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This work is a contribution to the thermal characterization of a selected binary system of two di-n-alkyl adipates that can be used as phase change material for thermal energy storage at low temperatures. The construction of the solid–liquid phase diagram using differential scanning calorimetry (DSC), complemented with Raman Spectroscopy studies for the system composed by diethyl and dibutyl adipates is presented. The solidus and liquidus equilibrium temperatures were determined by DSC for the pure components and 30 binary mixtures at selected molar compositions were used to construct the corresponding solid–liquid phase diagram. The binary system of diethyl and dibutyl adipates presents eutectic behaviour at low temperatures. The eutectic temperature was found at 240.46 K, and the eutectic composition was determined to occur at the molar fraction xdibutyl = 0.46. Additionally, the system shows a polymorphic transition, characteristic of dibutyl adipate, occurring at ca. 238 K, confirmed by optical microscopy. To the best of our knowledge, no reference to the phase diagram of the present system could be found in the literature. Raman spectroscopy was essential to complement the construction of the phase equilibrium diagram, enabling the identification of the solid and liquid phases of the system. Finally, the liquidus curve of the phase diagram was also successfully predicted using a suitable fitting equation, being the root mean square deviation of the data from the correlation equal to 0.54 K. In addition, this fitting operation enabled a correct prediction of the eutectic composition of the system. [ABSTRACT FROM AUTHOR]

[Display omitted] • A new GC–MS method was proposed for determining nine plasticizers in bee pollen. • Sample treatment consists of a modified QuEChERS (acetonitrile and EMR-lipid). • Good recovery percentages have been achieved for all the compounds (77 %–104 %). • The LOQs were lower than the SMLs established by current legislation. • Residues of five plasticizers were detected in some of the analyzed samples. The determination of plasticizers in bee pollen may be important not only to evaluate the contamination of the hive environment, but also to verify the safety for consumers of this food supplement, since to date it has not been studied. Therefore, a new analytical methodology for the determination of nine plasticizers (phthalate esters: di-(2-ethylhexyl) phthalate, dibutyl phthalate, dimethyl phthalate, diethyl phthalate, benzyl butyl phthalate, and di- n -octyl phthalate; diphenyl ethers: 4-bromodiphenyl ether and 4-chlorodiphenyl ether; adipate: bis(2-ethylhexyl) adipate) in bee pollen using gas chromatography-mass spectrometry was developed. An efficient sample treatment (modified QuEChERS, quick, easy, cheap, effective, rugged & safe) is proposed (with average analyte recoveries between 77 % and 104 %) involving extraction with acetonitrile followed by a dispersive solid phase extraction (enhanced matrix removal lipid sorbent). Chromatographic analysis (<21 min) was performed in an Agilent HP-5MS column under programmed temperature conditions, and analyses were performed in selected ion monitoring mode. The method was validated in terms of selectivity, limits of detection (0.2–17.2 μg kg−1) and quantification (0.5–57.5 μg kg−1), linearity, matrix effect, trueness, and precision (relative standard deviation < 15 %). Finally, an analysis of thirty samples from different sources (commercial or experimental apiaries) revealed the presence of residues of five plasticizers in all samples. Quantification was possible in several cases, with overall concentrations ranging from 0.056 to 3.152 mg kg−1. This study not only reports for the first time the presence of some plasticizers in bee pollen, but also corroborates the usefulness of bee pollen as bioindicator of environmental contamination. [ABSTRACT FROM AUTHOR]

Understanding impacts of secondary organic aerosol (SOA) in air requires a molecular-level understanding of particle growth via interactions between gases and particle surfaces. The interactions of three gaseous organic nitrates with selected organic substrates were measured at 296 K using attenuated total reflection Fourier transform infrared spectroscopy. The organic substrates included a long chain alkane (triacontane, TC), a keto-acid (pinonic acid, PA), an amorphous ester oligomer (poly(ethylene adipate) di-hydroxy terminated, PEA), and laboratory-generated SOA from α-pinene ozonolysis. There was no uptake of the organic nitrates on the non-polar TC substrate, but significant uptake occurred on PEA, PA, and α-pinene SOA. Net uptake coefficients (γ) at the shortest reaction times accessible in these experiments ranged from 3 × 10-4 to 9 × 10-6 and partition coefficients (K) from 1 × 107 to 9 × 104. Trends in γ did not quantitatively follow trends in K, suggesting that the intermolecular forces involved in gas-surface interactions are not the same as those in the bulk, which is supported by theoretical calculations. Kinetic modeling showed that nitrates diffused throughout the organic films over several minutes, and that the bulk diffusion coefficients evolved as uptake/desorption occurred. A plasticizing effect occurred upon incorporation of the organic nitrates, whereas desorption caused decreases in diffusion coefficients in the upper layers, suggesting a crusting effect. Accurate predictions of particle growth in the atmosphere will require knowledge of uptake coefficients, which are likely to be several orders of magnitude less than one, and of the intermolecular interactions of gases with particle surfaces as well as with the particle bulk.

