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1.
J Environ Sci (China) ; 149: 242-253, 2025 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-39181639

RESUMEN

Poly(butylene succinate-co-furandicarboxylate) (PBSF) and poly(butylene adipate-co-furandicarboxylate) (PBAF) are novel furandicarboxylic acid-based biodegradable copolyesters with great potential to replace fossil-derived terephthalic acid-based copolyesters such as poly(butylene succinate-co-terephthalate) (PBST) and poly(butylene adipate-co-terephthalate) (PBAT). In this study, quantum chemistry techniques after molecular dynamics simulations are employed to investigate the degradation mechanism of PBSF and PBAF catalyzed by Candida antarctica lipase B (CALB). Computational analysis indicates that the catalytic reaction follows a four-step mechanism resembling the ping-pong bibi mechanism, with the initial two steps being acylation reactions and the subsequent two being hydrolysis reactions. Notably, the first step of the hydrolysis is identified as the rate-determining step. Moreover, by introducing single-point mutations to expand the substrate entrance tunnel, the catalytic distance of the first acylation step decreases. Additionally, energy barrier of the rate-determining step is decreased in the PBSF system by site-directed mutations on key residues increasing hydrophobicity of the enzyme's active site. This study unprecedently show the substrate binding pocket and hydrophobicity of the enzyme's active site have the potential to be engineered to enhance the degradation of copolyesters catalyzed by CALB.


Asunto(s)
Proteínas Fúngicas , Lipasa , Poliésteres , Lipasa/metabolismo , Lipasa/química , Proteínas Fúngicas/metabolismo , Proteínas Fúngicas/química , Poliésteres/química , Poliésteres/metabolismo , Biodegradación Ambiental , Simulación de Dinámica Molecular , Hidrólisis , Modelos Químicos
2.
Sci Total Environ ; 953: 176129, 2024 Sep 08.
Artículo en Inglés | MEDLINE | ID: mdl-39255933

RESUMEN

Understanding the environmental fate of biodegradable plastics in aquatic systems is crucial, given the alarming amount of plastic waste and microplastic particles transported through aquatic pathways. In particular, there is a need to analyze the biodegradation of commercialized biodegradable plastics upon release from wastewater treatment plants into natural aquatic systems. This study investigates the biodegradation behaviors of poly(butylene adipate terephthalate) (PBAT) and poly(vinyl alcohol) (PVA) in wastewater, freshwater, and seawater. Biodegradation of PBAT and PVA assessed through biochemical oxygen demand (BOD) experiments and microcosm tests revealed that the type of aquatic system governs the biodegradation behaviors of each plastic, with the highest biodegradation rate achieved in wastewater for both PBAT and PVA (25.6 and 32.2 % in 30 d, respectively). Plastic release pathway from wastewater into other aquatic systems simulated by sequential incubation in different microcosms suggested that PBAT exposed to wastewater and freshwater before reaching seawater was more prone to degradation than when directly exposed to seawater. On the other hand, PVA displayed comparable biodegradation rate regardless of whether it was directly exposed to seawater or had passed through other environments beforehand. Metagenome amplicon sequencing of 16S rRNA genes revealed distinct community shifts dependent on the type of plastics in changing environments along the simulated aquatic pathway. Several bacterial species putatively implicated in the biodegradation of PBAT and PVA are discussed. Our findings underscore the significant influence of pollution routes on the biodegradation of PBAT and PVA, highlighting the potential for wastewater treatment to facilitate rapid degradation compared to direct exposure to pristine aquatic environments.

