Exploring the substrate spectrum of phylogenetically distinct bacterial polyesterases.

The rapid escalation of plastic waste accumulation presents a significant threat of the modern world, demanding an immediate solution. Over the last years, utilization of the enzymatic machinery of various microorganisms has emerged as an environmentally friendly asset in tackling this pressing global challenge. Thus, various hydrolases have been demonstrated to effectively degrade polyesters. Plastic waste streams often consist of a variety of different polyesters, as impurities, mainly due to wrong disposal practices, rendering recycling process challenging. The elucidation of the selective degradation of polyesters by hydrolases could offer a proper solution to this problem, enhancing the recyclability performance. Towards this, our study focused on the investigation of four bacterial polyesterases, including DaPUase, IsPETase, PfPHOase, and Se1JFR, a novel PETase-like lipase. The enzymes, which were biochemically characterized and structurally analyzed, demonstrated degradation ability of synthetic plastics. While a consistent pattern of polyesters' degradation was observed across all enzymes, Se1JFR stood out in the degradation of PBS, PLA, and polyether PU. Additionally, it exhibited comparable results to IsPETase, a benchmark mesophilic PETase, in the degradation of PCL and semi-crystalline PET. Our results point out the wide substrate spectrum of bacterial hydrolases and underscore the significant potential of PETase-like enzymes in polyesters degradation.

A meta-analysis of risk factors for a Dacron-cuffed catheter related infection in hemodialysis.

OBJECTIVE: To provide theoretical basis for prevention of a Dacron-cuffed catheter related infection (CRI), the risk factors of CRI in hemodialysis patients were systematically evaluated. METHODS: Eight databases, including PubMed, Cochrane library, EMBASE, Web of Science, China National Knowledge Infrastructure (CNKI), Chinese Biomedical Database (CBM), Wanfang Database and Chinese Scientific Journal Database (VIP), were searched to screen out literatures related to the risk factors of long-term indwelling a Dacron-cuffed CRI in hemodialysis. Meta-analysis of risk factors for a Dacron-cuffed CRI in hemodialysis and publication bias test were performed using RevMan 5.4 software. RESULTS: After screening, 13 literatures involving a Dacron-cuffed CRI were included, with a total of 625 patients, and the infection rate was 11.7%. The combined OR value and 95% confidence interval (CI) of all factors were: Combined with Diabetes (1.94, 1.51 ~ 2.50), Hb (1.82, 1.35 ~ 2.44), age (2.38, 1.06 ~ 5.34), catheter indwelling time (1.79, 1.21 ~ 2.66), serum albumin (2.26, 1.25 ~ 4.08), catheter indwelling site (3.29, 1.74 ~ 6.23) and the number of tube placement (5.40, 2.65 ~ 11.02). CONCLUSIONS: The main risk factors for a Dacron-cuffed CRI in hemodialysis were combined with diabetes, hemoglobin level, age, catheter indwelling time, serum albumin level, femoral vein catheter indwelling and catheterization times. In other words, hemodialysis patients are at higher risk of CRI if they have diabetes, or if they have a lower hemoglobin level, or if they are older, or if they have a longer duration of catheterization, or if they have a lower serum albumin level, or if they have a femoral vein catheter, or if they have more catheters.

[Structure motif guided mining of MHET hydrolase and development of a two-enzyme cascade for plastics depolymerization at mild temperature].

The utilization of polyethylene terephthalate (PET) has caused significant and prolonged ecological repercussions. Enzymatic degradation is an environmentally friendly approach to addressing PET contamination. Hydrolysis of mono(2-hydroxyethyl) terephthalate (MHET), a competitively inhibited intermediate in PET degradation, is catalyzed by MHET degrading enzymes. Herein, we employed bioinformatic methods that combined with sequence and structural information to discover an MHET hydrolase, BurkMHETase. Enzymatic characterization showed that the enzyme was relatively stable at pH 7.5-10.0 and 30-45 ℃. The kinetic parameters kcat and Km on MHET were (24.2±0.5)/s and (1.8±0.2) µmol/L, respectively, which were similar to that of the well-known IsMHETase with higher substrate affinity. BurkMHETase coupled with PET degradation enzymes improved the degradation of PET films. Structural analysis and mutation experiments indicated that BurkMHETase may have evolved specific structural features to hydrolyze MHET. For MHET degrading enzymes, aromatic amino acids at position 495 and the synergistic interactions between active sites or distal amino acids appear to be required for MHET hydrolytic activity. Therefore, BurkMHETase may have substantial potential in a dual-enzyme PET degradation system while the bioinformatic methods can be used to broaden the scope of applicable MHETase enzymes.

