Depolymerization Products Research Articles

Identification and characterization of a novel polyamide hydrolase

The widespread use of non-naturally degradable plastics is causing increasingly serious harm to the environment. Reducing plastic pollutants has become the core of ecological and environment management. Biological methods such as enzymes demonstrate advantages in depolymerizing plastics with mild reaction conditions and recycling of depolymerization products. However, there are few reports on the biological depolymerization of polyamide plastics. In this study, by using 4-nitropropionanilide as the model substrate, we screened against our plastic depolymerase library and obtained a Meiothermus ruber-derived enzyme (MrABH) that can hydrolyze the polyamide bond. We expressed this enzyme in Escherichia coli and purified the protein by affinity chromatography. Furthermore, we investigated the catalytic properties, enzymatic properties, and catalytic products of this enzyme with polyamide as the substrate. MrABH had good stability at pH 8.0-10.0, with the optimal performance at pH 9.0 and 30 ℃. The catalytic performance of this enzyme for ester bonds and amide bonds was similar. MrABH can catalyze the depolymerization of PA6 and PA66 to produce monomers and oligomers, demonstrating the potential to be used in the depolymerization and recycling of polyamide.

Leaching behavior of microplastics during sludge mechanical dewatering and its effect on activated sludge

Dewatering is an indispensable link in sludge treatment, but its effect on the microplastics (MPs) remains inadequately understood. This study investigated the physicochemical changes and leaching behavior of MPs during the mechanical dewatering of sludge, as well as the impact of MP leachates on activated sludge (AS). After sludge dewatering, MPs exhibit rougher surfaces, decreased sizes and altered functional groups due to the addition of dewatering agents and the application of mechanical force. Meanwhile, plastic additives, depolymerization products, and derivatives of their interactions are leached from MPs during sludge dewatering process. The concentration of MP-based leachates in sludge is 2–25 times higher than that in water. The enhancement of pH and ionic strength caused by dewatering agents induces the release of MP leachates enriched with protein-like, fulvic acid-like, and soluble microbial by-product-like substances. The reflux of MP leachates in sludge dewatering liquor to the wastewater treatment system negatively impacts AS, leading to a decrease in COD removal rate and inhibition of the extracellular polymeric substances secretion. More importantly, MP leachates cause oxidative stress to microbial cells and alter the microbial community structure of AS at the phylum and genus levels. These findings confirm that MPs undergo aging and leaching during sludge dewatering process, and MP leachates may negatively affect the wastewater treatment system.

Compositional Analysis of Cutin in Maize Leaves.

The cuticle is a lipid barrier that covers the air-exposed surfaces of plants. It consists of waxes and cutin, a cell wall-attached lipid polyester of oxygenated fatty acids and glycerol. Unlike waxes, cutin is insoluble in organic solvents, and its composition is typically studied by chemical depolymerization followed by monomer analysis by gas chromatography (GC). Here, we describe a method for the chemical depolymerization of cutin in maize leaves and subsequent compositional analysis of the constituent lipid monomers. The method has been adapted from protocols for cutin analysis developed for Arabidopsis, by both optimizing the amount of leaf tissue used and including a data analysis process specific to the monomers present in maize cutin. The approach uses base-catalyzed transmethylation, which produces fatty acid methyl esters, and silylation, which gives trimethylsilyl ether derivatives of hydroxyl groups for gas chromatographic analysis. For monomer identification, a few representative samples are first analyzed by GC-mass spectrometry (GC-MS). This is then followed by analysis of all replicates by gas chromatography coupled to a flame ionization detector (GC-FID) for monomer quantification, because the flame ionization detector provides a linear response over a wide mass range, is relatively simple to operate, and is more cost-effective to maintain compared to mass spectrometry detectors. Although the protocol bypasses time-consuming cuticle isolation steps by using whole-leaf samples, this means that a fraction of the compounds in the chromatographic profiles do not derive from cutin. Accordingly, we discuss some considerations for the interpretation of the resulting depolymerization products. Our protocol offers specific guidance on preparing maize leaf samples, ensuring reproducible results, and enabling the detection of subtle variations in cutin monomer composition among plant genotypes or developmental stages.

