Biodegradable Polyester Research Articles

Alanine Production by Chemical Upcycling of Polylactic Acid Waste Over Fe-Doped Ru/CeO2.

Biodegradable polyesters, such as polylactic acid (PLA), is one of the most promising plastics with great potential to contribute to enabling a sustainable global circular economy. However, the efficient chemical upcycling of PLA plastic waste into high-value chemicals remains a grand challenge. Herein, a series of Ru/CeFeOx catalysts with varying Ru loadings were developed for the catalytic amination of PLA plastic waste to alanine in the presence of ammonia. The as-prepared catalysts exhibited exceptional catalytic activity, high selectivity, and excellent recyclability, achieving an alanine yield of 70.5 % at 180 °C for 18 h, significantly surpassing previous reports. The outstanding catalytic performance can be primarily attributed to the presence of Fe species in Ru/CeFeOx, which generated more oxygen vacancies, provided abundant base sites, and enhanced reducibility, therefore accelerating the reaction rate and enhancing catalytic efficiency. This study presents an alternative strategy for the sustainable chemical upcycling of PLA plastic waste into alanine and the realization of a circular economy.

Hydrogenating Polyethylene Terephthalate into Degradable Polyesters

The recycling and upcycling of polyethylene terephthalate (PET), the most widely used polyester plastic globally, has attracted growing attention concerning its disposal as non‐degradable waste in the natural environment. Transforming end‐of‐life PET into (bio)degradable polyester offers a novel approach to managing its waste. In this study, we introduce a simple process capable of converting waste PET into degradable polyester, polyethylene terephthalate‐polyethylene‐1,4‐cyclohexanedicarboxylate (PET‐PECHD), by partly hydrogenating the aromatic rings (x) into aliphatic ones (y). The polyesters with variable x/y compositions ranging from 100/0 to 0/100 can be achieved, and the molecular weight (Mw) can be maintained when x/y > 87/13 due to the nonobvious depolymerization. Pronounced depolymerization would occur with deeper hydrogenation, which generates a blend of PET‐PECHD and polyethylene‐1,4‐cyclohexanedicarboxylate (PECHD) with lower Mw, and finally a single‐type polymer PECHD. The PET‐PECHD demonstrates comparable thermal stability and mechanical strength compared to PET, along with superior extensibility, barrier properties, and (bio)degradability in acidic, alkaline solutions, and moist soil. This research highlights the potential for cost‐effective, large‐scale production of degradable polyester from real‐life plastic waste.

Hydrogenating Polyethylene Terephthalate into Degradable Polyesters.

The recycling and upcycling of polyethylene terephthalate (PET), the most widely used polyester plastic globally, has attracted growing attention concerning its disposal as non-degradable waste in the natural environment. Transforming end-of-life PET into (bio)degradable polyester offers a novel approach to managing its waste. In this study, we introduce a simple process capable of converting waste PET into degradable polyester, polyethylene terephthalate-polyethylene-1,4-cyclohexanedicarboxylate (PET-PECHD), by partly hydrogenating the aromatic rings (x) into aliphatic ones (y). The polyesters with variable x/y compositions ranging from 100/0 to 0/100 can be achieved, and the molecular weight (Mw) can be maintained when x/y > 87/13 due to the nonobvious depolymerization. Pronounced depolymerization would occur with deeper hydrogenation, which generates a blend of PET-PECHD and polyethylene-1,4-cyclohexanedicarboxylate (PECHD) with lower Mw, and finally a single-type polymer PECHD. The PET-PECHD demonstrates comparable thermal stability and mechanical strength compared to PET, along with superior extensibility, barrier properties, and (bio)degradability in acidic, alkaline solutions, and moist soil. This research highlights the potential for cost-effective, large-scale production of degradable polyester from real-life plastic waste.

