Network of cyano-p-aramid nanofibres creates ultrastiff and water-rich hydrospongels.

The structure-property paradox of biological tissues, in which water-rich porous structures efficiently transfer mass while remaining highly mechanically stiff, remains unsolved. Although hydrogel/sponge hybridization is the key to understanding this phenomenon, material incompatibility makes this a challenging task. Here we describe hydrogel/sponge hybrids (hydrospongels) that behave as both ultrastiff water-rich gels and reversibly squeezable sponges. The self-organizing network of cyano-p-aramid nanofibres holds approximately 5,000 times more water than its solid content. Hydrospongels, even at a water concentration exceeding 90 wt%, are hard as cartilage with an elastic modulus of 50-80 MPa, and are 10-1,000 times stiffer than typical hydrogels. They endure a compressive strain above 85% through poroelastic relaxation and hydrothermal pressure at 120 °C. This performance is produced by amphiphilic surfaces, high rigidity and an interfibrillar, interaction-driven percolating network of nanofibres. These features can inspire the development of future biofunctional materials.

Study on the Synthetic Characteristics of Biomass-Derived Isosorbide-Based Poly(arylene ether ketone)s for Sustainable Super Engineering Plastic.

Demand for the development of novel polymers derived from biomass that can replace petroleum resources has been increasing. In this study, biomass-derived isosorbide was used as a monomer in the polymerization of poly(arylene ether ketone)s, and its synthetic characteristics were investigated. As a phase-transfer catalyst, crown ether has increased the weight-average molecular weight of polymers over 100 kg/mol by improving the reaction efficiency of isosorbide and minimizing the effect of moisture. By controlling the experimental parameters such as halogen monomer, polymerization solvent, time, and temperature, the optimal conditions were found to be fluorine-type monomer, dimethyl sulfoxide, 24 h, and 155 °C, respectively. Biomass contents from isosorbide-based polymers were determined by nuclear magnetic resonance and accelerator mass spectroscopy. The synthesized polymer resulted in a high molecular weight that enabled the preparation of transparent polymer films by the solution casting method despite its weak thermal degradation stability compared to aromatic polysulfone. The melt injection molding process was enabled by the addition of plasticizer. The tensile properties were comparable or superior to those of commercial petrochemical specimens of similar molecular weight. Interestingly, the prepared specimens exhibited a significantly lower coefficient of thermal expansion at high temperatures over 150 °C compared to polysulfone.

Structural evaluation of Poly(lactic acid) degradation at standardized composting temperature of 58 degrees.

The accumulation of petroleum-based plastics on our planet is causing serious environmental pollution. Biodegradable plastics, promoted as eco-friendly solutions, hold the potential to address this issue. However, their impact on the environment and the mechanisms of their natural degradation remain inadequately understood. Furthermore, the specific conditions set forth in international standards for evaluating the biodegradability of biodegradable plastics have led to misconceptions about their real-world behavior. To properly elucidate the relationship between their degradability and structure, this study mimics the thermal effect on poly(lactic acid) (PLA) under standardized composting temperature. The higher the crystallinity of PLA, the lower the degradation rate, which suggests that crystallinity is a key factor in determining degradation. The composting temperature of 58 °C induces crystallization by having a structural effect on the polymer, which in turn reduces the degradation rate of PLA. Therefore, control over temperature and crystallization during the processing and degradation of PLA is crucial, as it not only determines the biodegradability but also enhances the utility.

Ecotoxicity assessment of additives in commercial biodegradable plastic products: Implications for sustainability and environmental risk.

