Advances in lignin-based biosorbents for sustainable wastewater treatment.

The heavy metals, pesticides and dyes in agriculture and industry caused serious water pollution have increased the urgency for the advancement of biomass-based adsorbents due to their merits of low cost, high efficiency, and environmental sustainability. Thus, this review systematically examines the recent progress of lignin-based adsorbents dedicated to wastewater purification. Commencing with a succinct exposition on the intricate structure and prevalent forms of lignin, the review proceeds to expound rational design strategies tailored for lignin-based adsorbents coupled with adsorption mechanisms and regeneration methods. Emphasis is placed on the potential industrial applications of lignin-based adsorbents, accentuating their capacity for recovery and direct utilization post-use. The future challenges and outlooks associated with lignin-based adsorbents are discussed to provide novel perspectives for the development of high-performance and sustainable biosorbents, facilitating the effective removal of pollutants and the value-added utilization of resources in a sustainable manner.

Green and Low-Cost Alkali-Polyphenol Synergetic Self-Catalysis System Access to Fast Gelation of Self-Healable and Self-Adhesive Conductive Hydrogels for Self-Powered Triboelectric Nanogenerators.

Biomass-based hydrogels have attracted great attention in flexible and sustainable self-powered power sources but struggled to fabricate in a green, high-efficiency, and low-cost manner. Herein, a novel and facile alkali-polyphenol synergetic self-catalysis system is originally employed for the fast gelation of self-healable and self-adhesive lignin-based conductive hydrogels, which can be regarded as hydrogel electrodes of flexible triboelectric nanogenerators (TENGs). This synergy self-catalytic system comprises aqueous alkali and polyphenol-containing lignin, in which alkali-activated ammonium persulfate (APS) significantly accelerates the generation of radicals and initiates the polymerization of monomers, while polyphenol acts as a stabilizer to avoid bursting polymerization from inherent radical scavenging ability. Furthermore, multiple hydrogen bonds between lignin biopolymers and polyacrylamide (PAM) chains impart lignin-based hydrogels with exceptional adhesiveness and self-healing properties. Intriguingly, the alkaline conditions not only contribute to the solubility of lignin but also impart superior ionic conductivity of lignin-based hydrogel that is applicable to flexible TENG in self-powered energy-saving stair light strips, which holds great promise for industrial applications of soft electronics.

Surface Control Behavior toward Crystal Regulation and Anticorrosion Capacity for Zinc Metal Anodes.

The commercial application of high-safety aqueous zinc (Zn) secondary batteries is hindered by the poor cycling life of Zn metal anodes. Here we propose a dendrite growth and hydrogen evolution corrosion reaction mechanism from the binding energy of the deposited crystal plane on the Zn surface and the adsorption energy of H2O molecules on different crystal planes as well as the binding energy of H2O molecules with Zn2+ ions. The biomass-based alkyl polyglucoside (APG) surfactant is adopted as an electrolyte additive of 0.15% to regulate the preferential growth of a parallel Zn(002) plane and enhance the anticorrosion ability of Zn metal anodes. The robust binding and adsorption energies of APG with Zn2+ ions in the aqueous electrolyte and the Zn(002) plane on Zn surface generate a synergistic effect to increase the concentration of Zn2+ ions on the APG-adsorbed Zn(002) plane, endowing the continuous growth of the preferential parallel Zn(002) plane and the excellent anticorrosion capacity. Accordingly, the long-term cycle stability of 4000 h can be achieved for Zn anodes with APG additives, which is better than that with pure ZnSO4 electrolyte. With the addition of APG in the anolyte electrolyte, Zn-I2 full cells display excellent cycling performance (70 mAh g-1 after 20000 cycles) as compared with that without APG additives.

Lithium Bonds Enable Small Biomass Molecule-Based Ionoelastomers with Multiple Functions for Soft Intelligent Electronics.

Lipoic acid (LA), which originates from animals and plants, is a small biomass molecule and has recently shown great application value in soft conductors. However, the severe depolymerization of LA places a significant limitation on its utilization. A strategy of using Li-bonds as both depolymerization quenchers and dynamic mediators to melt transform LA into high-performance ionoelastomers (IEs) is proposed. They feature dry networks while simultaneously combining transparency, stretchability, conductivity, self-healing ability, non-corrosive property, re-mouldability, strain-sensitivity, recyclability, and degradability. Most of the existing soft conductors' drawbacks, such as the tedious synthesis, non-renewable polymer networks, limited functions, and single-use only, are successfully solved. In addition, the multi-functions allow IEs to be used as soft sensors in human-computer interactive games and wireless remote sports assistants. Notably, the recycled IE also provides an efficient conductive filler for transparent ionic papers, which can be used to design soft transparent triboelectric nanogenerators for energy harvesting and multidirectional motion sensing. This work creates a new direction for future research involving intelligent soft electronics.