The development of a system for the operationally simple, scalable conversion of polyhydroxylated biomass into industrially relevant feedstock chemicals is described. This system includes a bimetallic Pd/Re catalyst in combination with hydrogen gas as a terminal reductant and enables the high-yielding reduction of sugar acids. This procedure has been applied to the synthesis of adipate esters, precursors for the production of Nylon-6,6, in excellent yield from biomass-derived sources.

Polyketides have enormous structural diversity, yet polyketide synthases (PKSs) have thus far been engineered to produce only drug candidates or derivatives thereof. Thousands of other molecules, including commodity and specialty chemicals, could be synthesized using PKSs if composing hybrid PKSs from well-characterized parts derived from natural PKSs was more efficient. Here, using modern mass spectrometry techniques as an essential part of the design-build-test cycle, we engineered a chimeric PKS to enable production one of the most widely used commodity chemicals, adipic acid. To accomplish this, we introduced heterologous reductive domains from various PKS clusters into the borrelidin PKS' first extension module, which we previously showed produces a 3-hydroxy-adipoyl intermediate when coincubated with the loading module and a succinyl-CoA starter unit. Acyl-ACP intermediate analysis revealed an unexpected bottleneck at the dehydration step, which was overcome by introduction of a carboxyacyl-processing dehydratase domain. Appending a thioesterase to the hybrid PKS enabled the production of free adipic acid. Using acyl-intermediate based techniques to "debug" PKSs as described here, it should one day be possible to engineer chimeric PKSs to produce a variety of existing commodity and specialty chemicals, as well as thousands of chemicals that are difficult to produce from petroleum feedstocks using traditional synthetic chemistry.

The dicarbonylation of 1,3‐butadiene to adipic acid derivatives offers the potential for a more cost‐efficient and environmentally benign industrial process. However, the complex reaction network of regioisomeric carbonylation and isomerization pathways, make a selective and direct transformation particularly difficult. Here, we report surprising solvent effects on this palladium‐catalysed process in the presence of 1,2‐bis‐di‐tert‐butylphosphin‐oxylene (dtbpx) ligands, which allow adipate diester formation from 1,3‐butadiene, carbon monoxide, and methanol with 97 % selectivity and 100 % atom‐economy under scalable conditions. Under optimal conditions a variety of di‐ and triesters from 1,2‐ and 1,3‐dienes can be obtained in good to excellent yields. [ABSTRACT FROM AUTHOR]

The stereospecificity of d-glucarate dehydratase (GlucD) is explored by QM/MM calculations. Both the substrate binding and the chemical steps of GlucD contribute to substrate specificity. Although the identification of transition states remains computationally intensive, we suggest that QM/MM computations on ground states or intermediates can capture aspects of specificity that cannot be obtained using docking or molecular mechanics methods.

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Elastomeric biocomposites based on poly(glycerol adipate urethane) and hydroxyapatite were fabricated for tissue regeneration. The poly(glycerol adipate urethane) (PGAU) elastomeric composite matrices were obtained by chemical crosslinking of the poly(glycerol adipate) prepolymer (pPGA) with diisocyanate derivative of L-lysine. Two series of composites varying in the amount of L-lysine diisocyanate ethyl ester (LDI) used as a crosslinking agent were manufactured. As a ceramic filler both unmodified and L-lysine surface-modified hydroxyapatite (HAP) particles were used. The novelty of our research consists in the manufactured elastomeric materials and characterization of their linear viscoelastic (LVE) properties. The LVE properties of the composites were investigated by means of dynamic thermomechanical analysis. Frequency sweep and amplitude sweep measurements were performed in shear mode. The influence of the crosslinking agent (LDI) amount, HAP content and surface modification of HAP on the LVE properties of the composites was determined based on the analysis of the master curves of storage (G') and loss (G″) moduli and of tanδ of the composites. Depending on the amount of LDI, HAP and surface modification, the materials differ in the values of rubber elasticity plateau modulus (G 0 ) and G' and G″ determined at selected shear frequencies and at the glassy state. G 0 ranges from 278 kPa to 3.98 MPa, G' in the glassy state is within the range of 219 MPa-459 MPa. The G 0 values of the PGAU-based composites are within the stiffness range of soft tissue. In view of the choice of HAP as the ceramic component and the G 0 values, elastomeric composites have the potential to be used as filling materials in small bone defects (due to their mechanical similarity to osteoid) as well as materials for cartilage tissue regeneration., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The exploitation of exciting features of plastics for diverse applications has resulted in significant plastic waste generation, which negatively impacts environmental compartments, metabolic processes, and the well-being of aquatic ecosystems biota. A shotgun metagenomic approach was deployed to investigate the microbial consortia, degradation pathways, and enzyme systems involved in the degradation of plastics in a tropical lentic pond sediment (APS). Functional annotation of the APS proteome (ORFs) using the PlasticDB database revealed annotation of 1015 proteins of enzymes such as depolymerase, esterase, lipase, hydrolase, nitrobenzylesterase, chitinase, carboxylesterase, polyesterase, oxidoreductase, polyamidase, PETase, MHETase, laccase, alkane monooxygenase, among others involved in the depolymerization of the plastic polymers. It also revealed that polyethylene glycol (PEG), polyhydroxyalkanoates (PHA), polyhydroxybutyrate (PHB), polylactic acid (PLA), polybutylene adipate terephthalate (PBAT), polyethylene terephthalate (PET), and nylon have the highest number of annotated enzymes. Further annotation using the KEGG GhostKOALA revealed that except for terephthalate, all the other degradation products of the plastic polymers depolymerization such as glyoxylate, adipate, succinate, 1,4-butanediol, ethylene glycol, lactate, and acetaldehyde were further metabolized to intermediates of the tricarboxylic acid cycle. Taxonomic characterization of the annotated proteins using the AAI Profiler and BLASTP revealed that Pseudomonadota members dominate most plastic types, followed by Actinomycetota and Acidobacteriota. The study reveals novel plastic degraders from diverse phyla hitherto not reported to be involved in plastic degradation. This suggests that plastic pollution in aquatic environments is prevalent with well-adapted degrading communities and could be the silver lining in mitigating the impacts of plastic pollution in aquatic environments., (© 2024. The Author(s), under exclusive licence to Springer Nature B.V.)