Microbial degradation of low-density polyethylene, polyethylene terephthalate, and polystyrene by novel isolates from plastic-polluted environment.

Biodegradation is an eco-friendly measure to address plastic pollution. This study screened four bacterial isolates that were capable of degrading recalcitrant polymers, i.e., low-density polyethylene, polyethylene terephthalate, and polystyrene. The unique bacterial isolates were obtained from plastic polluted environment. Dermacoccus sp. MR5 (accession no. OP592184) and Corynebacterium sp. MR10 (accession no. OP536169) from Malaysian mangroves and Bacillus sp. BS5 (accession no. OP536168) and Priestia sp. TL1 (accession no. OP536170) from a sanitary landfill. The four isolates showed a gradual increase in the microbial count and the production of laccase and esterase enzymes after 4 weeks of incubation with the polymers (independent experiment set). Bacillus sp. BS5 produced the highest laccase 15.35 ± 0.19 U/mL and showed the highest weight loss i.e., 4.84 ± 0.6% for PS. Fourier transform infrared spectroscopy analysis confirmed the formation of carbonyl and hydroxyl groups as a result of oxidation reactions by enzymes. Liquid chromatography-mass spectrometry analysis showed the oxidation of the polymers to small molecules (alcohol, ethers, and acids) assimilated by the microbes during the degradation. Field emission scanning electron microscopy showed bacterial colonization, biofilm formation, and surface erosion on the polymer surface. The result provided significant insight into enzyme activities and the potential of isolates to target more than one type of polymer for degradation.

Ex vivo evaluation of 3 different right ventricular outflow tract substitutes.

OBJECTIVES: The Ross procedure represents an excellent treatment option in younger patients with aortic stenosis but is limited by poor availability of homografts. In this study, we investigated the hydrodynamic performance of 3 different types of right ventricular outflow tract replacement with pericardium or synthetic material. METHODS: Three different types of valved conduits were constructed using pericardium and/or synthetic material (Group PEPE: pericardial cusps and pericardial conduit, Group PEPR: pericardial cusps and Dacron conduit, Group PRPR: expanded polytetrafluoroethylene cusps and Dacron conduit). The conduits were designed according to the Ozaki method. Their hydrodynamic performance (effective orifice area, mean pressure gradient and leakage volume) were evaluated in a mock circulation loop at different hydrodynamic conditions. RESULTS: Hydrodynamic assessment showed significantly larger effective orifice area of PEPE and PEPR compared to PRPR under all conditions and there were no significant differences between PEPE and PEPR [for condition 2: PEPE 2.43 (2.35-2.54) cm2, PEPR: 2.42 (2.4-2.5) cm2, PRPR: 2.08 (1.97-2.21) cm2, adjusted pairwise comparisons: PEPE versus PEPR: P = 0.80, PEPE versus PRPR: P < 0.001, PEPR versus PRPR: P < 0.001]. Mean pressure gradient was significantly lower for PEPE and PEPR compared with PRPR, whereas no significant differences were seen between PEPE and PEPR. Leakage volume was significantly lower for PEPE and PEPR compared with PRPR under all conditions while leakage was similar between PEPE and PEPR. CONCLUSIONS: Pulmonary graft reconstruction with pericardium cusps showed superior hydrodynamic performance compared with polytetrafluoroethylene cusps. Our results suggest that it could be considered as an alternative substitute for right ventricular outflow tract replacement during the Ross procedure.

Chemical reactivity theory to analyze possible toxicity of microplastics: Polyethylene and polyester as examples.