Highly Conductive and Mechanically Robust Cellulose Nanocomposite Hydrogels with Antifreezing and Antidehydration Performances for Flexible Humidity Sensors.

Conductive hydrogels are emerging as an appealing material platform for flexible electronic devices owing to their attractive mechanical flexibility and conductive properties. However, the conventional water-based conductive hydrogels tend to inevitably freeze at subzero temperature and suffer from continuous water evaporation under ambient conditions, leading to a decrease in their electrical conductivities and mechanical properties. Thus, it is extremely necessary, but generally challenging, to create an antifreezing and antidehydration conductive gel for maintaining high and stable performances in terms of electrical conductivity and mechanical properties. Herein, we fabricated a cellulose nanofibril (CNF)-reinforced and highly ion-conductive organogel featuring excellent antifreezing and antidehydration performances by immersing it in the CaCl2/sorbitol solution for solvent displacement. The incorporation of a rigid CNF serving as a dynamic connected bridge provided a hierarchical honeycomb-like cellular structure for the obtained CS-nanocomposite (NC) organogel networks, facilitating significant mechanical reinforcement. The synergy effects of sorbitol and CaCl2 allowed high-performance integration with excellent antifreezing tolerance, antidehydration ability, and ionic conductivity. Strong hydrogen bonds were formed between water molecules and sorbitol molecules to impede the formation of ice crystals and water evaporation, thereby imparting the CS-NC organogels with extreme-temperature tolerance as low as -50 °C and pre-eminent antidehydration performance with over 90% weight retention. Furthermore, this CS-NC organogel exhibited high humidity sensitivity in a wide humidity detection range (23∼97% relative humidity) because of the ready formation of hydrogen bonds between water molecules and numerous hydrophilic groups in the binary solvent and elaborated polymer chains, which can be assembled as a stretchable humidity sensor to monitor human respiration with a fast response. This work provides a new prospect for fabricating intrinsically stretchable and high-performance humidity sensors using cellulose-based humidity-responsive materials for the emerging wearable applications.

Chitosan-based multifunctional flexible hemostatic bio-hydrogel.

Realizing the potential application of chitosan as an effective biomedical hemostatic agent has become an emerging research hotspot. However, fabricating a flexible chitosan-based hemostatic bio-hydrogel with self-adhesion feature in humid conditions and rapid hemostasis capability remains a challenge. Herein, we reported the development of chitosan-based hydrogels (DCS-PEGSH gels) with typical multilevel pore structures, which were cross-linked by 3-(3,4-dihydroxyphenyl) propionic acid-modified chitosan (DCS) and sebacic acid-terminated polyethylene glycol modified by p-hydroxybenzaldehyde (PEGSH). By precisely regulating the proportion of PEGSH, the fabricated bio-hydrogels displayed favorable cytocompatibility, suitable stretchability (∼780%), and blood absorbability (1300% ± 50%). Moreover, the strong adhesion (∼68.5 kPa) of the assembled bio-hydrogel ensured its firm adherence on pigskin and on bleeding wound in both static and dynamic humid environments without shedding, thus providing a long service life. The fabricated hydrogels exhibited shorter blood clotting time (50 s) and lower blood clotting index (BCI, 41) than the commercial chitosan sponge (288 s, BCI 65). Notably, the amount of blood loss from the liver in mice was reduced by almost 90% as compared to that for the control group. This study paves a solid way for developing a chitosan-based hydrogel with self-adhesive, self-healing, stretchability, biocompatibility, and antibacterial and antioxidant properties through molecular design and structural regulation, which will enable the biomedical application of chitosan in emergency hemostasis, particularly in joints and extremities. STATEMENT OF SIGNIFICANCE: The design and preparation of multifunctional integrated green adhesive bio-hydrogels while avoiding the use of organic solvents and toxic chemical reagents has been an emerging challenge. Herein, a flexible chitosan-based hemostatic bio-hydrogel that integrates multifunctional properties was successfully synthesized. The bio-hydrogel displayed suitable stretchability (780%) and blood absorbability (1300% ± 50%). Moreover, the strong adhesion (68.5 kPa) ensured firm adherence of the assembled hydrogel on pigskin and on the bleeding wound site in both static and dynamic humid environments without shedding, thus providing a long service life. In addition, the designed hydrogel showed good compatibility and antibacterial performance. The dynamic Schiff base endowed the bio-hydrogel with excellent self-healing performance without any external stimuli.