Biodegradable plastics have gained popularity as environmentally friendly alternatives to conventional petroleum-based plastics, which face recycling and degradation challenges. Although the biodegradability of these plastics has been established, research on their ecotoxicity remains limited. Biodegradable plastics may still contain conventional additives, including toxic and non-degradable substances, to maintain their functionality during production and processing. Despite degrading the polymer matrix, these additives can persist in the environment and potentially harm ecosystems and humans. Therefore, this study aimed to assess the potential ecotoxicity of biodegradable plastics by analyzing the phthalate esters (PAEs) leaching out from biodegradable plastics through soil leachate. Sixteen commercial biodegradable plastic products were qualitatively and quantitatively analyzed using gas chromatography-mass spectrometry to determine the types and amounts of PAE used in the products and evaluate their ecotoxicity. Among the various PAEs analyzed, non-regulated dioctyl isophthalate (DOIP) was the most frequently detected (ranging from 40 to 212 µg g-1). Although the DOIP is considered one of PAE alternatives, the detected amount of it revealed evident ecotoxicity, especially in the aquatic environment. Other additives, including antioxidants, lubricants, surfactants, slip agents, and adhesives, were also qualitatively detected in commercial products. This is the first study to quantify the amounts of PAEs leached from biodegradable plastics through water mimicking PAE leaching out from biodegradable plastics to soil leachate when landfilled and evaluate their potential ecotoxicity. Despite their potential toxicity, commercial biodegradable plastics are currently marketed and promoted as environmentally friendly materials, which could lead to indiscriminate public consumption. Therefore, in addition to improving biodegradable plastics, developing eco-friendly additives is significant. Future studies should investigate the leaching kinetics in soil leachate over time and toxicity of biodegradable plastics after landfill disposal.

Circular waste management: Superworms as a sustainable solution for biodegradable plastic degradation and resource recovery.

Bioplastics offer a promising solution to plastic pollution, however, their production frequently relies on edible biomass, and their degradation rates remain inadequate. This study investigates the potential of superworms (Zophobas atratus larvae) for polybutylene succinate (PBS) waste management, aiming to achieve both resource recovery and biodegradation. Superworms exclusively fed on PBS for a month exhibited the same survival rate as those on a standard bran diet. PBS digestion yielded a 5.13% weight gain and a 23.23% increase in protein composition in superworms. Additionally, carbon isotope analyses substantiated the conversion of PBS into superworm components. Gut microbes capable of PBS biodegradation became progressively prominent, further augmenting the degradation rate of PBS under composting conditions (ISO 14855-1). Gut-free superworms fed with PBS exhibited antioxidant activities comparable to those of blueberries, renowned for their high antioxidant activity. Based on these findings, this study introduces a sustainable circular solution encompassing recycling PBS waste to generate insect biomass, employing insect gut and frass for PBS degradation and fertilizer, and harnessing insect residue as a food source. In essence, the significance of this research extends to socio-economic and environmental spheres, impacting waste management, resource efficiency, circular economy promotion, environmental preservation, industrial advancement, and global sustainability objectives. The study's outcomes possess the potential to reshape society's approach to plastic waste, facilitating a shift toward more sustainable paradigms.

Analysis of volatile organic compounds produced during incineration of non-degradable and biodegradable plastics.

As plastic consumption has increased, environmental problems associated with the accumulation of plastic wastes have started to emerge. These include the non-degradability of plastic and its disintegration into sub-micron particles. Although some biodegradable plastic products have been developed to relieve the landfill and leakage burden, a significant portion of discarded plastics are inevitably still incinerated. The concern here is that incinerating plastics may result in the emission of toxic volatile organic compounds (VOCs). Moreover, lack of policy and the limited market share contributes to the indiscriminate discarding of biodegradable plastics, whereby it is mixed and subsequently incinerated with non-degradable plastics. The aim of this study was therefore to qualitatively and quantitatively analyze the VOCs emitted from both non-degradable and biodegradable plastics during combustion employing gas chromatography mass spectrometry. Here, non-degradable poly(vinyl chloride) and poly(ethylene terephthalate) emitted 10-115 and 6-22 ppmv of VOCs, respectively. These emission levels were more than 100 times higher than the VOC concentrations of 0.1-0.5 and 0.1-1.8 ppmv obtained for biodegradable polyhydroxyalkanoate and polylactic acid, respectively. Notably, due to the presence of a repeating butylene group in both non-degradable and biodegradable plastics, 1,3-butadiene accounted for the highest concentration among the VOCs identified, with concentrations of 6-116 ppmv and 0.5-558 ppmv obtained, respectively. During the evaluation of gas barrier films employed for food packaging purposes, non-degradable aluminum-coated multilayered films emitted 9-515 ppmv of VOCs, compared to the 2-41 ppmv VOCs emitted by biodegradable nanocellulose/nanochitin-coated films. Despite the significantly lower levels of VOCs emitted during the incineration of biodegradable plastics, this does not represent suitable waste treatment solution because VOCs are still emitted during incomplete combustion. This study aims to encourage further research into diverse combustion conditions for plastics and stimulate discussions on the fate of discarded plastics.