Biodegradable mulches are widely recognized as ecologically friendly substances. However, their degradation percentage upon entering soils may vary based on mulch type and soil microbial activities, raising concerns about potential increases in microplastics (MPs). The effects of using different types of mulch on soil carbon pools and its potential to accelerate their depletion have not yet well understood. Therefore, we conducted an 18-month experiment to investigate mulch biodegradation and its effects on CO 2 emissions. The experiment included burying soil with biodegradable mulch made of polylactic acid (PLA) and polybutylene adipate terephthalate (PBAT), and control treatments with traditional mulch (PE) and no mulch (CK). The results indicated that PE did not degrade, and the degradation percentage of PLA and PBAT were 46.2% and 88.1%, and the MPs produced by the degradation were 6.7 × 10 4 and 37.2 × 10 4 items/m 2 , respectively. Biodegradable mulch, particularly PLA, can enhance soil microbial diversity and foster more intricate bacterial communities compared to PE. The CO 2 emissions were 0.58, 0.74, 0.99, and 0.86 g C/kg in CK , PE , PLA, , PBAT, respectively. A positive correlation was observed between microbial abundance and diversity with CO 2 emissions, while a negative correlation was observed with soil total organic carbon. Biodegradable mulch enhanced the transformation of soil organic C into CO 2 by stimulating microbial activity., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Active packaging relies on controlled release of antimicrobials for food protection; however, uncontrolled migration due to environmental factors poses safety and functionality challenges. This study investigated the stability of zinc oxide nanoparticle (ZnONP) in poly(butylene-adipate-co-terephthalate)/thermoplastic starch (PBAT/TPS) biopolymer film for active food packaging applications. While incorporating ZnONP significantly enhanced the properties and active functionalities (UV-light blocking, antimicrobial activity) of PBAT/TPS film, food simulants posed significant stability challenges. Notably, exposure to 3 % acetic acid (acidic food simulant) triggered complete detachment and dissolution of ZnONPs from the film surface, leading to pore formation and subsequent internal ZnO dissolution. This resulted in dramatic alterations to the bionanocomposite films, including increased opacity, water vapor permeability, and decreased thermal stability, mechanical properties, and active functionalities. In contrast, 10 % ethanol (aqueous food simulant) had minimal impact, suggesting higher ZnO stability in neutral environments. Importantly, ZnO migration analysis revealed thresholds for safe application: 1 % ZnONP for acidic food contact and up to 5 % for aqueous foodstuffs. These findings highlight the critical role of environmental factors in ZnONP stability and emphasize the need for strategic optimization of ZnO content for achieving both functionality and safety in active biopolymer packaging., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Microbial biodegradation of commercially available poly(butylene adipate-co-terephthalate)-polylactic acid-thermoplastic starch based bio-plastic has been pursued at high temperatures exceeding 55 °C. Herein, we first reported three newly isolated fungal strains from farmland soil samples of Republic of Korea namely, Pyrenochaetopsis sp. strain K2, Staphylotrichum sp. S2-1, and Humicola sp. strain S2-3 were capable of degrading a commercial bio-plastic film with degradation rates of 9.5, 8.6, and 12.2%, respectively after 3 months incubation at ambient conditions. Scanning electron microscopy (SEM) analyses showed that bio-plastic film was extensively fragmented with severe cracking on the surface structure after incubation with isolated fungal strains. X-ray diffraction (XRD) analysis also revealed that high crystallinity of the commercial bio-plastic film was significantly decreased after degradation by fungal strains. Liquid chromatography-mass spectrometry (LC-MS) analyses of the fungal culture supernatants containing the bio-plastic film showed the peaks for adipic acid, terephthalic acid (TPA), and terephthalate-butylene (TB) as major metabolites, suggesting cleavage of ester bonds and accumulation of TPA. Furthermore, a consortium of fungal strain K2 with TPA degrading bacterium Pigmentiphaga sp. strain P3-2 isolated from the same sampling site exhibited faster degradation rate of the bio-plastic film within 1 month of incubation with achieving complete biodegradation of accumulated TPA. We assume that the extracellular lipase activity presented in the fungal cultures could hydrolyze the ester bonds of PBAT component of bio-plastic film. Taken together, the fungal and bacterial consortium investigated herein could be beneficial for efficient biodegradation of the commercial bio-plastic film at ambient conditions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Green polymeric foams are an important research topic for sustainable development. In this study, a natural multifunctional flame-retardant additive based on food waste was developed and evaluated for its ability to replace the commercial additives tricresyl phosphate (TCP) and trioctyl phosphate (TOP) in a polylactide/poly(butylene adipate-co-terephthalate) (PLA/PBAT) foam. A series of blend foams with additives were prepared by melt extrusion. According to the results, the blend foam with 20 phr of TCP showed the best combination of impact toughness and flame retardancy. TCP, however, poses health and environmental risks. Therefore, natural flame retardants (NFRs) were used to partially replace the commercial flame retardant (CFR). A combination of TCP and soybean residue (SB) produced an impact toughened and flame-retardant blend foam. When compared to the neat PLA/PBAT foam, the impact toughness of the best sample was increased by about 256 %. The optimal foam showed excellent flame resistance with a V-0 UL-94 rating and a high LOI value (31.8 %). SB has the potential to partially replace TCP as flame retardant and could be used in a broad range of PLA/PBAT foam applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Despite the success of polyethylene glycol-based (PEGylated) polyesters in the drug delivery and biomedical fields, concerns have arisen regarding PEG's immunogenicity and limited biodegradability. In addition, inherent limitations, including limited chemical handles as well as highly hydrophobic nature, can restrict their effectiveness in physiological conditions of the polyester counterpart. To address these matters, an increasing amount of research has been focused towards identifying alternatives to PEG. One promising strategy involves the use of bio-derived polyols, such as glycerol. In particular, glycerol is a hydrophilic, non-toxic, untapped waste resource and as other polyols, can be incorporated into polyesters via enzymatic catalysis routes. In the present study, a systematic screening is conducted focusing on the incorporation of 1,6-hexanediol (Hex) (hydrophobic diol) into both poly(glycerol adipate) (PGA) and poly(diglycerol adipate) (PDGA) at different (di)glycerol:hex ratios (30:70; 50:50 and 70:30 mol/mol) and its effect on purification upon NPs formation. By varying the amphiphilicity of the backbone, we demonstrated that minor adjustments influence the NPs formation, NPs stability, drug encapsulation, and degradation of these polymers, despite the high chemical similarity. Moreover, the best performing materials have shown good biocompatibility in both in vitro and in vivo (whole organism) tests. As preliminary result, the sample containing diglycerol and Hex in a 70:30 ratio, named as PDGA-Hex 30%, has shown to be the most promising candidate in this small library analysed. It demonstrated comparable stability to the glycerol-based samples in various media but exhibited superior encapsulation efficiency of a model hydrophobic dye. This in-depth investigation provides new insights into the design and modification of biodegradable (di)glycerol-based polyesters, potentially paving the way for more effective and sustainable PEG-free drug delivery nano-systems in the pharmaceutical and biomedical fields., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Blending poly (butylene adipate-co-terephthalate) (PBAT) and polylactic acid (PLA) is a cost-effective strategy to obtain biodegradable plastic with complementary properties. However, the incompatibility between PBAT and PLA is a great challenge for fabricating high-performance composite films. Herein, the ethyl acetate fractionated lignin with the small glass transition temperature and low molecular weight was achieved and incorporated into the PBAT/PLA composite as a compatibilizer. The fractionated lignin can be uniformly dispersed within the PBAT/PLA matrix through a melt blending process and interact with the molecular chain of PBAT and PLA as a bonding bridge, which enhances the intermolecular interactions and reduces the interfacial tension of PBAT/PLA. By adding fractionated lignin, the tensile strength of the PBAT/PLA composite increased by 35.4 % and the yield strength increased by 37.7 %. Owing to lignin, the composite films possessed the ultraviolet shielding function and exhibited better water vapor barrier properties (1.73 ± 0.08 × 10 -13  g·cm/cm 2 ·s·Pa). This work conclusively demonstrated that fractionated lignin can be used as a green compatibilizer and a low-cost functional filler for PBAT/PLA materials, and provides guidance for the application of lignin in biodegradable plastics., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Gut microbiota plays a vital role in obtaining nutrition from bamboo for giant pandas. However, low cellulase activity has been observed in the panda's gut. Besides, no specific pathway has been implicated in lignin digestion by gut microbiota of pandas. Therefore, the mechanism by which they obtain nutrients is still controversial. It is necessary to elucidate the precise pathways employed by gut microbiota of pandas to degrade lignin. Here, the metabolic pathways for lignin degradation in pandas were explored by comparing 209 metagenomic sequencing data from wild species with different feeding habits. Lignin degradation central pathways, including beta-ketoadipate and homogentisate pathway, were enriched in the gut of wild bamboo-eating pandas. The gut microbiome of wild bamboo-eating specialists was enriched with genes from pathways implicated in degrading ferulate and p -coumarate into acetyl-CoA and succinyl-CoA, which can potentially provide the raw materials for metabolism in pandas. Specifically, Pseudomonas , as the most dominant gut bacteria genus, was found to be the main bacteria to provide genes involved in lignin or lignin derivative degradation. Herein, three Pseudomonas -associated strains isolated from the feces of wild pandas showed the laccase, lignin peroxidase, and manganese peroxidase activity and extracellular lignin degradation ability in vitro . A potential mechanism for pandas to obtain nutrition from bamboo was proposed based on the results. This study provides novel insights into the adaptive evolution of pandas from the perspective of lignin metabolism., Importance: Although giant pandas only feed on bamboo, the mechanism of lignin digestion in pandas is unclear. Here, the metabolic pathways for lignin degradation in wild pandas were explored by comparing gut metagenomic from species with different feeding habits. Results showed that lignin degradation central pathways, including beta-ketoadipate and homogentisate pathway, were enriched in the gut of wild bamboo-eating pandas. Genes from pathways involved in degrading ferulate and p -coumarate via beta-ketoadipate pathway were also enriched in bamboo-eating pandas. The final products of the above process, such as acetyl-CoA, can potentially provide the raw materials for metabolism in pandas. Specifically, Pseudomonas , as the most dominant gut bacteria genus, mainly provides genes involved in lignin degradation. Herein, Pseudomonas -associated strains isolated from the feces of pandas could degrade extracellular lignin. These findings suggest that gut microbiome of pandas is crucial in obtaining nutrition from lignin via Pseudomonas , as the main lignin-degrading bacteria., Competing Interests: The authors declare no conflict of interest.