Self-immolative Polymer Hydrogels via In Situ Gelation.

Hydrogels are of interest for a wide range of applications. The ability to control when the hydrogel degrades can provide beneficial properties such as controlled degradation in the environment or the stimulated release of drugs or cells. Self-immolative polymers are a class of degradable polymers that undergo complete end-to-end depolymerization upon the application of a stimulus. They have been explored for hydrogel development, but the ability to prepare and selectively degrade self-immolative hydrogels under neutral aqueous conditions has so far been limited. We describe here the preparation of water-soluble polyglyoxylamides with cross-linkable pendent azides and their cross-linking to form hydrogels with 4-arm poly(ethylene glycol)s having unstrained and strained alkynes using copper-assisted and strain-promoted azide-alkyne click chemistry respectively. The influence of pendent azide density and solution polymer content on the resulting hydrogels was evaluated. A polyglyoxylamide with a 70 : 30 ratio of pendent hydroxyl:azide successfully provided hydrogels with compressive moduli ranging from 1.3-6.3 kPa under copper-free conditions at 10-20 % (w/w) of polymer in phosphate-buffered saline. Selective depolymerization and degradation of the hydrogels upon irradiation with light was demonstrated, resulting in reductions in the compressive moduli and the release of depolymerization products that were detected by NMR spectroscopy.

Maximizing the valorization potential of lignin through optimization of the Soda pulping conditions

The valorization potential of lignin is strongly dependent on the yield that can be obtained during the pulping process as well as its chemical structure. Both of these are determined by factors such as the biomass type, the selected extraction strategy and the employed conditions. Within this study, Miscanthus x giganteus biomass was subjected to systematically varying Soda pulping conditions, i.e., temperature (100 °C – 180 °C), OH– concentration (0.158 mol/L – 1.000 mol/L) and time (60 min – 360 min). These pulping conditions can be combined into a single factor, reflecting the processing severity, which in this work varied from approximately 1 to 5. The resulting black liquor, precipitated lignin, lignin stock solution (i.e., lignin dissolved in the solvent used in the subsequent depolymerization step) and product pool after mild reductive catalytic depolymerization (200 °C, 10 bar H2 initial, 4 h) were thoroughly characterized using a plethora of analysis techniques. Increasing the severity factor of the pulping was found to result in an enhancement of the delignification degree from 25.3 ± 2.6 % to 95.4 ± 9.9 %. However, beyond a severity factor of 3, fragmentation of native ether linkages and condensation reactions start to cause unfavourable changes in the chemical structure of the lignin and depolymerization product pool. Furthermore, these reactions significantly reduce the total mass yield from biomass to depolymerization product pool. An Adaboost model with quadratic base estimator was trained against the experimental data, and subsequently used to optimize the pulping conditions, aiming at a maximum total mass yield with minimal fragmentation and, hence, condensation, of the lignin. The optimum was experimentally validated, which resulted in a lignin with high β-O-4 content (42.7 ± 2.8 linkages per 100 aromatic units) and a total mass yield of 30.9 ± 3.4 wt% and a pulp with a residual lignin content of 8.25 ± 0.94 wt%.

Strategic design of degradable polyurethanes: Site-specific depolymerization, film-forming behavior, and reprocessability

This paper reports on the rational design of linear sustainable polyurethanes with on-demand depolymerization capabilities and film-forming properties. In this molecular approach, self-immolative urethane motifs are engineered to not only induce rapid degradation in response to an external stimulus via sequential elimination but also provide sufficient inter-chain interactions to yield nanofibers or free-standing films. Amalgamation with various isocyanate or polyol components results in a range of degradable polyurethanes, while doping with europium complexes or carbon black leads to the formation of free-standing hybrid films with photoluminescent or conductive properties, respectively. These films can be reversibly cast using a facile dissolution process, and the predetermined depolymerization products can then be used to generate upcycled materials such as polyurea or polyacrylate films. We believe that our conceptual design for sustainable polyurethanes can be advanced further when combined with conventional engineering techniques to meet industrial and environmental requirements and create desirable materials for contemporary applications.

