Cartilage-Inspired, High-Strength, and Heat-Tolerant Lubricating Hydrogels by Macrophase Separation.

Hydrogels are considered as a potential cartilage replacement material based on their structure being similar to natural cartilage, which are of great significance in repairing cartilage defects. However, it is difficult for the existing hydrogels to combine the high load bearing and low friction properties (37 °C) of cartilage through sample methods. Herein, we report a facile and new fabrication strategy to construct the PNIPAm/EYL hydrogel by using the macrophase separation of supersaturated N-isopropylacrylamide (NIPAm) monomer solution to promote the formation of liposomes from egg yolk lecithin (EYL) and asymmetric template method. The PNIPAm/EYL hydrogels possess a relatively high compressive strength (more than 12 MPa), fracture energy (9820 J/m2), good fatigue resistance, lubricating properties, and excellent biocompatibility. Compared with the PNIPAm hydrogel, the friction coefficient (COF 0.046) of PNIPAm/EYL hydrogel is reduced by 50%. More importantly, the COF (0.056) of PNIPAm/EYL hydrogel above lower critical solution temperature (LCST) does not increase significantly, exhibiting heat-tolerant lubricity. The finite element analysis further proves that PNIPAm/EYL hydrogel can effectively disperse the applied stress and dissipate energy under load conditions. This work not only provides new insights for the design of high-strength lubricating hydrogels but also lays a foundation for the treatment of cartilage injury as a substitute material.

An Integrative Chemical Recycling Approach for Catalytic Oxidation of Epoxy Resin and in situ Separation of Degraded Products.

Although many approaches have been proposed to recycling waste epoxy resin (EP), the separation of mixed degraded products remains a challenge due to their similar structures. To address this, we present a catalytic oxidation strategy that enables mild degradation of EP and in situ separation of degraded products through supramolecular interactions. The oxidative degradation relies on FeIV=O radicals with strong oxidizing properties, which are generated from the electron transfer of FeCl2 with reaction reagents. As the FeIV=O radicals attacked the C-N bonds of EP, EP was broken into fragments rich in active functional groups. Meanwhile, the FeIV=O radicals were reduced to iron ions that can coordinate with the carboxyl groups on the fragments. As a result, the degraded products with different carboxyl content can be effortlessly separated into liquid and solid phase by coordinating with the catalyst. The success of this work lays the foundation for high-value application of degraded products and provides new design ideas for recycling waste plastics with complex compositions.

Oxidative Upcycling of Polyethylene to Long Chain Diacid over Co-MCM-41 Catalyst.

Plastic pollution is an emerging global threat due to lack of effective methods for transforming waste plastics into useful resources. Here, we demonstrate a direct oxidative upcycling of polyethylene into high-value and high-volume saturated dicarboxylic acids in high carbon yield of 85.9 % in which the carbon yield of long chain dicarboxylic (C10-C20) acids can reach 58.9% over cobalt-doped MCM-41 molecular sieves, in the absence of any solvent or precious metal catalyst. The distribution of the dicarboxylic acids can be controllably adjusted from short-chain (C4-C10) to long-chain ones (C10-C20) through changing cobalt loading of MCM-41 under nanoconfinement. Highly and sparsely dispersed cobalt along with confined space of mesoporous structure enables complete degradation of polyethylene and high selectivity of dicarboxylic acid in mild condition. So far, this is the first report on highly selective one-step preparation of long chain dicarboxylic acids. The approach provides an attractive solution to tackle plastic pollution and a promising alternative route to long chain diacids.

Amphibious Nastic Hydrogel Based on the Tropic Movement of Gelatin and Its Opposite Phase Transition to PNIPAm.