Micro- and nanoplastics are widespread throughout the world. In particular, polyethylene (PE) and polyethylene terephthalate or polyester (PET) are two of the most common polymers, used as plastic bags and textiles. To analyze the toxicity of these two polymers, oligomers with different numbers of units were used as models. The use of oligomers as polymeric templates has been used previously with success. We started with the monomer and continued with different oligomers until the chain length was greater than two nm. According to the results of quantum chemistry, PET is a better oxidant than PE, since it is a better electron acceptor. Additionally, PET has negatively charged oxygen atoms and can promote stronger interactions than PE with other molecules. We found that PET forms stable complexes and can dissociate the guanine-cytosine nucleobase pair. This could affect DNA replication. These preliminary theoretical results may help elucidate the potential harm of micro- and nanoplastics.

Production of hydrogen-rich fuel gas from waste plastics using continuous plasma pyrolysis reactor.

There is a serious concern about the large amount of accumulated plastic waste all around the world. Synthetic polymers such as polyethylene terephthalate (PET), polypropylene (PP), and polyethylene (HDPE, LDPE) are substantially present in the plastic waste generated. There are various methods reported to minimise such plastics waste with certain limitations. To overcome such limitations the present study have been carried out in which thermal decomposition of plastic waste of PET, PP, HDPE, and LDPE studied using a novel plasma pyrolysis reactor. The major objective of this work is to investigate the viability of the continuous plasma pyrolysis process for the treatment of various plastic wastes with respect to waste volume reduction and production of combustible hydrogen-rich fuel gas. The effect of temperature and feed flow rate on product gas yield, product gas efficiency, solid residue yield, and H2/CO ratio has been evaluated. The experiments have been carried out at different temperatures within the range of 700-1000 °C. Plasma pyrolysis system exhibited combustible hydrogen-rich gas as a product and solid residue. Liquid products have not been observed during plasma pyrolysis, unlike conventional pyrolysis. The reaction mechanism of plastic cracking has been discussed based on literature and products obtained in the present work. The effects of feed flow rate and temperature on exergy efficiency were studied using the response surface method. The mass, energy, and exergy analyses have also been carried out for all the experiments, which are in the range of 0.95-0.99, 0.48 to 0.77, and 0.30 to 0.69, respectively.

New insights into changes in phosphorus profile at sediment-water interface by microplastics: Role of benthic bioturbation.

Microplastics (MPs) have attracted increasing attention due to their ubiquitous occurrence in freshwater sediments and the detrimental effects on benthic invertebrates. However, a clear understanding of their downstream impacts on ecosystem services is still lacking. This study examines the effects of bio-based polylactic acid (PLA), fuel-based polyethylene terephthalate (PET), and biofilm-covered PET (BPET) MPs on the bioturbator chironomid larvae (Tanypus chinensis), and the influence on phosphorus (P) profiles in microcosms. The changes in biochemical responses and metabolic pathways indicated that MPs disrupted energy synthesis by causing intestinal blockage and oxidative stress in T. chinensis, leading to energy depletion and impaired bioturbation activity. The impairment further resulted in enhanced sedimentary P immobilization. For larval treatments, the internal-P loadings were respectively 11.4%, 8.6%, and 9.0% higher in the PLA, PET, and BPET groups compared to the non-MP control. Furthermore, the influence of bioturbation on P profiles was MP-type dependent. Both BPET and PLA treatments displayed more obvious impacts on P profiles compared to PET due to the changes in MP bioavailability or sediment microenvironment. This study connects individual physiological responses to broader ecosystem services, showing that MPs alter P biogeochemical processes by disrupting the bioturbation activities of chironomid larvae.

Functional upcycling of waste PET plastic to the hybrid magnetic microparticles adsorbent for cesium removal.