3.
Polymers (Basel) ; 16(17)2024 Aug 29.
Artículo en Inglés | MEDLINE | ID: mdl-39274078

RESUMEN

As an important biodegradable and partially biobased copolyester, poly(butylene succinate-co-terephthalate) (PBST) possesses comparable thermal and mechanical properties and superior gas barrier performance when compared with poly(butylene adipate-co-terephthalate) (PBAT), but it was found to display poorer melt processability during pelletizing and injection molding. To make clear its melt crystallization behavior under rapid cooling, PBST48 and PBST44 were synthesized, and their melt crystallization was investigated comparatively with PBAT48. PBST48 showed a PBAT48-comparable melt crystallization performance at a cooling rate of 10 °C/min or at isothermal conditions, but it showed a melt crystallization ability at a cooling rate of 40 °C/min which was clearly poorer. PBST44, which has the same mass composition as PBAT48, completely lost its melt crystallization ability under the rapid cooling. The weaker chain mobility of PBST, resulting from its shorter succinate moiety, is responsible for its inferior melt crystallization ability and processability. In comparison with PBAT48, PBST48 displayed higher tensile modulus, and both PBST48 and PBST44 showed higher light transmittance. The findings in this study deepen the understanding of PBST's properties and will be of guiding significance for improving PBST's processability and application development.

4.
Sci Total Environ ; : 176421, 2024 Sep 19.
Artículo en Inglés | MEDLINE | ID: mdl-39306119

RESUMEN

With the increasing demand for plastics, plastic pollution is growing rapidly. A significant amount of plastic has leaked into the environment, leading to severe environmental issues. Biodegradable plastics are considered promising alternatives to conventional durable plastics, and the environmental impacts of biodegradable plastics have received increasing attention. Poly (butylene adipate-co-terephthalate) (PBAT) is a commercial and cost-competitive biodegradable polymer and has been applied in the packaging and agriculture sectors. The environmental performances of PBAT with second-generation feedstocks from forestry waste have been rarely investigated. Since China is the leading global producer and exporter of PBAT polymer, Chinese cradle-to-gate life cycle inventories of PBAT were compiled in this study. A comparative life cycle assessment (LCA) was conducted to explore the potential for environmental performance of PBAT with second-generation biobased feedstock compared to fossil-derived PBAT and conventional plastics. The results showed that feedstocks contributed to more than 70 % of 18 environmental impact categories of fossil-derived PBAT. In comparison, PBAT with 2nd generation biobased feedstock reduces the environmental loads in 16 impact categories by 15-85 %, and renewable energy substitution has the potential to reduce environmental impacts by 10 %. Biobased PBAT performs better than PVC, PP, HDPE, LDPE, and PET in 16 impact categories by 15-80 %. Biobased PBAT has GWP of 3.72 kg CO2 eq, which is 37 % lower than fossil-derived PBAT (5.89 kg CO2 eq) and 18-32 % lower than conventional plastics. Since feedstock dominates the environmental performance of PBAT, the development of biomanufacturing technologies for biobased polymers and chemicals could significantly improve environmental performance of biodegradable plastics and promote the sustainable development of the plastic industry. Results could serve as the basis for environmental impact and mitigation strategies for biodegradable plastics with biobased feedstocks, as well as the sustainable development of the PBAT industry.

5.
Int J Biol Macromol ; 279(Pt 4): 135579, 2024 Sep 11.
Artículo en Inglés | MEDLINE | ID: mdl-39270900

RESUMEN

To enhance the mechanical properties of polylactic acid (PLA) material, the PLA-based composite films are prepared by using Pueraria lobata (Willd.) Ohwi root microcrystalline cellulose (PRMCC) treated with 3-aminopropyl triethoxysilane (KH550) silane coupling agent as the dispersed phase through solvent casting method. The effects of the concentrations of PRMCC and KH550 as well as the KH550 pretreating condition (ethanol concentration) on the tensile properties of PLA-based composite films are investigated. The PLA-based composite film treated with 5 wt% PRMCC and 18 wt% KH550 (pretreated by 90 % EtOH) exhibits the greatest performance. Its elongation at break value is detected to be 4.0 %, 1.6 times as large as that of pure PLA film. The water absorption of the as-prepared PLA-based composite film is reduced from 0.49 % of the unmodified PLA/PRMCC film to 0.12 %. Moreover, the modified PLA-based composite film has a hydrophobic surface and exhibits good thermal stability. Compared with pure PLA film, the modified PLA-based composite film exhibits improved UV shielding performance with acceptable transparency. Furthermore, after adding poly(butylene adipate-co-terephthalate) (PBAT) to the composite system, the elongation at break of the PLA-based composite film is up to 7.2 %. This research can provide theoretical guidance for enhancing the performance of PLA products.