Bio-based epoxidized cardanol sorbate as an interface-localized compatibilizer for enhancing poly(lactic acid) (PLA) and poly(3-hydroxybutyric acid-co-4-hydroxybutyric acid) (P34HB) blend

PLA is a bio-based polyester with limited barrier and flexible properties. Adding poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (P34HB), a biodegradable polyester known for its outstanding barrier properties, was the strategy employed to boost PLA performance. However, the blend’s immiscibility necessitates compatibilizers to bolster interfacial adhesion and dispersion. This study designed a novel bio-based compatibilizer, epoxidized cardanol sorbate (ECD-SA), to improve the compatibility of the blend. The molecular design of ECD-SA has been optimized to minimize steric hindrance, thereby enhancing interfacial reactions more effectively. Two commercial compatibilizers, specifically ADR 4468 and NC-514, were selected for comparison. Theoretical model was employed to calculate dispersion preferences of three different compatibilizers in the blend. A systematic investigation was carried out to analyze the effects of compatibilizers on the structure and properties of PLA/P34HB blends. The findings suggest that ECD-SA functions as an interface-localized compatibilizer in PLA/P34HB blends, enhancing their compatibility and performance significantly. Specifically, the incorporation of 2 phr (parts per hundred resin) ECD-SA into the PLA/P34HB film resulted in a marked increase in tensile strength from 35.6 MPa and 23.5 MPa to 48.6 MPa and 36 MPa in the longitudinal and transverse directions, respectively, and an increase in elongation at break from 31.9 % and 9.2 % to 104.8 % and 48.3 %, respectively. This underscores its significant potential as a compatibilizer for PLA/P34HB, pointing towards extensive application possibilities in present-day packaging industries.

Review on Biodegradable Aliphatic Polyesters: Development and Challenges.

Biodegradable polymers are gaining attention as alternatives to non-biodegradable plastics to address environmental issues. With the rising global demand for plastic products, the development of non-toxic, biodegradable plastics is a significant topic of research. Aliphatic polyester, the most common biodegradable polyester, is notable for its semi-crystalline structure and can be synthesized from fossil fuels, microbial fermentation, and plants. Due to great properties like being lightweight, biodegradable, biocompatible, and non-toxic, aliphatic polyesters are used in packaging, medical, agricultural, wearable devices, sensors, and textile applications. The biodegradation rate, crucial for biodegradable polymers, is discussed in this review as it is influenced by their structural properties and environmental conditions. This review discusses currently available biodegradable polyesters, their emerging applications, and the challenges in their commercialization. As research in this area grows, this review emphasizes the innovation in biodegradable aliphatic polyesters and their role in advancing environmental sustainability.

Genome sequence of the marine alphaproteobacterium Lentilitoribacter sp. EG35 isolated from the temperate octocoral Eunicella gazella.

We report the genome sequence of Lentilitoribacter sp. strain EG35 isolated from the octocoral Eunicella gazella sampled off the coast of Portugal. We reveal the coding potential for the biosynthesis of polyhydroxyalkanoates - biodegradable polyesters that may serve bioplastics production, diverse homoserine lactone-like communication signals, and four putatively novel natural products.

Mucoadhesive poly(ethylene glycol)-based biodegradable polyesters with in-chain model drug

Mucoadhesive polymers have received significant interest in drug delivery due to the prolonged residence time on various mucus gel layers. Not only local effects but also the systemic uptake of active pharmaceutical ingredients can be enhanced by such mucoadhesive excipients. In this study, we design novel poly(ethylene glycol) based mucoadhesive polyesters bearing unsaturated or sulfhydryl functionalities and model drug fluorescein polymerized in the polymeric backbone. The structure of polyesters was confirmed via 1H NMR and FTIR, while their molar masses, determined by gel permeation chromatography, were found to be between 3.6 and 4.0 kDa. Enzymatic degradation studies showed the ability of lipase to degrade the polymeric chains. Because of the mucoadhesive groups, the viscosity of mucus mixtures with these polymers increased 1.8-fold for the double bond, while 4.3-fold for thiol functional polymers, compared to PEG. Prolonged residence time on porcine intestinal mucosa was detected, as 3 h after application, up to 69 % of the polymers were still on the mucosa, whereas PEG was completely removed within 30 mins. Highly pH and enzyme-dependent release of fluorescein was noticed; only pH > 6.8 caused significant drug release. According to the results of this study, PEG-based unsaturated and thiolated polyesters with in-chain model drugs are great mucoadhesive and biodegradable drug carriers with sustained release properties.