Accumulation of mismanaged plastic in the environment and the appearance of emerging plastic-derived pollutants such as microplastics strongly demand technologies for waste plastic utilization. In this study, polyethylene terephthalate (PET) from waste plastic bottles was directly utilized to prepare a matrix of an adsorbent for cesium (Cs+) removal. The organic matrix of PET-derived oligomers obtained by aminolysis depolymerization was impregnated with bentonite clay and magnetite nanoparticles (Fe3O4 NPs), playing the roles as a major adsorptive medium for Cs+ removal and as a functional component to primarily provide efficient separation of the hybrid adsorbent from aqueous system, respectively. The obtained hybrid composite microparticles were next tested as an adsorbent for the removal of Cs+ cation from aqueous solutions. The adsorption process was characterized by fast kinetics reaching ca. 60% of the equilibrium adsorption capacity within 5 min and the maximum adsorption capacity toward Cs+ was found to be 26.8 mg/g. The adsorption process was primarily dominated by the cationic exchange in bentonite, which was not significantly affected by the admixture of the competing mono- and divalent cations (Na+, K+, and Mg2+). The proposed approach here exploits the sustainable utilization scenario of plastic waste-derived material to template complex multifunctional nanocomposites that can find applications for pollution cleaning and environmental remediation.

In vitro cell-transforming potential of secondary polyethylene terephthalate and polylactic acid nanoplastics.

Continuous exposure to plastic pollutants may have serious consequences on human health. However, most toxicity assessments focus on non-environmentally relevant particles and rarely investigate long-term effects such as cancer induction. The present study assessed the carcinogenic potential of two secondary nanoplastics: polyethylene terephthalate (PET) particles generated from plastic bottles, and a biodegradable polylactic acid material, as respective examples of environmentally existing particles and new bioplastics. Pristine polystyrene nanoplastics were also included for comparison. A broad concentration range (6.25-200 µg/mL) of each nanoplastic was tested in both the initiation and promotion conditions of the regulatory assessment-accepted in vitro Bhas 42 cell transformation assay. Parallel cultures allowed confirmation of the efficient cellular internalisation of the three nanoplastics. Cell growth was enhanced by polystyrene in the initiation assay, and by PET in both conditions. Moreover, the number of transformed foci was significantly increased only by the highest PET concentration in the promotion assay, which also showed dose-dependency, indicating that nano PET can act as a non-genotoxic tumour promotor. Together, these findings support the carcinogenic risk assessment of nanoplastics and raise concerns regarding whether real-life co-exposure of PET nanoplastics and other environmental pollutants may result in synergistic transformation capacities.

Survival and hormone production of isolated mouse follicles in three-dimensional artificial scaffolds after stimulation with bpV(HOpic).

PURPOSE: To preserve fertility before gonadotoxic therapy, ovarian tissue can be removed, cryopreserved, and transplanted back again after treatment. An alternative is the artificial ovary, in which the ovarian follicles are extracted from the tissue, which reduces the risk of reimplantation of potentially remaining malignant cells. The PTEN inhibitor bpV(HOpic) has been shown to activate human, bovine and alpacas ovarian follicles, and it is therefore considered a promising substance for developing the artificial ovary. The purpose of this study was to examine the impact of different scaffolds and the vanadate derivative bpV(HOpic) on mice follicle survival and hormone secretion over 10 days. METHODS: A comparative analysis was performed, studying the survival rates (SR) of isolated mice follicle in four different groups that differed either in the scaffold (polycaprolactone scaffold versus polyethylene terephthalate membrane) or in the medium-bpV(HOpic) versus control medium. The observation period of the follicles was 10 days. On days 2, 6, and 10, the viability and morphology of the follicles were checked using fluorescence or confocal microscopy. Furthermore, hormone levels of estrogen (pmol/L) and progesterone (nmol/L) were determined. RESULTS: When comparing the SR of follicles among the four groups, it was observed that on day 6, the study groups utilizing the polycaprolactone scaffold with bpV(HOpic) in the medium (SR: 0.48 ± 0.18; p = 0.004) or functionalized in the scaffold (SR: 0.50 ± 0.20; p = 0.003) exhibited significantly higher survival rates compared to the group using only the polyethylene terephthalate membrane (SR: 0). On day 10, a significantly higher survival rate was only noted when comparing the polycaprolactone scaffold with bpV(HOpic) in the medium to the polyethylene terephthalate membrane group (SR: 0.38 ± 0.20 versus 0; p = 0.007). Higher levels of progesterone were only significantly associated with better survival rates in the group with the polycaprolactone scaffold functionalized with bpV(HOpic) (p = 0.017). CONCLUSION: This study demonstrates that three-dimensional polycaprolactone scaffolds improve the survival rates of isolated mice follicles in comparison with a conventional polyethylene terephthalate membrane. The survival rates slightly improve with added bpV(HOpic). Furthermore, higher rates of progesterone were also partly associated with improved survival.