The preparation and characterization of lignin nanoparticles (LNPs) were described. LNPs were produced via the precipitation technique. Nanocomposites of LNPs with poly (butylene adipate-co-terephthalate) (PBAT) were prepared by melt mixing with various concentrations up to 6 wt% of LNPs. The assessment of the effects of LNP addition on the mechanical, thermal, morphological, cytotoxicity, antioxidant, antibacterial, and antiviral properties of nanocomposites was carefully performed. The addition of LNPs to PBAT enhances the thermal stability of the nanocomposites. The antioxidant effect of LNPs on PBAT increased with increasing filler content. LNPs showed higher efficiency as antioxidant agents than lignin particles (LP). The tensile modulus increased by 20 % for the nanocomposites with 6 % LNPs in comparison with neat PBAT. The crystallization peak temperature of PBAT was 80 °C, which increased to 104.6 °C with the addition of 6 wt% of LNPs, suggesting their strong nucleation activity. Antibacterial tests demonstrated the bacteriostatic activities of LNP, LP, and nanocomposites. Both LP and LNP showed considerable antiviral activity against herpes simplex virus type 1 and human coronavirus 229e. The antiviral activity of LNP was concentration-dependent. The findings suggest that LNP is a promising bio-additive for PBAT and can enhance its properties for various applications, including food packaging., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Microplastics from mulch films can be a source of chemical contamination to agricultural soils. In this context, biodegradable films have been widely positioned as a greener choice. However, their sorption/desorption capabilities, in contrast to the conventional plastic types remain understudied. It is for this reason that objective evaluation of their interactions with residual agricultural contaminants becomes important. Our findings reveal that polyethylene (PE) mulch films retained lower amounts of pesticide residues and demonstrated a higher desorption/release [median desorption = 71.86 μg/L or about 50%], while polybutylene adipate terephthalate (PBAT) mulch films retained higher amounts of pesticide residues onto their surface and demonstrated a much lower desorption [median desorption = 24.27 μg/L or about 17%] after a spraying event. A higher ambient temperature had no significant effect on final desorption amounts in both PE [median = 65.27 μg/L at 20 °C and 74.23 μg/L at 40 °C] and PBAT [median = 24.26 μg/L at 20 °C and 24.78 μg/L at 40 °C] mulch films. However, it did favour a faster desorption pace in PE films. Desorption in PBAT and PE plastic types was correlated with the log K ow value [Spearman's correlation: 0.857 and 0.837 respectively, p < 0.05]. However, only a moderate correlation with pKa was observed in PBAT [Spearman's correlation: 0.478, p < 0.05], while none for PE plastic type. Sorption of pesticides onto biodegradable PBAT microplastics were best explained by Elovich [R 2 : 0.937-0.959] and pseudo-second order kinetics [R 2 : 0.942-0.987], suggesting the presence of chemisorption. Furthermore, Weber Morris plots suggested the presence of a multi-step process and Boyd plots indicated that film diffusion or chemical bond formation was the rate-limiting step governing this phenomenon., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