A mussel-inspired flexible chitosan-based bio-hydrogel as a tailored medical adhesive.

The significant progress in efforts to design hydrogel adhesive mimicking mussels' functions has been witnessed in recent years. However, it is still an arduous challenge to fabricate self-adhesive hydrogel adhesive that tradeoff of exalting features containing scalability, self-healing, degradability, biocompatibility, and antibacterial properties. Herein, we manufactured a multi-functional physical hydrogel adhesive by integrating catechol groups modified chitosan and polyvinyl alcohol (PVA). Intriguingly, the physical gels reinforce durable and repeatable adhesiveness due to the limited auto-oxidation of catechol groups of the 3-(3,4-dihydroxyphenyl) propionic acid modified chitosan (DCS), which can be adhered diametrically on human skin without shedding and residue. Additionally, the dynamic H-bonds between DCS and PVA endows the hydrogel to self-heal under a relatively mild stimulation. The assembly of silver nano armor remarkably enhances the mechanical strength and antibacterial of the hydrogel. Meanwhile, the metal coordination formed between the nano-silver and the hydroxyl groups of catechol and the electrostatic interaction between the silver ions and the hydroxyl groups also contribute to the hydrogel to achieve self-healing. This work provides a neoteric prospect in designing degradable hydrogels with stretchability, self-adhesion, self-healing, antibacterial and biocompatibility for potential applications in tissue adhesion and wound healing.

Tannic Acid-Silver Dual Catalysis Induced Rapid Polymerization of Conductive Hydrogel Sensors with Excellent Stretchability, Self-Adhesion, and Strain-Sensitivity Properties.

The application of conductive hydrogels in intelligent biomimetic electronics is a hot topic in recent years, but it is still a great challenge to develop the conductive hydrogels through a rapid fabrication process at ambient temperature. In this work, a versatile poly(acrylamide) @cellulose nanocrystal/tannic acid-silver nanocomposite (NC) hydrogel integrated with excellent stretchability, repeatable self-adhesion, high strain sensitivity, and antibacterial property, was synthesized via radical polymerization within 30 s at ambient temperature. Notably, this rapid polymerization was realized through a tannic acid-silver (TA-Ag) mediated dynamic catalysis system that was capable of activating ammonium persulfate and then initiated the free-radical polymerization of the acrylamide monomer. Benefiting from the incorporation of TA-Ag metal ion nanocomplexes and cellulose nanocrystals, which acted as dynamic connecting bridges by hydrogen bonds to efficiently dissipate energy, the obtained NC hydrogels exhibited prominent tensile strain (up to 4000%), flexibility, self-recovery, and antifatigue properties. In addition, the hydrogels showed repeatable adhesiveness to different substrates (e.g., glass, wood, bone, metal, and skin) and significant antibacterial properties, which were merits for the hydrogels to be assembled into a flexible epidermal sensor for long-term human-machine interfacial contact without concerns about the use of external adhesive tapes and bacterial breeding. Moreover, the remarkable conductivity (σ ∼ 5.6 ms cm-1) and strain sensitivity (gauge factor = 1.02) allowed the flexible epidermal sensors to monitor various human motions in real time, including huge movement of deformations (e.g., wrist, elbow, neck, shoulder) and subtle motions. It is envisioned that this work would provide a promising strategy for the rapid preparation of conductive hydrogels in the application of flexible electronic skin, biomedical devices, and soft robotics.

Autonomous Self-Healing Silk Fibroin Injectable Hydrogels Formed via Surfactant-Free Hydrophobic Association.