Molecular Insights into the Enhanced Activity and/or Thermostability of PET Hydrolase by D186 Mutations.

PETase exhibits a high degradation activity for polyethylene terephthalate (PET) plastic under moderate temperatures. However, the effect of non-active site residues in the second shell of PETase on the catalytic performance remains unclear. Herein, we proposed a crystal structure- and sequence-based strategy to identify the key non-active site residue. D186 in the second shell of PETase was found to be capable of modulating the enzyme activity and stability. The most active PETaseD186N improved both the activity and thermostability with an increase in Tm by 8.89 °C. The PET degradation product concentrations were 1.86 and 3.69 times higher than those obtained with PETaseWT at 30 and 40 °C, respectively. The most stable PETaseD186V showed an increase in Tm of 12.91 °C over PETaseWT. Molecular dynamics (MD) simulations revealed that the D186 mutations could elevate the substrate binding free energy and change substrate binding mode, and/or rigidify the flexible Loop 10, and lock Loop 10 and Helix 6 by hydrogen bonding, leading to the enhanced activity and/or thermostability of PETase variants. This work unraveled the contribution of the key second-shell residue in PETase in influencing the enzyme activity and stability, which would benefit in the rational design of efficient and thermostable PETase.

Influence of polyethylene terephthalate (PET) microplastic on selected active substances in the intramural neurons of the porcine duodenum.

BACKGROUND: Currently, society and industry generate huge amounts of plastics worldwide. The ubiquity of microplastics is obvious, but its impact on the animal and human organism remains not fully understood. The digestive tract is one of the first barriers between pathogens and xenobiotics and a living organism. Its proper functioning is extremely important in order to maintain homeostasis. The aim of this study was to determine the effect of microplastic on enteric nervous system and histological structure of swine duodenum. The experiment was carried out on 15 sexually immature gilts, approximately 8 weeks old. The animals were randomly divided into 3 study groups (n = 5/group). The control group received empty gelatin capsules once a day for 28 days, the first research group received daily gelatin capsules with polyethylene terephthalate (PET) particles as a mixture of particles of various sizes (maximum particle size 300 µm) at a dose of 0.1 g/animal/day. The second study group received a dose ten times higher-1 g/animal/day. RESULTS: A dose of 1 g/day/animal causes more changes in the enteric nervous system and in the histological structure of duodenum. Statistically significant differences in the expression of cocaine and amphetamine regulated transcript, galanin, neuronal nitric oxide synthase, substance P, vesicular acetylcholine transporter and vasoactive intestinal peptide between control and high dose group was noted. The histopathological changes were more frequently observed in the pigs receiving higher dose of PET. CONCLUSION: Based on this study it may be assumed, that oral intake of microplastic might have potential negative influence on digestive tract, but it is dose-dependent.

Response mechanism of non-biodegradable polyethylene terephthalate microplastics and biodegradable polylactic acid microplastics to nitrogen removal in activated sludge system.

The issue of microplastics (MPs) has gained more attention among researchers and the public; however, there is still a lot to be studied about its impact on biological wastewater treatment. In this study, the effects of non-biodegradable polyethylene terephthalate (PET) and biodegradable polylactic acid (PLA) on wastewater treatment by sequencing batch reactor (SBR) were compared. The results showed that PET and PLA reduced the removal efficiency of NH4+-N by 1.7 % and 21.2 %, respectively. Structural equation functional model (SEM) analysis was used to infer the potential mechanism of PLA affecting ammonia oxidation. PLA primarily inhibits the activity of ammonia monooxygenase (AMO), while promoting an increase in reactive oxygen species (ROS) and antioxidant enzyme activity. Accordingly, the toxic effect of PLA further reduced the abundance of ammonia-oxidizing bacteria. This study showed that biodegradable MPs have a greater potential impact on wastewater treatment than non-biodegradable MPs, which warrants further investigation.

Differences in toxicity induced by the various polymer types of nanoplastics on HepG2 cells.