Mimicking the anisotropic structure and environmental adaptation of organisms in nature remains a key objective in the field of hydrogels. However, it has been very challenging due to complex fabrication and confined application only in water. Here, we demonstrate a new strategy of spontaneous fabrication of an anisotropic hydrogel based on our finding in the tropic movement of gelatin toward the Teflon template. The obtained hydrogel exhibits fast response and recovery under temperature stimuli both in aqueous and non-aqueous environments, making use of the approximate transition temperature and opposite phase transition behavior of gelatin and poly(N-isopropylacrylamide) (PNIPAm). Its recovery performance in water is more than 50 times faster than that of the PNIPAm hydrogel. Furthermore, the PNIPAm/gelatin hydrogel can achieve 3D complex deformations, stealth deformation, erasable and reprogrammed surface patterning, and multistage encryption by simply modulating the location and shape of gelatin to achieve an anisotropic structure. The work provides a simple and versatile way to obtain an anisotropic hydrogel with a definite and predictable structure, which is demonstrated across a range of different monomers. It improves the responsive performance and broadens the hydrogel application to the non-aqueous environment. Additionally, this tropic movement of gelatin can be extended for the design of new types of anisotropic materials and thus endows the materials with diverse functionality.

Dual Photo-Responsive Diphenylacetylene Enables PET In-Situ Upcycling with Reverse Enhanced UV-Resistance and Strength.

A novel in situ chemical upcycling strategy for plastic waste is proposed by the customized diphenylacetylene monomer with dual photo-response. That is, diphenylacetylene reactive monomers are in situ inserted into the macromolecular chain of polyethylene terephthalate (PET) plastics/fibers through one-pot transesterification of slight-depolymerization and re-polymerization. On the one hand, the diphenylacetylene group absorbs short-wave high-energy UV rays and then releases long-wave low-energy harmless fluorescence. On the other hand, the UV-induced photo-crosslinking reaction among diphenylacetylene groups produces extended π-conjugated structure, resulting in a red-shift (due to decreased HOMO-LUMO separation) in the UV absorption band and locked crosslink points between PET chains. Therefore, with increasing UV exposure time, the upcycled PET plastics exhibit reverse enhanced UV resistance and mechanical strength (superior to original performance), instead of serious UV-photodegradation and damaged performance. This upcycling strategy at oligomer-scale not only provides a new idea for traditional plastic recycling, but also solves the common problem of gradual degradation of polymer performance during use.

PEG-Induced Controllable Thin-Thickness Gradient and Water Retention: A Simple Way to Programme Deformation of Hydrogel Actuators.

Building the differential growth through the thickness is a promising and challenging approach to design the morphing structures of hydrogel actuators. Besides retaining the size of the hydrogel actuators under environmental stimuli still remains a big challenge. Herein, a facile and universal approach is developed to address both issues by introducing PEG during the polymerization of N-isopropylacrylamide (NIPAm) via one step method using asymmetric mold. Both composition gradient and pore gradient are obtained in micro level along the thickness direction of the final hydrogel, while thin-thickness gradient in macro level. The thickness gradient and water retention can be controllably adjusted by changing PEG concentration. The introduction of PEG effectively improves both responsive and non-shrunken performance by the interaction with PNIPAm. The resultant anisotropic PNIPAm/PEG hydrogel respond quickly and reach maximum deformation (360°) within 10 s at low temperature (40 °C). The various 3D shape and biomimetic movement can be programmed by simply controlling the PEG concentration and mold shape. This strategy can provide new insights into the design intelligent soft materials with 3D morphing for bioinspired and biomedical applications.

Autofluorescence of hydrogels without a fluorophore.

Fluorescent hydrogels have recently attracted great attention for medical diagnostics, bioimaging and environmental monitoring. However, additional phosphors or fluorophores are always required to label the hydrogels, and they suffer from marker bleaching, signal drifts, or information misrepresentation. Here we report autofluorescence that universally exists in carbonyl-containing hydrogels without any traditional fluorophore. The fluorescence is successfully employed to self-monitor the gelation process since the fluorescence signal is closely related to the internal structural change of the gels. The crosslinked structure is beneficial to the fluorescence efficiency. Specifically, the fluorescence intensity is amplified with decreasing water content of the gels. The system realizes aggregation-induced emission in a water-deficient environment. The fluorescence is quenched by the addition of some specific metal ions, which can realize the successfully erasure and rewriting of information under visible light and ultraviolet light respectively. We believe that the spontaneous fluorescence of a gel provides the most reliable basis for the detection of a gel structure and opens new prospects in the application of hydrogels.