Crystallization and melting of Poly(4-hydroxybutyrate) characterized by fast scanning calorimetry

Poly (4-hydroxybutyrate) (P4HB) is a marine biodegradable polyester with promising applications. Unfortunately, the crystallization and melting behavior of P4HB has not been systematically studied, due to the rapid crystallization near room temperature. In particular, the characterization of crystallization and melting of P4HB by fast scanning calorimetry (FSC) has not been reported previously. In this article, the common differential scanning calorimeter (DSC), polarized optical microscopy (POM), atomic force microscopy (AFM) and FSC were performed to investigate the crystallization and melting behavior of P4HB. The results indicated that melt crystallization facilitated the formation of fragmented crystals rather than complete spherulites. Furthermore, the P4HB exhibited a broad crystallization temperature range from −19 °C to 49 °C, and the crystallization and melting of P4HB was notably affected by the temperature, in addition to the heating or cooling rates. The higher crystallization temperature and lower cooling rates facilitated the formation of well-developed crystals. Remarkably, the P4HB is found to be unable to crystallize at heating or cooling rates exceeding 6 K/s. Moreover, double melting peaks could be discerned at moderate isothermal crystallization temperature exhibiting faster crystallization rate. The findings will provide theoretical guidance on how to optimize the processing parameters in modulating the crystallization of P4HB.

Biomimetic microgels for articular cartilage regeneration. A minipig knee model

The aim of this study is to explore, with an in vivo model, the regeneration of articular cartilage that can be obtained with a strategy that combines the stimulation of the subchondral bone with the implantation of a biomimetic microgel at the site of the cartilage defect. The microgel consists of an agglomerate of two types of microspheres: ones rigid, made of a biodegradable polyester, and the other ones composed of a polymeric network of gelatin and hyaluronic acid that encapsulate platelet-rich plasma (PRP) obtained from circulating autologous blood. A defect of 7 mm in diameter and full depth was performed in the in the articular cartilage at the trochlea of the animal knee, using a minipig model. Microdrilling was performed in the underlying bone and the defect was filled with the microgel in which the platelets it contains were previously activated with calcium chloride. The whole defect containing the microgel was covered with a synthetic membrane to avoid the release of microspheres. The results of the in vivo follow-up of the experiment, the histological analysis and the mechanical measurements of the regenerated tissue 9 months after implantation were compared with those of a group of animals in which only microdrilling was performed and the defect was covered with the membrane and with another group in which a clinical use commercial collagen mesh was implanted. The mean value of the elastic modulus of the newly formed tissue was not significantly different from that of the native tissue in the case of microgel implantation while its content of GAGs, was significantly better than in the other groups.

Melt processing of biodegradable poly(butylene succinate) (PBS)—a critical review

AbstractThis review paper presents a comprehensive analysis of the melt processing of polybutylene succinate (PBS) blends and composites. PBS, a biodegradable and eco-friendly thermoplastic polyester, has garnered significant interest in sustainable material research. The paper collates and examines a wide range of studies focusing on the processability, optimization of processing parameters, and resultant mechanical properties of PBS when processed through several extrusion techniques and by injection molding. Key parameters such as melt temperature, screw speed, and mold temperature are considered for their impact on the quality and performance of the final product. The review highlights advancements in processing technologies and material modifications that enhance PBS properties, making it a viable alternative to traditional petroleum-based plastics. Furthermore, challenges and limitations in the current processing techniques are discussed, offering insights into potential areas for future research. The synthesis of findings from various studies provides a holistic understanding of the state-of-the-art in PBS processing, aiming to guide further developments in the field of biodegradable polymers. Overall, this review underscores the importance of optimized melt processing techniques in maximizing the potential of PBS as a sustainable material in diverse applications. Graphical abstract

Chemolysis for Efficient and Sustainable Upcycling of Biodegradable Polyester Waste to Value-Added Products