How to effectively improve the poor interfacial adhesion between polylactic acid/poly(butylene adipate-co-terephthalate) (PLA/PBAT) matrix and thermoplastic starch (TPS) is still a challenge. Therefore, this work aims to introduce a convenient method to enhance the performance of PLA/PBAT/TPS blend by melt reactive extrusion. Here, using 4,4'-methylene-bis(N,N-diglycidyl-aniline) (MBDG) containing four epoxy groups as a reactive compatibilizer, and respectively using 1-methylimidazole (MI) or triethylenediamine (TD) as a catalyzer, serial PLA/PBAT/TPS ternary bio-composites are successfully prepared via melt reactive extrusion. The results showed that, under the catalysis of organic base, especially MI, the epoxy groups of MBDG can effectively react with hydroxyl and carboxyl groups of PLA/PBAT and hydroxyl groups in TPS to form chain-expanded and cross-linked structures. The tensile strength of the composites is increased by 20.0 % from 21.1 MPa, and the elongation at break is increased by 182.4 % from 17.6 % owing to the chain extension and the forming of cross-linked structures. The molecular weight, thermal stability, crystallinity, and surface hydrophobicity of the materials are gradually improved with the increase of MBDG content. The melt fluidity of the composites is also improved due to the enhancement of compatibility. The obtained PLA/PBAT/TPS materials have the potential to be green plastic products with good properties., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