A Fast, Reversible, and Robust Gradient Nanocomposite Hydrogel Actuator with Water-Promoted Thermal Response.

Poly(N-isopropylacrylamide)/Laponite (PNIPAM/Laponite) gradient nanocomposite hydrogel actuators are developed as temperature-controlled actuators with excellent performance using a facile electrophoresis method. The actuators exhibit a rapid (20 s response time) and reversible response, as well as large deformation (bending angle of 231°), which is due to the graded forces generated by the thermo-induced anisotropic shrinkage and extension of the gradient hydrogels. A good linear relationship is observed between the maximum bending angles and the corresponding temperatures for the actuators with fixed sizes. Moreover, the gradient hydrogel with high water content achieved larger actuation angles and shorter response time than the one with low water content, showing an interesting water-promoted effect. Meanwhile, different types of actuators are designed to suit for more specific scenarios, and may be used for various applications, such as biosensing, artificial organization, and transportation of targeted objects.

Tough dual nanocomposite hydrogels with inorganic hybrid crosslinking.

A dual nanocomposite hydrogel with inorganic hybrid crosslinking was fabricated through a simultaneous sol-gel technique and free radical polymerization. Due to the multi-strengthening mechanism of the dual nanocomposite, the hydrogel was super tough and strong with a compressive stress of 32.00 MPa without rupture even at 100% strain, while it exhibited excellent fatigue resistant properties.

The effect of polysaccharide types on adsorption properties of LbL assembled multilayer films.

Three types of biocompatible films were fabricated via electrostatic layer-by-layer (LbL) adsorption of oppositely charged cationic polyurethane and anionic polysaccharides with different primary structures, including sodium hyaluronate, sodium carboxymethyl cellulose and sodium alginate. The adsorption behaviors of films were investigated by using the cationic dye methylene blue (MB) as a model drug at various pH values and salt concentrations. The relationship between the type of polysaccharide and the adsorption behavior of LbL films was comparatively studied. It was found that the adsorption capacity increased with an increase of the initial concentration of MB in the concentration range of the experiment to all of the films, and the pH of environment ranged from 3.0 to 9.0. The Langmuir equation fit perfectly to the experiment data. In addition, a pseudo second-order adsorption model can well describe the adsorption behaviors of MB for three films. The results showed that the type of side chains and the charge density of the polysaccharides played key roles in the adsorption properties of the PU/polysaccharide multilayer films.

Waste treats waste: Facile fabrication of porous adsorbents from recycled PET and sodium alginate for efficient dye removal.

Dye-contaminated water and waste plastic both pose enormous threats to human health and the ecological environment, and simultaneously solving these two issues in a sustainable and resource-saving way is highly important. In this work, a sodium alginate-polyethylene terephthalate-sodium alginate (SA@PET) composite adsorbent for efficient dye removal is fabricated using wasted PET bottle and marine plant-based SA via simple and energy-efficient nonsolvent-induced phase separation (NIPS) method. Benefiting from its porous structure and the abundant binding sites, SA@PET shows an excellent methylene blue (MB) adsorption capacity of 1081 mg g-1. The Redlich-Peterson model more accurately describes the adsorption behavior, suggesting multiple adsorption mechanisms. In addition to the electrostatic attractions of SA to MB, polar interactions between the PET matrix and MB are also identified as adsorption mechanisms. It is worth mentioning that SA@PET could be recycled 7 times without a serious decrease in performance, and the trifluoroacetic acid-dichloromethane solvent involved in the NIPS process has the possibility of reuse and stepwise recovery. Finally, the discarded adsorbent could be completely degraded under mild conditions. This work provides not only a composite adsorbent with excellent cationic dye removal performance for wastewater treatment, but also an upcycling strategy for waste PET.

Upcycling Waste Thermosetting Polyimide Resins into High-Performance and Sustainable Low-Temperature-Resistance Adhesives.