Biodegradable, Water-Resistant, Anti-Fizzing, Polyester Nanocellulose Composite Paper Straws.

Among plastic items, single-use straws are particularly detrimental to marine ecosystems because such straws, including those made of poly(lactic acid) (PLA), are sharp and extremely slowly degradable in the ocean. While paper straws are promising alternatives, they exhibit hydration-induced swelling even when coated with a non-degradable plastic coating and promote effervescence (fizzing) in soft drinks owing to their surface heterogeneities. In this study, upgraded paper straw is coated with poly(butylene succinate) cellulose nanocrystal (PBS/CNC) composites. CNC increases adhesion to paper owing to their similar chemical structures, optimizes crystalline PBS spherulites through effective nucleation, and reinforces the matrix through its anisotropic and rigid features. The straws are not only anti-fizzing when used with soft drinks owing to their homogeneous and seamless surface coatings, but also highly water-resistant and tough owing to their watertight surfaces. All degradable components effectively decompose under aerobic composting and in the marine environment. This technology contributes to United Nations Sustainable Development Goal 14 (Life Below Water).

Pd-catalyzed decarboxylative coupling of propiolic acids: one-pot synthesis of 1,4-disubstituted 1,3-diynes via Sonogashira-homocoupling sequence.

One-pot synthesis of symmetric 1,4-disubstituted 1,3-diynes from iodoarenes and propiolic acid via Sonogashira reaction followed by Pd-catalyzed decarboxylative homocoupling is developed in high yields. Also, this system allows the one-pot synthesis of unsymmetric 1,4-disubstituted 1,3-diynes by cross-coupling of two different 3-substituted propiolic acids.

Biosynthesis of Polyhydroxybutyrate with Cellulose Nanocrystals Using Cupriavidus necator.

Polyhydroxybutyrate (PHB) is a natural polyester synthesized by several microorganisms. Moreover, it has excellent biodegradability and is an eco-friendly material because it converts water and carbon dioxide as final decomposition products. However, the applications of PHB are limited because of its stiffness and brittleness. Because cellulose nanocrystals (CNCs) have excellent intrinsic mechanical properties such as high specific strength and modulus, they may compensate for the insufficient physical properties of PHB by producing their nanocomposites. In this study, natural polyesters were extracted from Cupriavidus necator fermentation with CNCs, which were well-dispersed in nitrogen-limited liquid culture media. Fourier-transform infrared spectroscopy results revealed that the additional O-H peak originating from cellulose at 3500-3200 cm-1 was observed for PHB along with the C=O and -COO bands at 1720 cm-1. This suggests that PHB-CNC nanocomposites could be readily obtained using C. necator fermented in well-dispersed CNC-supplemented culture media.

Aramid Nanofiber Templated In Situ SNAr Polymerization for Maximizing the Performance of All-Organic Nanocomposites.

The performance limits of conventional super engineering plastics with inorganic nanofillers are surpassed by all-organic nanocomposites prepared via in situ SNAr polymerization of polysulfone (PSU) in the presence of a highly dispersed aramid nanofiber (ANF) solution. The latter is directly used, bypassing the energy-consuming, nanostructure-damaging workup process. Using only a 0.15 wt % nanofiller, the all-organic nanocomposite shows an ultimate tensile strength 1.6× higher and 3.4× tougher than neat PSU and its blending counterpart due to the mutually interactive filler and maximally homogenized matrix. The exceptional toughness of the ANF/PSU nanocomposite originates from the grafted PSU on the surface of ANF; it drives stress-delocalized deformation, as revealed by stress-absorbable viscoelastic behavior and ductile elongation of materials. This material is a promising candidate for use as a filler-interactive, high-performance nanocomposite.

Sustainable and recyclable super engineering thermoplastic from biorenewable monomer.

Environmental and health concerns force the search for sustainable super engineering plastics (SEPs) that utilise bio-derived cyclic monomers, e.g. isosorbide instead of restricted petrochemicals. However, previously reported bio-derived thermosets or thermoplastics rarely offer thermal/mechanical properties, scalability, or recycling that match those of petrochemical SEPs. Here we use a phase transfer catalyst to synthesise an isosorbide-based polymer with a high molecular weight >100 kg mol-1, which is reproducible at a 1-kg-scale production. It is transparent and solvent/melt-processible for recycling, with a glass transition temperature of 212 °C, a tensile strength of 78 MPa, and a thermal expansion coefficient of 23.8 ppm K-1. Such a performance combination has not been reported before for bio-based thermoplastics, petrochemical SEPs, or thermosets. Interestingly, quantum chemical simulations show the alicyclic bicyclic ring structure of isosorbide imposes stronger geometric restraint to polymer chain than the aromatic group of bisphenol-A.