The wide application of fully biodegradable polylactic acid/polybutylene terephthalate (PLA/PBAT) blends in environmentally friendly packaging were limited because of poor compatibility. Normal compatibilizers suffer from poor thermal stability and non-biodegradability. In this work, epoxy copolymer (MDOG) with different molecular structures were made of 2-methylene-1, 3-dioxoheptane, and glycidyl methacrylate as raw materials by free radical copolymerization. MDOG copolymers have good biodegradability and a high thermal decomposition temperature of 361 °C. The chemical reaction of the epoxy groups in MDOG with PLA and PBAT during the melting reaction improved the interfacial bonding by decreasing the particle size of PBAT. Compared to the PLA/PBAT blends, the tensile strength and fracture toughness of PLA/PBAT/MDOG blends were enhanced to 34.6 MPa and 115.8 MJ/m 3 , which are 25 % and 81 % higher, respectively. As a result, this work offers new methods for developing thermally stable and biodegradable compatibilizers, which will hopefully promote the development of packaging industry., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Developing biobased materials is a considerably effective approach to save fossil resources and reduce emissions. Biobased polyamide 56 (PA56) is an excellent engineering material, but it has low toughness. Herein, to enhance the toughness of PA56, an ultra-tough biodegradable material, i.e., poly (butylene adipate-co-terephthalate) (PBAT) was introduced into PA56. Moreover, a self-synthesized epoxy-terminated hyperbranched polyester (EHBP) was used to improve the compatibility of the blended materials. The results of differential scanning calorimetry and Fourier-transform infrared spectroscopy indicated that the epoxide group of EHBP could react with PA56 and PBAT to form a block-like polymer structure and limit the crystallization behavior of the blends. The scanning electron microscopy results show that the addition of EHBP considerably reduced the dispersed-phase size in the blends, forming a nanoscale island structure. Moreover, the hydrogen bonds formed between EHBP and PA56/PBAT enhanced the intermolecular interaction between the two materials. Thus, PA56 blends with ultrahigh toughness were successfully prepared. The prepared PA56/PBAT/EHBP blend exhibited a notch impact strength of 20.71 kJ/m 2 and a breaking elongation of 38.3 %, which represent increases of 427.3 % and 252.8 %, respectively, compared with those of pure PA56. Thus, the proposed method is suitable for toughening PA56 and broadening its applications., Competing Interests: Declaration of competing interest The authors declare that there is no conflict of interest., (Copyright © 2024. Published by Elsevier B.V.)

Poly (butylene adipate-co-terephthalate) (PBAT) wastewater is a highly concentrated, acidic, and toxic wastewater generated from biodegradable plastics production. Large amounts of alkali would be consumed when treating PBAT wastewater by anaerobic digestion due to the low pH value. This study employed acidic anaerobic digestion to treat PBAT wastewater and compared to neutral anaerobic digestion. The results indicated that the COD removal rates in the acidic upflow anaerobic sludge blanket (UASB) reactor were 65.5% and 59.9%, respectively at influent pH 6.0 and 5.0 with the COD concentration of around 11,000 mg L -1 , and the methane conversion efficiency were 172.5 and 183.8 mLCH 4 /gCOD r (gCOD r : COD removed amount), respectively. Correspondingly, the average COD removal and methane conversion efficiency in the neutral UASB reactor were 63.2% and 188.0 mLCH 4 /gCOD r , respectively. The treatment efficiency of acidic and neutral UASB reactors for PBAT wastewater was similar. The hydrogenotrophic methanogenic activity was further enhanced in the acidic UASB reactor compared to the neutral one. The increase of alkalinity in the acidic UASB reactor (2.4 mmol L -1 ) was higher than the neutral (2.0 mmol L -1 ). A higher level of syntrophic acetate oxidation bacteria and hydrogenotrophic methanogen was enriched in the acidic UASB reactor, ensuring efficient treatment and saving costs., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