6.
Aquat Toxicol ; 275: 107065, 2024 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-39213726

RESUMEN

The extensive use of traditional non-biodegradable plastics results in the generation of microplastics (MPs), forming a new pollutant that can pose significant environmental risks. Biodegradable plastics (BP) possess degradation properties and can partially replace conventional plastics, thereby reducing pollution. However, further investigation is needed into the toxicity of biodegradable microplastics (BMPs) on aquatic organisms. This study explores the toxic effects of PBAT microplastics (PBAT-BMPs) and microplastics produced from degradable PBAT/TPS (thermoplastic starch) composite film (PBAT/TPS-BMPs) on zebrafish embryos. Our findings indicate that the presence of microplastics on the embryo's surface increases with higher BMPs concentration. Nonetheless, PBAT-BMPs tend to aggregate and are blocked by the embryonic membrane, thus diminishing their toxic effects on the embryo. Acute toxicity experiments revealed that 30 mg/L of PBAT-BMPs significantly reduced the survival rate of zebrafish embryos, whereas PBAT/TPS-BMPs had a lesser effect on survival. Both types of BMPs influenced the hatching rate of the embryos, leading to prolonged incubation periods. Additionally, both types of BMPs impacted the locomotor behavior of zebrafish larvae, causing an increase in larval locomotor speed. However, these BMPs had little impact on larval body development and heartbeat behavior. Fluorescent microplastic tracer experiments demonstrated that PBAT-BMPs persisted in juvenile fish for at least 144 h and were difficult to metabolize and excrete. Our study aims to gain a better understanding of the potential effects of BMPs on aquatic ecosystems and biological health, as well as to propose effective strategies for reducing environmental pollution and protecting organisms.


Asunto(s)
Embrión no Mamífero , Microplásticos , Contaminantes Químicos del Agua , Pez Cebra , Animales , Pez Cebra/embriología , Microplásticos/toxicidad , Contaminantes Químicos del Agua/toxicidad , Embrión no Mamífero/efectos de los fármacos , Larva/efectos de los fármacos
7.
Polymers (Basel) ; 16(16)2024 Aug 10.
Artículo en Inglés | MEDLINE | ID: mdl-39204490

RESUMEN

The present work describes the synthesis of poly(butylene succinate) (PBSu)-cutin copolymers by the two-stage melt polycondensation method, esterification and polycondensation. Cutin was added in four different concentrations, 2.5, 5, 10, and 20 wt%, in respect to succinic acid. The obtained copolymers were studied using a variety of techniques such as Fourier transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), polarized light microscopy (PLM), as well as diffuse reflectance spectroscopy (DRS). A series of results, in agreement between different techniques, revealed the formation of PBSu-cutin interactions, confirming indirectly the successful in situ synthetic route of copolymers. DSC and XRD combined with PLM results provided indications that the crystallization temperature increases with the addition of small amounts of cutin and gradually decreases with increasing concentration. The crystallization process was easier and faster at 2.5%, 5%, and 10% concentrations, whereas at 20%, it was comparable to neat PBSu. The presence of cutin, in general, leads to the facilitated crystallizability of PBSu (direct effect), whereas a moderate drop in the glass transition temperature is recorded, the latter being an indirect effect of cutin via crystallization. The thermal stability improved in the copolymers compared to neat PBSu. Water contact angle measurements confirmed that the addition of cutin decreased the hydrophilicity. The local and segmental relaxation mapping is demonstrated for PBSu/cutin here for the first time. Enzymatic hydrolysis and soil degradation tests showed that, overall, cutin accelerated the decomposition of the polymers. The copolymers may be proven useful in several applications.