Discrimination and simultaneous quantification of poly(ethylene terephthalate) and poly(butylene terephthalate) microplastics in environmental samples via gas chromatography-tandem mass spectrometry.

A method has been developed to quantify PET and PBT microplastics (MPs) based on depolymerization and detection of depolymerization products by gas chromatography-tandem mass spectrometry (GC-MS/MS) without a complex separation process from environmental samples. Under the optimal depolymerization conditions, PET and PBT were efficiently convertedto ethylene glycol (78%) and 1,4-butanediol (87%), respectively. Subsequently, the linear curves were constructed between signal intensities of depolymerization products and polymer masses by GC-MS/MS, and the correlation coefficients of PET and PBT were 0.996 and 0.997, respectively. The spiking and recovery experiments of PET and PBT in the environmental samples showed that the recovery was stable in the range 89-100%, and the limit of detection was 4.95μg and 1.39μg of PET and PBT, respectively. The method has been proven to be capable of simultaneous identification and quantification of PBT and PET MPs in real environmental water samples without complex separation process, which provided a scheme for the determination of microplastics.

Eugenol Hydrodeoxygenation Over Mixed Mo-W Carbides.

The modification of molybdenum carbide catalysts by another transition metal has raised an increasing research interest due to the significant improvement of catalyst activity in hydrodeoxygenation of lignin derivatives. At par with the commonly used Co and Ni that add a strong hydrogenation functionality, it was found that the addition of the more oxophilic W restricts ring hydrogenation while allowing the deoxygenation of oxygenated compounds and thus yielding higher selectivity toward the formation of non-oxygenated aromatic compounds. The coexistence of Mo2C with W2C along with metallic W altered the electronic properties of Mo2C which resulted in an increase of catalyst active site density and facilitated further total eugenol deoxygenation. Propyl-benzene selectivity of up to 83 % was reached at close to 100 % eugenol conversion. These findings will allow a better overview of the effect of different metal phases of mixed carbides on the catalyst performance and raise the prospect of optimizing catalyst design for a hydrodeoxygenation processing of lignin depolymerization products.

Rapid characterization of kraft lignin depolymerisation products by high-resolution mass spectrometry with visualization of mass spectrometric data

Rapid characterization of kraft lignin depolymerisation products by high-resolution mass spectrometry with visualization of mass spectrometric data

Sequential extraction, depolymerization and quantification of polyethylene terephthalate nanoplastics using magnetic ZIF-8 nanocomposites

The detection and quantification of nanoplastics in aqueous medium is largely untapped because of an absence of appropriate sample processing methods. In this work, magnetic ZIF-8 nanoparticles (Nano-Fe@ZIF-8) have been applied for the magnetic extraction and depolymerization of polyethylene terephthalate (PET) nanoplastics. Nano-Fe@ZIF-8 enabled the fast aggregation and magnetic retrieval of PET nanoplastics from water. The Zn(II) present in Nano-Fe@ZIF-8 subsequently acted as a catalyst for the depolymerization of the extracted PET nanoplastics using ethylene glycol at 180 °C. PET nanoplastics were depolymerized in just 30 min, producing the depolymerization product bis(2-hydroxyethyl) terephthalate. The selective quantification of the depolymerization product using reversed-phase liquid chromatography enabled the measurement of the original PET nanoplastics present in water at parts-per-million level, and with a high reproducibility (RSD, 2.8–5.9 %). This is the first example of an integrated magnetic-catalytic nanomaterial enabling the isolation, depolymerization, and detection of nanoplastics from aqueous medium.

From Polyester Plastics to Diverse Monomers via Low-Energy Upcycling.

Polyester plastics, constituting over 10% of the total plastic production, are widely used in packaging, fiber, single-use beverage bottles, etc. However, their current depolymerization processes face challenges such as non-broad spectrum recyclability, lack of diversified high-value-added depolymerization products, and crucially high energy consumption. Herein, an efficient strategy is developed for dismantling the compact structure of polyester plastics to achieve diverse monomer recovery. Polyester plastics undergo swelling and decrystallization with a low depolymerization energy barrier via synergistic effects of polyfluorine/hydrogen bonding, which is further demonstrated via density functional theory calculations. The swelling process is elucidated through scanning electron microscopy analysis. Obvious destruction of the crystalline region is demonstrated through X-ray crystal diffractometry curves. PET undergoes different aminolysis efficiently, yielding nine corresponding high-value-added monomers via low-energy upcycling. Furthermore, four types of polyester plastics and five types of blended polyester plastics are closed-loop recycled, affording diverse monomers with exceeding 90% yields. Kilogram-scale depolymerization of real polyethylene terephthalate (PET) waste plastics is successfully achieved with a 96% yield.