The problem of microplastics (MPs) contamination in food has gradually come to the fore. MPs can be transmitted through the food chain and accumulate within various organisms, ultimately posing a threat to human health. The concentration of nanoplastics (NPs) exposed to humans may be higher than that of MPs. For the first time, we studied the differences in toxicity, and potential toxic effects of different polymer types of NPs, namely, polyethylene terephthalate (PET), polyvinyl chloride (PVC), and polystyrene (PS) on HepG2 cells. In this study, PET-NPs, PVC-NPs, and PS-NPs, which had similar particle size, surface charge, and shape, were prepared using nanoprecipitation and emulsion polymerization. The results of the CCK-8 assay showed that the PET-NPs and PVC-NPs induced a decrease in cell viability in a concentration-dependent manner, and their lowest concentrations causing significant cytotoxicity were 100 and 150 µg/mL, respectively. Moreover, the major cytotoxic effects of PET-NPs and PVC-NPs at high concentrations may be to induce an increase in intracellular ROS, which in turn induces cellular damage and other toxic effects. Notably, our study suggested that PET-NPs and PVC-NPs may induce apoptosis in HepG2 cells through the mitochondrial apoptotic pathway. However, no relevant cytotoxicity, oxidative damage, and apoptotic toxic effects were detected in HepG2 cells with exposure to PS-NPs. Furthermore, the analysis of transcriptomics data suggested that PET-NPs and PVC-NPs could significantly inhibit the expression of DNA repair-related genes in the p53 signaling pathway. Compared to PS-NPs, the expression levels of lipid metabolism-related genes were down-regulated to a greater extent by PET-NPs and PVC-NPs. In conclusion, PET-NPs and PVC-NPs were able to induce higher cytotoxic effects than PS-NPs, in which the density and chemical structure of NPs of different polymer types may be the key factors causing the differences in toxicity.

When polyethylene terephthalate microplastics meet Perfluorooctane sulfonate in thermophilic biogas upgrading system: Their effect on methanogenesis.

Microplastics (MPs) and Perfluorooctane sulfonate (PFOS) are two hard-biodegradable pollutants widely existing in the waste streams treated by anaerobic digestion. However, their synergistic effect on methanogenic metabolism is still unknown. This study investigated the impact of polyethylene terephthalate (PET) MPs alone and co-existing with PFOS on CO2 conversion to CH4 in a thermophilic biogas upgrading system. The results showed that either PET MPs addition alone or coexisting with PFOS improved the ultimate CH4 percentage and increased CO2 utilization rate. When Fe0 was added into the reactors with PET to enhance the interspecies electron transfer, a potential defluorination was observed with a defluorination rate of 15.88 ± 1.53%. Exposure of the reactor to PFOS of 300 µg/L could change the methanogenic pathway, resulting in a newly emerged Methanomassiliicoccus with dominance of 16%. Furthermore, under the exposure of PFOS, the number of predicted genes regulating enzymes in methanogenic steps from CO2 increased. These results suggest that the co-existence of PET MPs and PFOS will not inhibit the activity of hydrotrophic methanogenes, and a portion of PFOS may be biodegraded during the methanogenesis under Fe0 regulation.

Computational redesign of a hydrolase for nearly complete PET depolymerization at industrially relevant high-solids loading.

Biotechnological plastic recycling has emerged as a suitable option for addressing the pollution crisis. A major breakthrough in the biodegradation of poly(ethylene terephthalate) (PET) is achieved by using a LCC variant, which permits 90% conversion at an industrial level. Despite the achievements, its applications have been hampered by the remaining 10% of nonbiodegradable PET. Herein, we address current challenges by employing a computational strategy to engineer a hydrolase from the bacterium HR29. The redesigned variant, TurboPETase, outperforms other well-known PET hydrolases. Nearly complete depolymerization is accomplished in 8 h at a solids loading of 200 g kg-1. Kinetic and structural analysis suggest that the improved performance may be attributed to a more flexible PET-binding groove that facilitates the targeting of more specific attack sites. Collectively, our results constitute a significant advance in understanding and engineering of industrially applicable polyester hydrolases, and provide guidance for further efforts on other polymer types.