8.
Polymers (Basel) ; 16(16)2024 Aug 11.
Artículo en Inglés | MEDLINE | ID: mdl-39204500

RESUMEN

Amid the rapid development of modern society, the widespread use of plastic products has led to significant environmental issues, including the accumulation of non-degradable waste and extensive consumption of non-renewable resources. Developing healable, recyclable, bio-based materials from abundant renewable resources using diverse dynamic interactions attracts increasing global attention. However, achieving a good balance between the self-healing capacity and mechanical performance, such as strength and toughness, remains challenging. In our study, we address this challenge by developing a new type of dynamic network from epoxidized soybean oil (ESO) and poly(butylene adipate-co-terephthalate) (PBAT) with good strength and toughness. For the synthetic strategy, a thiol-epoxy click reaction was conducted to functionalize ESO with thiol and hydroxyl groups. Subsequently, a curing reaction with isocyanates generated dynamic thiourethane and urethane bonds with different bonding energies in the dynamic networks to reach a trade-off between dynamic features and mechanical properties; amongst these, the thiourethane bonds with a lower bonding energy provide good dynamic features, while the urethane bonds with a higher bonding energy ensure good mechanical properties. The incorporation of flexible PBAT segments to form the rational multi-phase structure with crystalline domains further enhanced the products. A typical sample, OTSO100-PBAT100, exhibited a tensile strength of 33.2 MPa and an elongation at break of 1238%, demonstrating good healing capacity and desirable mechanical performance. This study provides a promising solution to contemporary environmental and energy challenges by developing materials that combine mechanical and repair properties. It addresses the specific gap of achieving a trade-off between tensile strength and elongation at break in bio-based self-healing materials, promising a wide range of applications.

9.
Polymers (Basel) ; 16(16)2024 Aug 16.
Artículo en Inglés | MEDLINE | ID: mdl-39204545

RESUMEN

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is a very promising biodegradable copolyester of high interest in food packaging. Its inherent brittleness and narrow processing window make it necessary to blend it with flexible biopolyesters, such as poly(butylene succinate-co-adipate) (PBSA). However, the resultant biopolyester blends are thermodynamically immiscible, which impairs their performance and limits their applications. This study is the first to explore the use of poly(butylene succinate-co-adipate) grafted with maleic anhydride (PBS-g-MAH) as a novel reactive additive to compatibilize PHBV/PBSA blends. The compatibilizer was prepared by a reactive melt-mixing process of PBSA and maleic anhydride (MAH) using dicumyl peroxide (DCP) as an organic radical initiator, achieving a grafting degree (Gd) of 5.4%. Biopolyester blend films were thereafter prepared via cast extrusion and their morphological, thermal, mechanical, and barrier properties were characterized. Compatibilization by PBSA-g-MAH was confirmed by observing an improved phase interaction and lower dispersed domain sizes in the blends with 15 wt% PBSA. These compatibilized PHBV/PBSA blends were thermally stable up to 285 °C, showed enhanced ductility and toughness, as well as providing an improved barrier against water and limonene vapors and oxygen. These findings suggest that the use of MAH-grafted biopolyesters can represent an effective strategy to improve the properties of biopolyester blends and open up new opportunities for the application of PHBV-based formulations for food packaging.

10.
J Biomed Mater Res B Appl Biomater ; 112(9): e35464, 2024 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-39194038

RESUMEN

Injectable cell therapies offer several advantages compared with traditional open surgery, including less trauma to the patient, shorter recovery time, and lower risk of infection. However, a significant problem is the difficulty in developing effective cell delivery carriers that are cyto-compatible and maintain cell viability both during and after injection. In the presented study, it was aimed to develop poly(butylene adipate-co-terephthalate) (PBAT) microcarriers using the emulsion preparation-solvent evaporation technique. The optimized diameter of the PBAT microcarriers was determined as 104 ± 15 µm at 700 rpm and there would be no blockage after injection due to the nonswelling feature of microcarriers. Furthermore, the cellular activities of PBAT microcarriers were evaluated in static culture for 7 days using L929 mouse fibroblasts, MC3T3-E1 mouse pre-osteoblasts, and rat adipose-derived mesenchymal cells (AdMSCs). 3-[4,5-Dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide results and Sscanning electron microscope images showed that PBAT microcarriers increased the adhesion and proliferation properties of pre-osteoblasts and stem cells, while L929 fibroblasts formed aggregates by adhering to certain regions of the microcarrier surface and did not spread on the surface. These results emphasize that PBAT microcarriers can be used as injectable carriers, especially in stem cell therapies, but their surface properties need to be modified for some cells.