Chemolysis for Efficient and Sustainable Upcycling of Biodegradable Polyester Waste to Value-Added Products

Overcoming strength-ductility and functional period-degradability tradeoffs: Multifunctional biodegradable polyesters with ionic cluster skeleton and PDMS skin

To overcome the strength-ductility and functional period-degradability tradeoffs of biodegradable polyesters, we proposed a nanophase structure design strategy to construct a soft-hard dual phase in poly(butylene succinate) (PBS) copolymers by simultaneously introducing polydimethylsiloxane (PDMS) and isophthalate-5-sulfonate (SIPM) on PBS macromolecular chains to improve the stiffness, toughness, and multifunctionality. The high-resolution transmission electron microscope (HR-TEM) and energy dispersive X-Ray spectroscopy (EDX) tests indicated that PBS copolymers possessed continuous “ionic cluster skeleton” and “PDMS skin”. The hybrid liquid state theory and self-consistent field approach for copolymers further demonstrated the mechanism of microphase separation for PDMS blocks and SIPM segments. The copolymers showed excellent yield strength of 52 MPa, great impact strength of 171 J/m, large extensibility of 491 %, and long functional period in the acidic environment. The novel stereo nanostructure endowed the materials with advanced multifunctions that can be applied in various applications, such as the biomedical field and flexible electronic devices. Compared with PBS, copolymers possessed excellent in vitro attachment and proliferation of MC3T3-E1 cells. Furthermore, the synergistic effect of the ionic skeleton and PDMS skin improved the ionic conductivity of the materials. The copolymer film was innovatively employed as anion-exchanging separators of supercapacitors with acid-organized electrolytes. It has been testified that this newly designed strategy of a novel stereo nanophase structure was efficient in endowing the biodegradable polyesters with excellent combined properties and multifunctions.

Bioplastic production by harnessing cyanobacteria-rich microbiomes for long-term synthesis

Departing from the conventional axenic and heterotrophic cultures, our research ventures into unexplored territory by investigating the potential of photosynthetic microbiomes for polyhydroxybutyrate (PHB) synthesis, a biodegradable polyester that presents a sustainable alternative to conventional plastics. Our investigation focused on a cyanobacteria-enriched microbiome, dominated by Synechocystis sp. and Synechococcus sp., cultivated in a 3 L photobioreactor under non-sterile conditions, achieving significant PHB production—up to 28 % dry cell weight (dcw) over a span of 108 days through alternating cycles of biomass growth and PHB accumulation. Nile Blue staining and Transmission Electron Microscope visualization allowed to successfully confirm the presence of PHB granules within cyanobacteria cells. Furthermore, the overexpression of PHA synthase during the accumulation phase directly correlated with the increased PHB production. Also, gene expression changes revealed glycogen as the primary storage compound, but under prolonged macronutrient stress, there was a shift of the carbon flux towards favoring PHB synthesis. Finally, analysis through Raman, Fourier- transform infrared spectroscopy and proton Nuclear Magnetic Resonance further validated the extracted polymer as PHB. Overall, it was demonstrated for the first time the feasibility of using phototrophic microbiomes to continuous production of PHB in a non-sterile system. This study also offers valuable insights into the metabolic pathways involved.

Advancing H-Bonding Organocatalysis for Ring-Opening Polymerization: Intramolecular Activation of Initiator/Chain End.

Organocatalytic ring-opening polymerization (ROP) of lactones is a green method for accessing renewable and biodegradable polyesters. Developing new organocatalysts with high activity and controllability is a major and challenging research topic in this field. Here, we report a series of organocatalysts to achieve a fast and controlled ROP of lactones. These catalysts incorporate (thio)urea and alkoxide in one molecule and act as initiators in the ROP. Such catalysts enable an effective intramolecular activation of initiator/chain end, as revealed by computational studies, resulting in higher activity and fewer (thio)urea loads than existing (thio)urea/alkoxide binary systems. These organocatalysts exhibit ultrahigh activity comparable to metal complexes, i.e., turnover number up to 900 and turnover of frequency up to 4860 min-1, affording polyesters with tailor-made structure, predicted molecular weights, narrow dispersity, less epimerization, and minimal transesterification. The catalyst synthesis is simple and scalable, allowing widely tuned activities of the ROP.