Yield and distribution of products of lignin liquefaction catalyzed by molybdenum-vanadium-phosphorus heteropolyacids

ABSTRACT This paper focuses on the performance of Molybdenum-vanadium-phosphorus heteropolyacids (PMo12-xVx) with different V-doped amounts in catalyzing the conversion of lignin to bio-oil, and the distribution of liquefied products. Molybdenum-vanadium-phosphorus heteropolyacids (PMo11V1, PMo10V2, PMo9V3) with different amount (0, 2.5, 5, 10 wt%) were used to catalyze lignin liquefaction. The experimental results showed that PMo12-xVx could effectively catalyze the depolymerization of lignin to bio-oil, and the doping amount of the V atom in PMo12-xVx affects the distribution of lignin depolymerization products. The highest bio-oil yield (53.62wt%) and conversion (57.83wt%) could be obtained from lignin liquefaction at 2.5 wt% PMo9V3. With the increase of PMo12-xVx V-atom doped amount, the content of aliphatic hydrocarbons increased from 3.14% to 40.58%, the content of vanillin increased from none to 8.9%. Based on the analysis of bio-oil, FT-IR data, and DFT simulation results, it was found that the selective cleavage of the Cα-Cβ bond and the ring-opening of the carbon at the methyl end of lignin were the main reasons for the high yield of vanillin and aliphatic hydrocarbons during the depolymerization of lignin catalyzed by PMo12-xVx. Finally, a possible reaction pathway for the PMo12-xVx-catalyzed depolymerization of lignin to vanillin and aliphatic hydrocarbons was proposed.

Lignin oxidative depolymerization to phenolic compounds in a continuous-flow manufacturing platform

Effective oxidative depolymerization of lignin to phenolic monomers and oligomers is a crucial step in the economic feasibility of biorefinery. To date, most studies on the processing technical of lignin have focused on intermittent treatment, with little attention paid to microreactor. In this research, a novel and efficient process technical of oxidative depolymerization lignin via a continuous manufacturing platform was developed, in which the lignin alkaline solution is the disperse phase and the hydrogen peroxide is the continuous phase (oxidants, 8 wt%). The results show that different products can be obtained through varying the reaction conditions of lignin depolymerization. Under the optimized condition, 93.03 wt% conversion of raw lignin and 22.37 wt% yield of monomer was obtained. Besides, comparative characterizations on the samples of raw lignin and depolymerization products by GC-MS-FID and HSQC NMR analysis illustrated that 84.26 wt% of monomers (the sum of yield of 18.85 wt%) is phenolic compounds, with syringaldehyde (yield of 4.22 wt% and selectivity of 18.86 wt%) and vanillin (yield of 3.49 wt% and selectivity of 15.60 wt%) are the main products and the high yields attributed to the efficient cleavage of C-O linkages (mainly β-O-4 linkages) of lignin. Moreover, GPC and elemental analyses show that the light oil product with an oxygen content of 41.28% was mainly composed of dimers and trimers. This work demonstrating that continuous-flow oxidative depolymerization was an effective strategy on lignin processing technical and will be an interesting field of research on lignin comprehensive utilization.

Rapid biodegradation of microplastics generated from bio-based thermoplastic polyurethane

The accumulation of microplastics in various ecosystems has now been well documented and recent evidence suggests detrimental effects on various biological processes due to this pollution. Accumulation of microplastics in the natural environment is ultimately due to the chemical nature of widely used petroleum-based plastic polymers, which typically are inaccessible to biological processing. One way to mitigate this crisis is adoption of plastics that biodegrade if released into natural environments. In this work, we generated microplastic particles from a bio-based, biodegradable thermoplastic polyurethane (TPU-FC1) and demonstrated their rapid biodegradation via direct visualization and respirometry. Furthermore, we isolated multiple bacterial strains capable of using TPU-FC1 as a sole carbon source and characterized their depolymerization products. To visualize biodegradation of TPU materials as real-world products, we generated TPU-coated cotton fabric and an injection molded phone case and documented biodegradation by direct visualization and scanning electron microscopy (SEM), both of which indicated clear structural degradation of these materials and significant biofilm formation.

