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.

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.

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.

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.

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.

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.

Multicycling of Epoxy Thermoset Through a Two-Step Strategy of Alcoholysis and Hydrolysis using a Self-Separating Catalysis System.

Plastic has now become a contradiction between civilization and pollution that human society has to resolve. The recycling of thermosetting plastics in waste plastics is a huge challenge since they are difficult to remold like thermoplastic plastics due to their high crosslinking density. Here, a new strategy was developed to achieve multicycling of anhydride-cured epoxy thermosets. The process consisted of mild and high-efficiency alcoholysis catalyzed by potassium phosphate/low-boiling alcohol system, and subsequent fast hydrolysis to obtain degradation products rich of carboxyl groups. The degradation products were reused as curing agent to prepare new anhydride-cured epoxy thermosets without sacrifice of high strength and stability. Moreover, the new epoxy thermosets could still be repeatedly recycled using the same protocol. The insolubility of potassium phosphate in ethanol at room temperature made the separation and reuse of the catalyst more convenient. The use of low-boiling alcohol not only allowed high-efficiency degradation but also enabled easy separation from the degradation products. The excellent degradation performance was attributed to the improved swelling of the thermoset and the increased solubility of potassium phosphate induced by small amounts of water in the alcohol. This research provides a recycling method that can reintegrate thermoset waste plastics into remodeling ones under the background of circular economy.

Recycling waste thermosetting unsaturated polyester resins into oligomers for preparing amphiphilic aerogels.

The styrene-maleic acid copolymer (SMC) was obtained by selective and complete cleavage of ester groups from waste thermosetting unsaturated polyester resins (WTUPR). The degradation was performed in glycol at 180 °C for 5 h with potassium carbonate as a catalyst and the resultant potassium salt of SMC (SMC-K) can be very easily separated by precipitation using ethanol with a yield of 63.8%. The SMC-K was integrated with polyvinyl alcohol to form amphiphilic aerogels via freeze-thaw and freeze-drying processes. The aerogel exhibits a low density of 0.024 g·mL-1 due to hierarchical pore structures with a size range from nanometer to micrometer scale. Besides, the good compressibility and resilience of the aerogel are demonstrated. The amphiphilic aerogel displayed high absorption of both water and oily liquids (over 30 g.g-1 and 20 g.g-1 for water and dichloromethane respectively), together with a good recycle adsorption efficiency (>90% after 10 cycles). This work provides a new strategy on upcycling of WTUPR.

A new amphoteric superabsorbent hydrogel based on sodium starch sulfate.

A new amphoteric superabsorbent hydrogels were synthesized by graft copolymerization blending based on acrylamide (AM), diallydimethylammonium chloride (DMDAAC) and sodium starch sulfate (SSS). The effect of polymerization conditions on swelling capacity was investigated. The results showed that the swelling capacity was affected by various factors, such as polymerization temperature, concentration of initiator and crosslinker, and dose of AM. Additionally, the results testified that salt bond was a potential crosslinking factor in the amphoteric hydrogel. The maximum swelling capacity in distilled water and saline solution reached 1493.1 and 91.0 g/g, respectively. These results were compared with those obtained from original starch-based hydrogel.

Synthesis and characterization of a porous and hydrophobic cellulose-based composite for efficient and fast oil-water separation.

Oily wastewater is generated in diverse industrial processes, and its treatment has become crucial due to increasing environmental concerns. Herein, silanized cellulose was prepared by sol-gel reaction between microcrystalline cellulose (MCC) and hexadecyltrimethoxysilane (HDTMS) using for oil-water separation. The silanized cellulose was characterized by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and thermal gravimetric analysis (TGA). A higher mass ratio of HDTMS to MCC made silanized cellulose become looser, and showed lower water absorbency. The silanized cellulose exhibited specific separation performance towards vegetable oil-water mixture (not for mineral oil-water mixture) with separation efficiency of 99.93%. Moreover, the separation was fast with a water flux of 4628.5Lm(-2)h(-1). The separation efficiency still remained at 99.77% even after recycling for 10 times.

Direct determination of creatinine based on poly(ethyleneimine)/phosphotungstic acid multilayer modified electrode.

In this work, the direct determination of creatinine was achieved using a poly(ethyleneimine)/phosphotungstic acid multilayer modified electrode with the assistance of Copper(II) ions by cyclic voltammetry. The quantity of creatinine were determined by measuring the redox peak current of Cu(II)-creatinine complex/Cu(I)-creatinine complex. Factors affecting the response current of creatinine at the modified electrode were optimized. A linear relationship between the response current and the concentration of creatinine ranging from 0.125 to 62.5µM was obtained with a detection limit of 0.06µM. The proposed method was applied to determine creatinine in human urine, and satisfied results were gotten which was validated in accordance with high performance liquid chromatography. The proposed electrode provided a promising alternative in routine sensing for creatinine without enzymatic assistance.