Polyester nanoparticles delivering chemotherapeutics: Learning from the past and looking to the future to enhance their clinical impact in tumor therapy.

Polymeric nanoparticles (NPs), specifically those comprised of biodegradable and biocompatible polyesters, have been heralded as a game-changing drug delivery platform. In fact, poly(α-hydroxy acids) such as polylactide (PLA), poly(lactide-co-glycolide) (PLGA), and poly(ε-caprolactone) (PCL) have been heavily researched in the past three decades as the material basis of polymeric NPs for drug delivery applications. As materials, these polymers have found success in resorbable sutures, biodegradable implants, and even monolithic, biodegradable platforms for sustained release of therapeutics (e.g., proteins and small molecules) and diagnostics. Few fields have gained more attention in drug delivery through polymeric NPs than cancer therapy. However, the clinical translational of polymeric nanomedicines for treating solid tumors has not been congruent with the fervor or funding in this particular field of research. Here, we attempt to provide a comprehensive snapshot of polyester NPs in the context of chemotherapeutic delivery. This includes a preliminary exploration of the polymeric nanomedicine in the cancer research space. We examine the various processes for producing polyester NPs, including methods for surface-functionalization, and related challenges. After a detailed overview of the multiple factors involved with the delivery of NPs to solid tumors, the crosstalk between particle design and interactions with biological systems is discussed. Finally, we report state-of-the-art approaches toward effective delivery of NPs to tumors, aiming at identifying new research areas and re-evaluating the reasons why some research avenues have underdelivered. We hope our effort will contribute to a better understanding of the gap to fill and delineate the future research work needed to bring polyester-based NPs closer to clinical application. This article is categorized under: Therapeutic Approaches and Drug Discovery > Nanomedicine for Oncologic Disease Nanotechnology Approaches to Biology > Nanoscale Systems in Biology Therapeutic Approaches and Drug Discovery > Emerging Technologies.

Characterization of the conversion system of natural rubber to poly(3-Hydroxyalkanoate) in Piscinibacter gummiphilus strain NS21T

Poly(3-hydroxyalkanoate) (PHA), a bacteria-synthesized biodegradable polyester, is a useful alternative to fossil resources, and current systems for its production rely predominantly on edible resources, raising concerns about microbial competition for nutrients. Therefore, we investigated mechanisms underlying PHA production from non-edible resources by Piscinibacter gummiphilus strain NS21T. Strain NS21T can utilize natural rubber as a carbon source on solid media and potentially produces PHA. Gas chromatography and nuclear magnetic resonance analyses of NS21T cell extracts revealed the production of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly(3-hydroxybutyrate) from natural rubber and glucose, respectively. Transcriptional analysis suggested that phaC is involved in PHA production. An increased PHBV accumulation rate under nitrogen-limiting conditions indicates the potential of this strain to be used as a PHBV production enhancement strategy. Furthermore, the disruption of PHA depolymerase genes resulted in enhanced PHA production, indicating the involvement of these genes in PHA degradation. These findings highlight the potential of NS21T for PHBV production from natural rubber, a non-edible resource.

Ionized copolyesters with pH-responsive degradability: Accelerated degradation in specific environments

The development of environmentally responsive biodegradable polymers is a promising solution for balancing the stability and degradability of biodegradable plastics. In this study, a commercial biodegradable polyester, poly(butylene adipate-co-butylene terephthalate) (PBAT), was used as the substrate and was synthetically modified with a small amount of anionic sodium 1–3-isophthalate-5-sulfonate (SIPA) to obtain the ionized random poly(butylene adipate-co-butylene terephthalate-co-butylene 5-sodiosulfoisophthalate) (PBATS). The introduction of the sodium sulfonate ionic group enhanced the mechanical and heat-resistant properties of the material, while significantly improving the hydrophilicity and water absorption of the copolyesters of PBATSs and endowing them with special pH-responsive degradation properties. Compared with PBAT, PBATS copolyesters could accelerate degradation in acidic or alkaline buffer solutions and natural seawater, while degradation was inhibited in neutral buffer solutions at pH 7.2. Degradation experiments in simulated gastric, intestinal, and body fluids revealed that the copolyester showed specific and rapid degradation in acidic gastric fluids. This environmentally-responsive degradable material greatly expands the special applications of biodegradable polyesters in the fields of environmental remediation and medical applications.