Sustainable Boron Nitride Nanosheet-Reinforced Cellulose Nanofiber Composite Film with Oxygen Barrier without the Cost of Color and Cytotoxicity.

This paper introduces a boron nitride nanosheet (BNNS)-reinforced cellulose nanofiber (CNF) film as a sustainable oxygen barrier film that can potentially be applied in food packaging. Most commodity plastics are oxygen-permeable. CNF exhibits an ideal oxygen transmission rate (OTR) of <1 cc/m²/day in highly controlled conditions. A CNF film typically fabricated by the air drying of a CNF aqueous solution reveals an OTR of 19.08 cc/m²/day. The addition of 0⁻5 wt % BNNS to the CNF dispersion before drying results in a composite film with highly improved OTR of 4.7 cc/m²/day, which is sufficient for meat and cheese packaging. BNNS as a 2D nanomaterial increases the pathway of oxygen gas and reduces the chances of pinhole formation during film fabrication involving water drying. In addition, BNNS improves the mechanical properties of the CNF films (Young's modulus and tensile strength) without significant elongation reductions, probably due to the good miscibility of CNF and BNNS in the aqueous solution. Addition of BNNS also produces negligible color change, which is important for film aesthetics. An in vitro cell experiment was performed to reveal the low cytotoxicity of the CNF/BNNS composite. This composite film has great potential as a sustainable high-performance food-packaging material.

Superior Toughness and Fast Self-Healing at Room Temperature Engineered by Transparent Elastomers.

The most important properties of self-healing polymers are efficient recovery at room temperature and prolonged durability. However, these two characteristics are contradictory, making it difficult to optimize them simultaneously. Herein, a transparent and easily processable thermoplastic polyurethane (TPU) with the highest reported tensile strength and toughness (6.8 MPa and 26.9 MJ m-3 , respectively) is prepared. This TPU is superior to reported contemporary room-temperature self-healable materials and conveniently heals within 2 h through facile aromatic disulfide metathesis engineered by hard segment embedded aromatic disulfides. After the TPU film is cut in half and respliced, the mechanical properties recover to more than 75% of those of the virgin sample within 2 h. Hard segments with an asymmetric alicyclic structure are more effective than those with symmetric alicyclic, linear aliphatic, and aromatic structures. An asymmetric structure provides the optimal metathesis efficiency for the embedded aromatic disulfide while preserving the remarkable mechanical properties of TPU, as indicated by rheological and surface investigations. The demonstration of a scratch-detecting electrical sensor coated on a tough TPU film capable of auto-repair at room temperature suggests that this film has potential applications in the wearable electronics industry.

Environmentally-Friendly Synthesis of Carbonate-Type Macrodiols and Preparation of Transparent Self-Healable Thermoplastic Polyurethanes.

Carbonate-type macrodiols synthesized by base-catalyzed polycondensation of co-diols and dimethyl carbonate as an environmentally-friendly route were subsequently utilized for the preparation of transparent and self-healable thermoplastic polyurethanes (TPUs) containing a carbonate-type soft segment. Three types of macrodiols, obtained from mono, dual and triple diol-monomers for target molecular weights of 1 and 1.5 kg mol-1, were analyzed by ¹H NMR integration and the OH titration value. Colorless transparent macrodiols in a liquid state at a room temperature of 20 °C were obtained, except the macrodiol from mono 1,6-hexanediol. Before TPU synthesis, macrodiols require pH neutralization to prevent gelation. TPUs synthesized by a solution pre-polymer method with 4,4'-methylene(bisphenyl isocyanate) and 1,4-butanediol as a chain extender exhibited moderate molecular weights, good transparencies and robust mechanical properties. Especially, the incorporation of 3-methyl-1,5-pentanediol within carbonate-type macrodiols enhanced the transparency of the resultant TPUs by decreasing the degree of microphase separation evidenced by ATR-FTIR and DSC. Interestingly, packing density of hard segments and the degree of microphase separation determined the self-healing efficiency of TPUs, which showed good performances in the case of sourced macrodiols from triple diol-monomers.