Asunto(s)
Poliésteres , Animales , Ratones , Poliésteres/química , Ratas , Fibroblastos/metabolismo , Fibroblastos/citología , Línea Celular , Células Madre Mesenquimatosas/citología , Células Madre Mesenquimatosas/metabolismo , Osteoblastos/metabolismo , Osteoblastos/citología , Propiedades de Superficie , Proliferación Celular/efectos de los fármacos , Células 3T3 , Técnicas de Cultivo de Célula , Adhesión Celular/efectos de los fármacos
11.
Int J Biol Macromol ; 277(Pt 3): 134505, 2024 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-39106933

RESUMEN

In this work, the modification of poly(butylene adipate-co-terephthalate) (PBAT) was combined with the development of active packaging films. PBAT, starch, plasticizer, and tea polyphenols (TP) were compounded and extrusion-blown into thermoplastic starch (TPS)/PBAT-TP active films. Effects of TPS contents on physicochemical properties, functional activities, biodegradability, and release kinetics of PBAT-based active films were explored. Starch interacted strongly with TP through hydrogen bonding and induced the formation of heterogeneous structures in the films. With the increase in TPS contents, surface hydrophilicity and water vapor permeability of the films increased, while mechanical properties decreased. Blending starch with PBAT greatly accelerated degradation behavior of the films, and the T30P70-TP film achieved complete degradation after 180 days. As TPS contents increased, swelling degree of the films increased and TP release were improved accordingly, resulting in significantly enhanced antioxidant and antimicrobial activities. This work demonstrated that filling starch into PBAT-based active films could achieve different antioxidant and antimicrobial activities of the films by regulating film swelling and release behavior.


Asunto(s)
Plásticos Biodegradables , Embalaje de Alimentos , Poliésteres , Polifenoles , Almidón , Poliésteres/química , Almidón/química , Plásticos Biodegradables/química , Polifenoles/química , Camellia sinensis/química , Biodegradación Ambiental , Antioxidantes/química , Antiinfecciosos/química , Interacciones Hidrofóbicas e Hidrofílicas
12.
Polymers (Basel) ; 16(14)2024 Jul 10.
Artículo en Inglés | MEDLINE | ID: mdl-39065288

RESUMEN

In this study, a twin-screw extruder was used to fabricate poly(lactic acid) (PLA)/poly(butylene adipate-co-terephthalate) (PBAT) blends and blend-based nanocomposites with carbon nanotube (CNT) or nanocarbon black (CB) as nanofillers. The fabricated samples were subsequently treated with supercritical carbon dioxide (scCO2) to fabricate the corresponding foams. Bi-phasic morphology and selective distribution of CNTs or CBs in the PBAT phase were observed in the blends/composites through scanning electron microscopy. After the scCO2 treatment, the selective foaming of the PBAT phase in the prepared blends/composites was confirmed. The cellular structure of PBAT phase in scCO2-treated blends is similar to the size/shape of PBAT domains in untreated blends or treated neat PBAT foam. The addition of CNTs or CBs in the blends led to a slight reduction in cell size of the foamed PBAT phase, demonstrating CNT/CB-induced cell nucleation. Differential scanning calorimetry (DSC) results showed that CNTs and CBs played as nucleating agents and increased the initial crystallization temperature up to 14 °C compared with neat PBAT for PBAT in different composites during cooling. The scCO2 treatment induced the bimodal stability of PBAT crystals in different samples, which melted mainly in two temperature regions in DSC studies. Thermogravimetric analyses revealed that compared with parent blends, the addition of CNTs or CBs increased the temperature at 80 wt.% loss (degradation of PBAT portion) up to 6 °C. The electrical resistivity decreased by more than six orders of magnitude for certain CNT- or CB-added composites compared with the parent blends. The hardness of the blends slightly increased after forming the corresponding composites and then declined after the scCO2 treatment.