There is an increasing demand for bio-based dicarboxylic acids (DCA) as an eco-friendly alternatives to chemically synthesized DCA. Adipic acid, which is not naturally produced by microorganisms, is an essential DCA with significant industrial importance. This study aimed to develop a platform strain using Yarrowia lipolytica for efficient bioconversion of renewable resources into adipic acid. To prevent the complete oxidation of adipic acid, peroxisomal β-oxidation was engineered by selectively disrupting acyl-CoA oxidases. Furthermore, ω-oxidation activity was improved via introducing an additional copy of cytochrome P450 monooxygenase (ALK5) and reductase (CPR1) with fatty alcohol oxidase (FAO1). The production phase used SP92D medium in a two-stage bioconversion process, during which the engineered strain exhibited the highest production level, achieving a remarkable 9.7-fold increase compared to that of the parental strain. To our knowledge, this is the first report demonstrating that engineered Y. lipolytica can produce adipic acid from fatty acid methyl esters., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

To reduce the white pollution, the eco-friendly biodegradable poly (butylene adipate-co-terephthalate) (PBAT)-based films had attracted increasing interests worldwide. However, the high-cost of the PBAT had limited the large-scale development and application. In this work, 10 wt% low-cost lignin was introduced into the PBAT to prepare composite films by melt blending and blow molding, and the POSS (epoxy)8 was selected as the compatibilizer to improve the compatibility of PBAT and lignin. The maximum tensile strength and the nominal strain at break subsequently increased by 48.2 % and 21.4 % respectively, while the water vapor permeability enhanced by 9.9 %. Furthermore, the UV aging resistance of PBAT/lignin films were significantly improved, with only 1 wt% POSS (epoxy)8 content. This work provides an efficient strategy to foster the end-user confidence in the low-cost and eco-friendly biodegradable polymer materials with efficient performance., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Melt processing of cellulose nanocrystals (CNCs) reinforced nanocomposites is still a serious challenge due to the hydrophilic nature of CNCs and their severe agglomeration tendency within the polymer melt. In this study, chemical modification of CNC through grafting poly(glycidyl methacrylate) (PGMA) with various degrees was implemented. Wettability of the modified CNCs (mCNCs) were controlled and their structure was characterized through Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), optical microscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The nanocomposites of polybutylene adipate terephthalate (PBAT) with 3 wt% CNC and mCNC were prepared using an internal melt mixer. To differentiate the effects of CNC and PGMA molecules on the final properties of nanocomposites, PBAT/PGMA compounds were separately prepared. To confirm the chain characterization and molecular weight of the synthesized PGMAs, 1 H NMR and gel permeation chromatography (GPC) analysis were conducted. Melt rheological analysis, dynamic mechanical analysis (DMA), DSC, and atomic force microscopy (AFM) were used to monitor the mCNC dispersion quality and the effect of PGMA modification in PBAT compounds. The results revealed that grafting CNC with longer PGMA considerably improved the CNCs' dispersion quality within PBAT. Such dispersion enhancement of long-chain mCNCs and interfacial interaction of PGMA and PBAT resulted in a noticeable increase in storage modulus and complex viscosity of the final nanocomposites., Competing Interests: Declaration of competing interest Authors do not have any declaration of interest., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The demand for sustainable development has led to increasing attention in biobased polyesters due to their adjustable thermal and mechanical properties and biodegradability. In this study, we used a novel bioderived aromatic diacid, 2,5-thiophenedicarboxylic acid (TDCA) to synthesize a list of novel aromatic-aliphatic poly(alkylene adipate- co -thiophenedicarboxylate) (PAATh) copolyesters through a facile melt polycondensation method. PAAThs are random copolyesters with weight-average molecular weights of 58400 to 84200 g·mol -1 and intrinsic viscosities of 0.80 to 1.27 dL·g -1 . All PAAThs exhibit sufficiently high thermal stability as well as the highest tensile strength of 6.2 MPa and the best gas barrier performances against CO 2 and O 2 , 4.3- and 3.3-fold better than those of poly(butylene adipate- co -terephthalate) (PBAT). The biodegradability of PAAThs was fully evaluated through a degradation experiment and various experimental parameters, including residue weights, surface morphology, and molecular compositions. The state-of-the-art molecular dynamics (MD) simulations were applied to elucidate the different enzymatic degradation behaviors of PAAThs due to the effect of diols with different chain structures. The sterically hindered carbonyl carbon of the PHATh-enzyme complex was more susceptible to nucleophilic attack and exhibited a higher tendency to enter a prereaction state. This study has introduced a group of novel biobased copolyesters with their structure-property relationships investigated thoroughly, and the effect of diol components on the enzymatic degradation was revealed by computational analysis. These findings may lay the foundation for the development of promising substitutes for commercial biodegradable polyesters and shed light on their complicated degradation mechanisms.