Thermosetting polyimide (PI) has attracted extensive attention for its excellent properties, but the approaches to its end-of-life management are not sustainable, posing great threat to the ecosystem. Herein, this work proposes a mild, sustainable, and full recovery path for recycling waste carbon fiber reinforced phenylethynyl end-capped PI resin composites. In addition to recycling reaction reagent and woven carbon fiber, degraded products (DPETI) can be fully and directly used as high-performance and sustainable adhesives. DPETI exhibits strong adhesion to various surfaces, with a maximum adhesion strength of 1.84 MPa. Due to the strong supramolecular polymerization behavior without solvent dependence, DPETI demonstrates higher adhesive strength of 2.22 MPa in the extreme environment (-196 °C), which is maintained even after 10 cycles. This work sparks a new thinking for plastic wastes recycling that is to convert unrecyclable wastes into new and sustainable materials, which has the potential to establish new links within circular economies and influence the development of materials science.

Internal water circulation mediated synergistic co-hydrolysis of PET/cotton textile blends in gamma-valerolactone.

Recycling strategies for mixed plastics and textile blends currently aim for recycling only one of the components. Here, we demonstrate a water coupling strategy to co-hydrolyze polyester/cotton textile blends into polymer monomers and platform chemicals in gamma-valerolactone. The blends display a proclivity for achieving an augmented 5-hydroxymethylfurfural yield relative to the degradation of cotton alone. Controlled experiments and preliminary mechanistic studies underscore that the primary driver behind this heightened conversion rate lies in the internal water circulation. The swelling and dissolving effect of gamma-valerolactone on polyester enables a fast hydrolysis of polyester at much lower concentration of acid than the one in the traditional hydrolysis methods, effectively mitigating the excessive degradation of cotton-derived product and undesirable product formation. In addition, the system is also applicable to different kinds of blends and PET mixed plastics. This strategy develops an attractive path for managing end-of-life textiles in a sustainable and efficient way.

Gradient hydrogel actuator with fast response and self-recovery in air.

The driving principle of a thermal-responsive hydrogel that loses water at high temperature and absorbs water at low temperature limits its application in an aqueous environment. Here, a gradient hydrogel actuator was developed by introducing sodium hyaluronate into poly(N-isopropylacrylamide) hydrogel by an asymmetric mold method. The hydrogel exhibited a fast response above the LCST in air and unusual self-recovery without the need for further temperature stimuli. The actuation behavior was related to conversion from free water to bound water and water retention within the gradient matrix. The self-recovery mechanism was explored. This work provides a new insight into designing bionic hydrogels applied in a non-aqueous environment.

Water-solvent regulation on complete hydrolysis of thermosetting polyester and complete separation of degradation products.

As one of the largest productions of thermosetting plastics, unsaturated polyester resin (UPR) is difficult to be effectively chemcycled after it is discarded due to its dense network structure. Herein, we demonstrate a mild method for efficient alkaline hydrolysis of UPR into useful feedstocks in mixed solvents of polar aprotic solvent and a small amount of H2O by utilizing the fragmentation effect of the solvent on the UPR and the swelling effect of H2O on the subsequent partially hydrolyzed UPR respectively. The mixed solvents also play a key role in the aggregation and solubility of the degradation products. It is worth noting that the tetrahydrofuran (THF)-H2O system achieved 100 % separation of degradation products in an energy-efficient way taking advantage of the insolubility of the carboxylate-containing products in THF and the low boiling point of THF. The participation of non-reactive mixed solvents greatly promotes both the degradation and the separation process of thermosetting polymers.

Tandem oxidative and thermal cracking of polypropylene at low temperatures.

Polypropylene waste was upcycled into terminal functionalized long-chain chemicals with the aid of anionic surfactants. The reaction only needs to be heated at 80 °C for 5 min by coupling exothermic oxidative cracking with endothermic thermal cracking. This work opens a new way to rapidly convert plastic waste into high-value-added chemicals under mild conditions.

Mechanically tunable ion-crosslinked alginate-based gradient hydrogels by electrolysis-electrophoresis method.