13.
Int J Biol Macromol ; 276(Pt 1): 133786, 2024 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-38992551

RESUMEN

The poor interfacial compatibility of natural fiber-reinforced polymer composites has become a major challenge in the development of industry-standard high-performance composites. To solve this problem, this study constructs a novel rigid-flexible balanced molecular crosslinked network transition interface in composites. The interface improves the interfacial compatibility of the composites by balancing the stiffness and strength of the fibers and the matrix, effectively improving the properties of the composites. The flexural strength and flexural modulus of the composites were enhanced by 38 % and 44 %, respectively. Water absorption decreased by 30 %. The initial and maximum thermal degradation temperatures increased by 20 °C and 16 °C, respectively. The maximum storage modulus increased by 316 %. Furthermore, the impact toughness was elevated by 41 %, attributed to the crosslinked network's efficacy in absorbing and dissipating externally applied energy. This innovative approach introduces a new theory of interfacial reinforcement compatibility, advancing the development of high-performance and sustainable biocomposites.


Asunto(s)
Materiales Biocompatibles , Materiales Biocompatibles/química , Butadienos/química , Ensayo de Materiales , Reactivos de Enlaces Cruzados/química , Sasa/química , Polímeros/química , Temperatura , Agua/química , Adipatos/química , Resistencia a la Tracción
14.
ACS Appl Mater Interfaces ; 16(31): 41461-41474, 2024 Aug 07.
Artículo en Inglés | MEDLINE | ID: mdl-39049199

RESUMEN

The demand for underwater pressure sensitive adhesives (PSAs) is rapidly increasing in fields such as underwater engineering and biomedicine. However, the achievement of underwater adhesion of PSAs remains a challenge because of the hydration layer that hinders the interaction between the adhesive and the substrate. Herein, a new type of underwater PSA was synthesized by the copolymerization of hydrophobic unsaturated poly(1,2-butylene oxide) (UPBO) and hydrophilic itaconic acid monomers using solvent-free ultraviolet curing. The PSA has demonstrated substrate-independent underwater adhesion strengths ranging from 108 to 141 kPa on both hydrophilic (glass, wood, steel) and hydrophobic (PET, PMMA, PTFE) substrates. The underwater adhesion performance of PSA remains stable during 30 adhesion-detachment cycles and incubation in water for 20 days. Notably, PSA shows cytocompatibility, antimicrobial, and degradable properties and can be used for rapid hemostasis of skin wounds. Experimental characterizations confirm that the process of underwater adhesion is achieved by hydrophobic alkyl side chains of the PBO chain segments, which repel water at the adhesive-substrate interface. This study should provide both practical and facile design strategies for multifunctional underwater PSAs that can be used in a variety of applications.

15.
J Mol Model ; 30(8): 293, 2024 Jul 30.
Artículo en Inglés | MEDLINE | ID: mdl-39080083

RESUMEN

CONTEXT: Thermoplastic elastomer styrene-ethylene-butylene-styrene block copolymer (SEBS) has excellent mechanical properties and aging resistance, so it has good application prospects in thermoplastic solid propellants. The selection of plasticizer is one of the keys to the formulation design of thermoplastic solid propellant. The compatibility of the plasticizer with the polymer determines the plasticizer's ability to plasticize the polymer's molecular chain segments. Herein, the compatibility of four plasticizers with SEBS was investigated, and the results declared that the order of compatibility between SEBS and the four plasticizers is SEBS/WO > SEBS/DOS > SEBS/DEP > SEBS/TA. METHODS: Physical compatibility of SEBS binder with plasticizer triacetin (TA), diethyl phthalate (DEP), dioctyl sebacate (DOS), and 26# industrial white oil (WO) was simulated using molecular dynamics (MD) method via Materials Studio 8.0, and the simulation results were verified experimentally. The results showed that the compatibility of SEBS with these plasticizers can be comprehensively evaluated by analyzing solubility parameters, radial distribution functions, and blend miscibility simulations.