Exposure to phthalates, adipates, bisphenol-A (BPA), and pesticides may have important health consequences for children, but little is known regarding their presence in school meals, a major food source for children. The aims of this study were to determine the presence of phthalates, adipates, BPA, and pesticides in school meals. Using a cross-sectional design, n = 50 school meal components were collected from four school districts in New England (n = 8 elementary/K-8 schools) differing preparation methods (on-site scratch cooking and pre-packaged heat and serve meals with plastic films) between 2019 and 2021. Meal components were tested for the presence of phthalates, adipates, BPA, and pesticides by an independent laboratory. One adipate, DEHA, was detected in 42% of samples (range 0.08 mg/kg - 50.39 mg/kg). Among the prepackaged foods, DEHA was detected in 86% of samples, which also contained the highest average concentrations among all the samples tested. The phthalate Diisononyl phthalate (DINP) was detected in only one sample, and BPA was not detected in any of the samples tested. Pesticides were detected in 64% of produce and 27% of entrées, but most had levels that were lower than the average levels detected by the USDA's Pesticide Data Program and only one sample had levels that exceeded those detected by the USDA (Cyfluthrin levels in one sample of apples were 0.038 mg/kg compared with an USDA average range of 0.004–0.032 mg/kg). Overall pesticides and phthalate levels in school meals are low and BPA was not detected. However, this study suggests that manufacturers may be changing to less studied plasticizers such as DEHA. More studies should examine the impact of DEHA on human health, particularly among children. As schools transition back from the COVID-19 pandemic, foods packaged in plastic should be minimized where possible. Overall, school meals remain one of the healthiest options for children and policies that support on site cooking can further strengthen the quality of school meals. • Pesticides and phthalate levels in school meals were low and BPA was not detected. • DEHA was detected in almost half of samples, particularly in prepackaged foods. • Policies that support on site cooking in schools can reduce exposures to DEHA. [ABSTRACT FROM AUTHOR]

Poly(butylene adipate-co-terephthalate) (PBAT), a promising biodegradable aliphatic-aromatic copolyester material, can be applied as an alternative material to reduce the adverse effects of conventional plastics. However, the degradation of PBAT plastics in soil is time-consuming, and effective PBAT-degrading microorganisms have rarely been reported. In this study, the biodegradation properties of PBAT by an elite fungal strain and related mechanisms were elucidated. Four PBAT-degrading fungal strains were isolated from farmland soils, and Purpureocillium lilacinum strain BA1S showed a prominent degradation rate. It decomposed approximately 15 wt.% of the PBAT films 30 days after inoculation. Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and Liquid chromatography mass spectrometry (LC‒MS) were conducted to analyze the physicochemical properties and composition of the byproducts after biodegradation. In the presence of PBAT, the lipolytic enzyme activities of BA1S were remarkably induced, and its cutinase gene was also significantly upregulated. Of note, the utilization of PBAT in BA1S cells was closely correlated with intracellular cytochrome P450 (CYP) monooxygenase. Furthermore, CreA-mediated carbon catabolite repression was confirmed to be involved in regulating PBAT-degrading hydrolases and affected the degradation efficiency. This study provides new insight into the degradation of PBAT by elite fungal strains and increases knowledge on the mechanism, which can be applied to control the biodegradability of PBAT films in the future. KEY POINTS: • Purpureocillium lilacinum strain BA1S was isolated from farmland soils and degraded PBAT plastic films at a prominent rate. • The lipolytic enzyme activities of strain BA1S were induced during coculture with PBAT, and the cutinase gene was significantly upregulated during PBAT degradation. • CreA-mediated carbon catabolite repression of BA1S plays an essential role in regulating the expression of PBAT-degrading hydrolases., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

This study compares the morphology, thermal, and dynamic-mechanical properties of composites based on polybutylene adipate terephthalate/polylactide biocomposites with sponge gourd waste treated code as R, and non-treated sponge gourd, coded as NR, by mechanical disc refining after milled process. Extrusion followed by compression molding was used to produce biocomposites with fiber contents of 0, 2.5, 5, 10, and 15% wt/wt for R and NR sponge gourd fibers. Scanning electron microscopy analysis reveals that NR has the morphology of a rigid tubular shape, whereas R is a thinner, twisted, and fibrillated fiber. Regardless of the type of sponge gourd fiber used, the thermal stability of the composite decreases as the sponge gourd content increases. At 25°C, the biocomposite with 10%wt/wt R fiber has the highest storage modulus value. The comparison of Tangent  peak values reveals that the presence of sponge gourd fibers reduces the energy dissipation of the biocomposites. The analysis of the loss modulus at 25°C reveals that R fiber contributes more to the reduction of energy dissipation of the biocomposites than NR. Furthermore, the Cole-Cole plot shows that R and NR fibers are dispersed and do not significantly change the homogeneity of the biopolymer systems.