Introducing the gradient structure into ion-crosslinked polysaccharide (ICP) hydrogels is an effective strategy to expand their application scope in biomedicine and smart materials. However, fast gelation between polysaccharide and metal ion makes it difficult to construct/regulate gradient structure. Here, we developed a new method to address the issue by combining electrolysis with electrophoresis. Making use of the gradual generation of copper ions from the Cu anode and continuous migration to the cathode, a Cu2+-crosslinked sodium alginate (SA)-based hydrogel was obtained with both crosslinking density gradient and SA distribution gradient. The gradient structure can be conveniently adjusted to achieve excellent mechanical properties and delicate patterning. The electrolysis-electrophoresis method is successfully extended to versatile hydrogels by varying different metal electrodes (Fe or Zn electrodes), or different types of polysaccharides (chitosan or sodium carboxymethyl cellulose). This work opens a new insight for designing gradient ICP hydrogels and provides the potential for bionic applications.

Coding and Noncoding RNA Expression Profiles of Spleen CD4+ T Lymphocytes in Mice with Echinococcosis.

Cystic echinococcosis (CE) is a severe and neglected zoonotic disease that poses health and socioeconomic hazards. So far, the prevention and treatment of CE are far from meeting people's ideal expectations. Therefore, to gain insight into the prevention and diagnosis of CE, we explored the changes in RNA molecules and the biological processes and pathways involved in these RNA molecules as E. granulosus infects the host. Interferon (IFN)-γ, interleukin (IL)-2, IL-4, IL-6, IL-10, IL-17A, and tumor necrosis factor (TNF)-α levels in peripheral blood serum of E. granulosus infected and uninfected female BALB/c mice were measured using the cytometric bead array mouse Th1/Th2/Th17 cytokine kit. mRNA, microRNA (miRNA), long noncoding RNA (lncRNA), and circular RNA (circRNA) profiles of spleen CD4+ T cells from the two groups of mice were analyzed using high-throughput sequencing and bioinformatics. The levels of IFN-γ, IL-2, IL-4, IL-6, IL-10, IL-17A, and TNF-α were significantly higher in the serum of the CE mice than in control mice (P < 0.01). In total, 1,758 known mRNAs, 37 miRNAs, 175 lncRNAs, and 22 circRNAs were differentially expressed between infected and uninfected mice (|fold change| ≥ 0.585, P < 0.05). These differentially expressed molecules are involved in chromosome composition, DNA/RNA metabolism, and gene expression in cell composition, biological function, and cell function. Moreover, closely related to the JAK/STAT signaling pathways, mitogen-activated protein kinase signaling pathways, P53 signaling pathways, PI3K/AKT signaling pathways, cell cycle, and metabolic pathways. E. granulosus infection significantly increased the levels of IFN-γ, IL-2, IL-4, IL-6, IL-10, IL-17A, and TNF-α in mouse peripheral blood of mice and significantly changed expression levels of various coding and noncoding RNAs. Further study of these trends and pathways may help clarify the pathogenesis of CE and provide new insights into the prevention and treatment of this disease.

Multifunctional Materials from Aerobic Degradation of Epoxy Thermoset via Phosphotungstic Acid-Involved Activation and Bonding.

The growing scale of production of wind turbines represents a big challenge for chemical recycling of amine-cured epoxy resin (EP) to achieve high-efficiency degradation and high-value utilization of degradation products. Here, H2 O2 /phosphotungstic acid (HPW) catalytic oxidation system is demonstrated to completely degrade EP thermoset with the solid recovery rate of 96% at a reaction temperature of 80 °C for 4 h. Owing to protonation and bonding effect of HPW to the amine groups, the degradation products had a weight-average molecular weight of 4285 with narrow molecular weight distribution. They were used as dye adsorption blend films and supramolecular adhesives based on hydrogen bonding and coordination bonding respectively. The work demonstrates a feasible and promising method to recover the EP thermoset into high-performance materials.

Exploiting valuable supramolecular materials from waste plastics.

A new family of supramolecular materials is exploited from waste thermosets via a one-step retrosynthetic approach, which exhibits distinguished adhesion properties in dry/wet environments, good corrosion resistance and dynamic reversibility. This work opens up a wide design space for supramolecular materials with excellent performances and proposes a new strategy for efficient utilization of hybrid degraded products.