Alternative feedstock for thermoplastic polyurethane chain extenders through chemical recycling of the polyurea fraction in a rigid PVC foam

Thermoplastic polyurethanes (TPUs) are synthetized by using the products from the chemical recycling of polyurea. In particular, the polyurea fraction included in PVC foams typically used in sandwich structures is depolymerized under glycolysis conditions with 1,4-butanediol (BD). After separation of the solid PVC fraction, the liquid part is used as it is, instead of pure BD, as chain extender. Two different depolymerization products obtained with 3/1 or 2/1 BD to foam ratio are tested in combination with methylene diphenyl diisocyanate (MDI) and poly(tetrahydrofuran). Reference samples are also synthetized with pure BD. The hard phase content is kept constant at 39 % of total TPU weight, while the weight ratio of chain extender to MDI is varied in the range from 13 to 25 %. The obtained polymers are characterized by GPC, FT-IR and NMR spectroscopy analyses in order to investigate the effect of the chain extender substitution and of the chain extender to MDI ratio on the macromolecular features. Furthermore, the obtained polymers are characterized by thermal (DSC, TGA) and mechanical analyses (Shore A, stress–strain). The results reveal that the depolymerization products can be used in substitution of pure BD as chain extender, giving TPU with mechanical properties comparable to the one of the reference samples, once the reaction conditions are properly scaled. Only a minor difference occurs in the shore A values, which decrease with the content of polyurea depolymerization fraction (FDP) in the mixture. Despite this, the mechanical properties of the newly synthesized FDP-based TPUs are suitable for several applications, e.g. in the footwear, cable & wire, hose and tube, film and sheet industries.

Impact of the T296S mutation in P450 GcoA for aryl-O-demethylation: a QM/MM study.

Lignin, a complex plant cell wall component, holds promise as a renewable aromatic carbon feedstock. p-Vanillin is a key product of lignin depolymerization and a precursor of protocatechuic acid (PCA) that has tremendous potential for biofuel production. While the GcoAB enzyme, native to Amycolatopsis sp., naturally catalyzes aryl-O-demethylation toward guaiacol, recent research introduced a single mutation, T296S, into the GcoAP450 enzyme, enabling it to catalyze aryl-O-demethylation of p-vanillin. This structural modification increases the efficiency of GcoAP450 for the natural substrate while being active for p-vanillin. This study reveals the increased flexibility of p-vanillin and its ability to adapt a favorable conformation by aligning the methoxy group in close proximity to Fe(IV) = O of Cpd I in the active site of the T296S variant. The QM/MM calculations in accordance with the experimental data validated that the rate-limiting step for the oxidation of p-vanillin is hydrogen atom abstraction and provided a detailed geometric structure of stationary and saddle points for the oxidation of p-vanillin.

Co@C synergistic alkali-catalyzed depolymerization of hydrolyzed lignin for the preparation of multifunctional ceramic additives

In this research endeavor, we report the successful synthesis of an aminosulfonic-based ceramic additive, HLDSA, was prepared by replacing part of phenol with HLDLP, a depolymerization product of hydrolysis lignin, through Co@C metal catalysts in the synergistic alkali-catalyzed depolymerization of hydrolysis lignin to achieve high-value lignin utilization. The preparation and application conditions of the depolymerized hydrolysis lignin HLDLP and its modified product HLDSA were studied, together with a brief analysis of their mechanism of action. During application of ceramic additive, the HLDSA showed a rather excellent dispersing and flexural strength performance, with a minimum slurry outflow time of 20.81 s and a maximum flexural strength of 2.79 MPa, which was a significant improvement over that of the blank sample (59.29 s and 1.77 MPa). Meanwhile, HLDSA was contrasted with other 8 ceramic additives that are widely available on the market. The application performance of HLDSA was also better than that other ceramic additives on the market, indicating that HLDSA has a promising application.