16.
Carbohydr Polym ; 339: 122240, 2024 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-38823910

RESUMEN

Creating multiple-reusable PBAT/TPS (PT) films presents a novel solution to reduce carbon emissions from disposable packaging, addressing challenges like the high creep of PBAT and the glycerol migration of TPS. Consequently, adopting reactive extrusion to fabricate reversible cross-linking TPS with high shape memory performance, low migration, and homogeneous dispersion in PBAT matrix was a fascinating strategy. Herein, starch, glycerol and CaCl2 (calcium chloride) were extruded to fabricate TPS-Ca with Ca2+ heterodentate coordination structure and confirmed by XPS, 1H NMR and temperature-dependent FTIR. The results of DMA, dynamic rheology, flow activation energy and SEM revealed that TPS-Ca exhibited significant temperature-sensitive reversible properties and robust melt flow capability, enabling micro-nano scale dispersion in PBAT. Noteworthy, PBAT/TPS-Ca (PT-Ca) would recover 100 % length within 20 s by microwave heating after being loaded under the hygrothermal environment. Meanwhile, the migration weight of glycerol decreased from 2.5 % to 1.2 % for the heat-moisture-treated PBAT/TPS (HPT) and PBAT/TPS-Ca (HPTCa). Remarkably, the tensile strength and elongation at the break of HPT-Ca increased to 20.0 MPa and 924 %, respectively, due to reduced stress concentration sites in the phase interface. In summary, our study provides a streamlined strategy for fabricating multiple-reusable PT, offering a sustainable solution to eliminate carbon emissions linked to disposable plastic.

17.
Heliyon ; 10(11): e31789, 2024 Jun 15.
Artículo en Inglés | MEDLINE | ID: mdl-38868060

RESUMEN

Perforation of the tympanic membrane (TM) is a common condition that often requires a scaffold as a support for surgery. However, because of the external environment of the auditory canal, the scaffold could become bacterially infected and prevent the TM from healing. As a result, the perfect scaffold should have both antibacterial and biomimetic qualities. In this study, the biodegradable biomaterial poly(1,4-butylene carbonate) (PBC) films containing levofloxacin (LEV) was successfully prepared for the first time. The results showed that the hydrophilicity of the LEV/PBC film was improved after the addition of LEV, and the tensile strength was also complied with the requirements of the standard. The created antibacterial film demonstrated excellent antibacterial properties. In vitro hemolysis experiments revealed no risk of hemolysis for the new material, and the cytotoxicity study further confirmed its non-cytotoxic nature. Overall, LEV was a good component of PBC/LEV film, which is expected to be used for TM repair in the future.

18.
Food Chem Toxicol ; 190: 114808, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38852758

RESUMEN

The chemical safety of poly (butylene adipate-co-terephthalate) (PBAT) based food contact articles (FCAs) has aroused increasing toxicological concerns in recent years, but the chemical characterization and associated risk assessment still remain inadequate as it fails to elucidate the distribution pattern and discern the potential genotoxic and carcinogenic hazards of the identified substances. Herein, the volatile organic compounds (VOCs) in 50 batches of PBAT-based FCAs of representative categories and 10 batches of PLA and PBAT pellets were characterized, by which 237 VOCs of 10 chemical categories were identified and exhibited characteristic distribution patterns in the chemical spaces derived from their molecular descriptors. Chemical hazards associated with the identified VOCs were discerned by a hazard-driven classification scheme integrating hazard-related knowledge from multiple publicly available sources, and 34 VOCs were found to bear genotoxic or carcinogenic hazards and to feature higher average molecular weight than the other VOCs. Finally, the Risk and hazard quotient (HQ) calculated as the metrics of risk suggested that all identified VOCs posed acceptable risks (Risk<10-4 or HQ < 1), whereas oxolane, butyrolactone, N,N-dimethylacetamide, 2-butoxyethanol, benzyl alcohol, and 1,2,3-trichloropropane posed non-negligible (Risk>10-6) genotoxic or carcinogenic risk and thus should be of prioritized concern to promote the chemical safety of PBAT-based FCAs.