New combined absorption/1H NMR method for qualitative and quantitative analysis of PET degradation products.

Poly(ethylene terephthalate) (PET) is a very valuable and beneficial material for industrial purposes, with various different applications. Due to the high annual production volume of over 50 million tons worldwide and the indiscriminate disposal by consumers, the polymers accumulate in the environment, causing negative effects on various ecosystems. Biodegradation via suitable enzymes represents a promising approach to combat the plastic waste issue so validated methods are required to measure the efficiency and efficacy of these enzymes. PETase and MHETase from Ideonella sakaiensis are suitable enzymes needed in combination to completely degrade PET into its environmentally friendly monomers. In this project, we compare and combine a previously described bulk absorbance measurement method with a newly established 1H NMR analysis method of the PET degradation products mono(2-hydroxyethyl) terephthalic acid, bis(2-hydroxyethyl) terephthalic acid and terephthalic acid. Both were optimized regarding different solvents, pH values and drying processes. The accuracy of the measurements can be confirmed with sensitivity limits of 2.5-5 µM for the absorption method and 5-10 µM for the 1H NMR analysis. The combination of the described methods therefore allows a quantitative analysis by using bulk absorption coupled with a qualitative analysis through 1H NMR. The methods established in our work can potentially contribute to the development of suitable recycling strategies of PET using recombinant enzymes.

Interfacial interactions of polyethylene terephthalate microplastics and malachite green, tetracycline in aqueous environments.

Polyethylene terephthalate microplastics (PET-MPs) are one of pivotal nondegradable emerging pollutant. Here the variation of the surface physicochemical characteristics of PET-MPs with UV irradiation aging and the adsorption behaviors of PET-MPs in malachite green (MG), tetracycline (TC) solution and the effect of coexisting Cu(II) were comparatively investigated. The yellowing, weakened hydrophobicity, and increased surface negative charge, crystallinity degree and oxygen-containing functional groups were manifested specifically by the aged PET-MPs. Different from the single system, the hydrophobic interaction and metal ion bridging complexation dominated the adsorption of MG and TC, respectively, in the binary solution. While in the ternary solution, cationic ion competition of Cu(II) with MG decreased its capture, and the formation of PET-Cu(II)-TC ternary complexes promoted TC adsorption. Moreover, PET-MPs could serve as an efficient vector for MG and TC in MG/TC/Cu(II) ternary system, indicating PET-MPs tend to carry more varieties in the complex environment, that may increase the environmental risk of PET-MPs.

From cracks to secondary microplastics - surface characterization of polyethylene terephthalate (PET) during weathering.

Secondary microplastics are a product of the fragmentation of plastic debris. Despite concerns regarding the omnipresence of microplastics in the environment, knowledge about the mechanics of their actual formation is still limited. Fragmentation is usually linked to weathering, which alters the properties of the plastic and allows fragmentation to occur. Therefore, in this study, polyethylene terephthalate (PET) samples were exposed to artificial UV light or a combination of UV light and water for a total of three months to simulate natural weathering. The samples included three forms of PET with different production histories: pellets, yarns, and films. The surface alterations to the samples during weathering were characterized using scanning electron microscopy and Raman spectroscopy. Results indicated that the three different types of PET developed markedly different surface defects and also exhibited signs of weathering within different time frames. Differences were also found between samples exposed only to UV and those exposed to UV and submerged in water. In water, the first surface changes were spotted within 30 days of initial submersion and later developed into an organized crack network. Upon the introduction of mild mechanical forces, pieces of the weathered surface started to delaminate. The fragments from films had an elongated shape with a median size of 16.1 × 2.1 × 1.8 µm, resembling a fibre. If the weathered surface of a film were to detach completely, it could create 1.4-7.9 million microplastic fragments/cm2. For pellets, this number would range between 0.4 and 2.2 million microplastics/cm2. In addition to particle formation by surface delamination, particles also emerged on the weathered surfaces of all studied samples, presenting another possible source of micro-sized particles during weathering. Overall, the results of this work show that the weathering of plastics and the formation of microplastics are heavily influenced not only by the weathering mechanism but also by the type and production history of the polymers.