Time-dependent underwater interaction between polyhydroxyalkanoate coatings and functionalized surfaces

Polyhydroxyalkanoates (PHAs), a family of naturally occurring biodegradable polyester, are considered environmentally friendly alternatives to conventional commodity plastics derived from petrochemicals.; however, their molecular interaction in water has not been elucidated. Here, we investigated the surface- and contact time-dependent underwater interaction characteristics of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P(3HB-co-4HB)), the most common PHA, using a surface forces apparatus (SFA). We found that PHA showed weak adhesion with functionalized surface and cohesion for a short-contact time (<30 mins) in the water. The adhesion to the functionalized surface was strong in the order of mica (negatively charged hydrophilic), APTES (positively charged hydrophilic), and PS (hydrophobic). However, the adhesive strength of PHA to the functionalized surfaces increased as contact time increased, which may be attributed to chain rearrangement, reorientation, or van der Waals forces of PHA in water. We also confirmed results similar to those for SFA by bulk testing on hydrophilic surfaces. As PHAs have attracted people’s attention as eco-friendly and biocompatible polymers, these results provide insights for the development of PHA-based composite, as well as for the biodegradation and fate of PHA post-use.

Preparation of biodegradable poly(lactic acid)/poly[(butylene diglycolate)‐co‐furandicarboxylate] blends with excellent toughness and gas barrier performance

AbstractPoly(lactic acid) (PLA) is known as one of the most promising biodegradable polyesters, while inherent brittleness and insufficient gas barrier performance limit its potential application as a film material. Herein, poly[(butylene diglycolate)‐co‐furandicarboxylate] (PBDF) with excellent flexibility and good gas barrier properties was synthesized and then melt‐blended with PLA. Compared with neat PLA, the elongation at break of the PLA/PBDF20 blend increased more than 40 times and reached over 176.7%. In addition, its O2, CO2 and H2O permeability coefficients decreased by 21.3%, 50.8% and 46.3%, respectively. Moreover, the PLA/PBDF20 blend also exhibited better biodegradability, with a weight loss rate increasing from 2.7% of neat PLA to 19.0% after 5 weeks of composting. Notably, incorporation of a multifunctional epoxy compatibilizer (Joncryl ADR®‐4368) into the PLA/PBDF blends further enhanced their toughness and gas barrier performance, which could be attributed to the improvement of the miscibility between PLA and PBDF. © 2024 Society of Chemical Industry.

Toxicological Assessment of Biodegradable Poli-ε-Caprolactone Polymer Composite Materials Containing Hydroxyapatite, Bioglass, and Chitosan as Potential Biomaterials for Bone Regeneration Scaffolds.

Polycaprolactone (PCL) is a biodegradable polyester that might be used in tissue engineering to obtain scaffolds for bone reconstruction using 3D-printing technologies. New material compositions based on PCL, with improved physicochemical properties and excellent biocompatibility, would improve its applicability in bone regeneration. The aim of this study was to assess the potential toxic effects of PCL-based composite materials containing 5% hydroxyapatite (PCL/SHAP), 5% bioglass (PCL/BIO), or 5% chitosan (PCL/CH) on MG-63 human fibroblast-like cells in vitro. Material tests were carried out using X-ray diffraction, differential thermal analysis/thermal gravimetry, BET specific surface analysis, and scanning electron microscopy. The effect of the biomaterials on the MG-63 cells was then assessed based on toxicity tests using indirect and direct contact methods. The analysis showed that the tested biomaterials did not significantly affect cell morphology, viability, proliferation, or migration. We concluded that biodegradable PCL-based scaffolds may be suitable for tissue scaffold production, and the addition of bioglass improves the growth of cultured cells.