Asunto(s)
Embalaje de Alimentos , Poliésteres , Compuestos Orgánicos Volátiles , Compuestos Orgánicos Volátiles/toxicidad , Compuestos Orgánicos Volátiles/química , Compuestos Orgánicos Volátiles/análisis , Medición de Riesgo/métodos , Poliésteres/química , Poliésteres/toxicidad , Humanos
19.
J Hazard Mater ; 474: 134797, 2024 Aug 05.
Artículo en Inglés | MEDLINE | ID: mdl-38865921

RESUMEN

Poly(butylene adipate-co-terephthalate) (PBAT) is widely utilized in the production of food packaging and mulch films. Its extensive application has contributed significantly to global solid waste, posing numerous environmental challenges. Recently, enzymatic recycling has emerged as a promising eco-friendly solution for the management of plastic waste. Here, we systematically investigate the depolymerization mechanism of PBAT catalyzed by cutinase TfCutSI with molecular docking, molecular dynamics simulations, and quantum mechanics/molecular mechanics calculations. Although the binding affinities for acid ester and terephthalic acid ester bonds are similar, a regioselective depolymerization mechanism and a "chain-length" effect on regioselectivity were proposed and evidenced. The regioselectivity is highly associated with specific structural parameters, namely Substrate@O4-Met@H7 and Substrate@C1-Ser@O1 distances. Notably, the binding mode of BTa captured by X-ray crystallography does not facilitate subsequent depolymerization. Instead, a previously unanticipated binding mode, predicted through computational analysis, is confirmed to play a crucial role in BTa depolymerization. This finding proves the critical role of computational modelling in refining experimental results. Furthermore, our results revealed that both the hydrogen bond network and enzyme's intrinsic electric field are instrumental in the formation of the final product. In summary, these novel molecular insights into the PBAT depolymerization mechanism offer a fundamental basis for enzyme engineering to enhance industrial plastic recycling.


Asunto(s)
Simulación del Acoplamiento Molecular , Poliésteres , Polimerizacion , Poliésteres/química , Poliésteres/metabolismo , Simulación de Dinámica Molecular , Ácidos Ftálicos/química , Ácidos Ftálicos/metabolismo , Estereoisomerismo , Hidrolasas de Éster Carboxílico
20.
Macromol Rapid Commun ; : e2400273, 2024 Jun 14.
Artículo en Inglés | MEDLINE | ID: mdl-38876477

RESUMEN

Poly(butylene succinate) (PBS) forms small and imperfect crystals of low melting temperature at high supercooling of the melt. Slow heating allows reorganization of the obtained semicrystalline structure with the changes of the crystallinity and of the size and perfection of crystals analyzed by differential scanning calorimetry (DSC) and temperature-resolved X-ray scattering techniques. Crystals generated at 20 °C begin to melt and reorganize at a few K higher temperature with their initial imperfection and thickness unchanged upon heating to 70-80 °C. Slow heating to temperatures higher than 70-80 °C yields a distinct exothermic peak in the DSC scan, paralleled by detection of crystals of larger size/higher perfection, beginning to melt at ≈100 °C. These observations suggest that below 70-80 °C, reorganization of the semicrystalline morphology is constrained such that only minor and local improvement of the structure of crystals are possible. The formation of both perfect and thicker crystal lamellae at higher temperature proceeds via melting of imperfect crystals followed by melt-recrystallization as for PBS solid-state thickening is impossible. The study shows the limit of low-temperature reorganization processes when not involving both complete melting of crystals and rearrangement of the lamellar-stack structure.

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