on materials in the absence of a compost environment was also studied. With the increasing time of degradation in compost, both melting temperature and maximum degradation temperature progressively decreased, while the crystallinity degree increased, indicating that the samples were definitely degrading and that the amorphous regions were preferentially eroded by bacteria.