The effect of linseed oil/canola oil blend on the coating and thermal properties of waste PET-based alkyd resins.

This study aims to prepare oil-modified alkyd resins using a linseed oil/canola oil (LO/CO) blend and waste PET depolymerization product, suitable for environmentally friendly coating applications. Waste PET flakes obtained from grinding post-consumer water bottles were depolymerized by the aminoglycolysis reaction at high pressure. Raw depolymerization product (DP) was used in the synthesis of four components, 50% oil alkyd resins by monoglyceride method. DP has partly replaced the dibasic acid component in the PET-based alkyd formulations. Besides PET-based alkyds, reference alkyds without DP were also synthesized for comparison. Then, the surface coating properties and thermal behaviors of alkyd films were determined. The effect of DP usage and the changing ratios of LO/CO blend on coating properties and thermal behaviors of alkyd films were investigated. In addition, the optimum LO/CO blend ratio which is compatible with alkyd formulation was attempted to be determined. At the end of this study, glossy, soft/medium-hard films were obtained with excellent adhesion, impact strength, and chemical resistance. Thermal resistance and final thermal oxidative degradation temperature increased with adding DP to the alkyd formulation. Using LO/CO blend in the formulations affected oxidation rate and ratio, hence, drying time/degree and oxidative stability of alkyd films.

Chemical recycling of polyolefins via ring-closing metathesis depolymerization.

The current insufficient recycling of commodity polymer waste has resulted in pressing environmental and human health issues in our modern society. In the quest for next-generation polymer materials, chemists have recently shifted their attention to the design of chemically recyclable polymers that can undergo depolymerization to regenerate monomers under mild conditions. During the past decade, ring-closing metathesis reactions have been demonstrated to be a robust approach for the depolymerization of polyolefins, producing low-strain cyclic alkene products which can be repolymerized back to new batches of polymers. In this review, we aim to highlight the recent advances in chemical recycling of polyolefins enabled by ring-closing metathesis depolymerization (RCMD). A library of depolymerizable polyolefins will be covered based on the ring size of their monomers or depolymerization products, including five-membered, six-membered, eight-membered, and macrocyclic rings. Moreover, current limitations, potential applications, and future opportunities of the RCMD approach will be discussed. It is clear from recent research in this field that RCMD represents a powerful strategy towards closed-loop chemical recycling of novel polyolefin materials.

Theoretical insight of reactive oxygen species scavenging mechanism in lignin waste depolymerization products.

Apart from natural products and synthesis, phenolic compounds can be produced from the depolymerization of lignin, a major waste in biofuel and paper production. This process yields a plethora of aryl propanoid phenolic derivatives with broad biological activities, especially antioxidant properties. Due to its versatility, our study focuses on investigating the antioxidant mechanisms of several phenolic compounds obtained from renewable and abundant resources, namely, syringol (Hs), 4-allylsyringol (HAs), 4-propenylsyringol (HPns), and 4-propylsyringol (HPs). Employing the density functional theory (DFT) approach in conjunction with the QM-ORSA protocol, we aim to explore the reactivity of these compounds in neutralizing hydroperoxyl radicals in physiological and non-polar media. Kinetic and thermodynamic parameter calculations on the antioxidant activity of these compounds were also included in this study. Additionally, our research utilizes the activation strain model (ASM) for the first time to explain the reactivity of the HT and RAF mechanisms in the peroxyl radical scavenging process. It is predicted that HPs has the best rate constant in both media (1.13 × 108 M-1 s-1 and 1.75 × 108 M-1 s-1, respectively). Through ASM analysis, it is observed that the increase in the interaction energy due to the formation of intermolecular hydrogen bonds during the reaction is an important feature for accelerating the hydrogen transfer process. Furthermore, by examining the physicochemical and toxicity parameters, only Hs is not suitable for further investigation as a therapeutic agent because of potential toxicity and mutagenicity. However, overall, all compounds are considered potent HOO˙ scavengers in lipid-rich environments compared to previously studied antioxidants.