Many natural materials, such as silk, animal bone, nacre, and plant fibers, achieve outstanding strength and toughness through the rupture of sacrificial bonds between chain segments in the organic phase. In this work, we present a bioinspired strategy to fabricate silk fibroin-based hydrophobic-association (HA) hydrogels by incorporating the hydrophobic interaction as a sacrificial bond into the alginate ionic network, which not only enhanced the mechanical extensibility, strength, and toughness of the hydrogels but also enabled self-recovery and self-healing properties via reversible hydrophobic interactions without external stimuli at room temperature. The hydrophobic interaction system consisted of the hydrophobic monomer stearyl methacrylate (C18M) and an amphiphilic regenerated silk fibroin (RSF) solution. The mechanical tests and rheometry indicated that the hydrophobic interaction served as the sacrificial bond that preferentially ruptures prior to the alginate ionic network under an external load, which dissipated enormous amounts of energy and conferred an improved mechanical performance. Moreover, the structure of HA gels could be quickly recovered after injection due to the existence of hydrophobic interactions. In addition, the degradability of the HA gels in a protease XIV solution was strongly dependent upon the C18M component, which significantly promoted the degradation rate of HA gels. The biomimetic mineralization process of HA gels within a simulated body fluid (SBF), mimicking the inorganic composition of human blood plasma, was performed and the calcium phosphate nanoparticles on the hydrogel were observed. Importantly, in vivo experiments illustrated that the HA gels exhibited satisfactory biocompatibility, and the mouse osteoblasts (MC3T3-E1) could attach and spread on the hydrogels. Overall, the self-healing, biocompatibility, and high mechanical properties of the HA gels render them potentially suitable for load-bearing applications in drug delivery or other soft tissue-engineering applications.

High-Strength, Self-Adhesive, and Strain-Sensitive Chitosan/Poly(acrylic acid) Double-Network Nanocomposite Hydrogels Fabricated by Salt-Soaking Strategy for Flexible Sensors.

As a promising functional material, hydrogels have attracted extensive attention, especially in flexible wearable sensor fields, but it remains a great challenge to facilely integrate excellent mechanical properties, self-adhesion, and strain sensitivity into a single hydrogel. In this work, we present high in strength, stretchable, conformable, and self-adhesive chitosan/poly(acrylic acid) double-network nanocomposite hydrogels for application in epidermal strain sensor via in situ polymerization of acrylic acid in chitosan acid aqueous solution with tannic acid-coated cellulose nanocrystal (TA@CNC) acting as nanofillers to reinforce tensile properties, followed by a soaking process in a saturated NaCl solution to cross-link chitosan chains. With addition of a small amount of TA@CNC, the double-network nanocomposite hydrogels became highly adhesive and mechanically compliant, which were critical factors for the development of conformable and resilient wearable epidermal sensors. The salt-soaking process was applied to cross-link chitosan chains by shielded electrostatic repulsions between positively charged amino groups, drastically enhancing the mechanical properties of the hydrogels. The obtained double-network nanocomposite hydrogels exhibited excellent tunable mechanical properties that could be conveniently tailored with fracture stress and fracture strain ranging from 0.39 to 1.2 MPa and 370 to 800%, respectively. Besides, the hydrogels could be tightly attached onto diverse substrates, including wood, glass, plastic, polytetrafluoroethylene, glass, metal, and skin, demonstrating high adhesion strength and compliant adhesion behavior. In addition, benefiting from the abundant free ions from strong electrolytes, the flexible hydrogel sensors demonstrated stable conductivity and strain sensitivity, which could monitor both large human motions and subtle motions. Furthermore, the antibacterial property originating from chitosan made the hydrogels suitable for wearable epidermal sensors. The facile soaking strategy proposed in this work would be promising in fabricating high-strength multifunctional conductive hydrogels used for wearable epidermal devices.

Strain Rate-Dependent Viscoelasticity and Fracture Mechanics of Cellulose Nanofibril Composite Hydrogels.

In this work, the composite hydrogel toughening behaviors as manifested by strain rate-dependent viscoelastic properties and enhanced fracture mechanics, that is, suppressed catastrophic crack propagation with increased resistance, are systematically examined by using cellulose nanofibrils (CNFs) as fillers in the polyacrylamide (PAAm) matrix. The uniaxial deformation tests show that the tearing energy increases with crack velocity and becomes dominated by the viscoelastic energy dissipation in front of the crack tip. The creep dynamics of the composite hydrogels under a constant stress is examined, and the results indicate that the incorporation of the CNF pronouncedly suppresses the creep deformation. In addition, the microdeformation and failure mechanisms are analyzed through the observation of morphology of arrested crack tips and the damage zone by transmission electron microscopy and scanning electron microscopy. By aligning the CNF along the crack direction, it is possible to focus on the study of interfacial slip mechanics and identify the role of interfacial slip during the energy dissipation process. The results indicate that the CNFs are largely orientated parallel to the loading direction to maximize the energy dissipation, where the initiation of crack propagation is the primary fracture mechanism in composite hydrogels. The coarse feature on the composite fracture surface implies that the CNF initiates deflection of crack propagation fronts and thus increases the strain energy for continuation of the fracture. It is envisioned that with the incorporation of interdisciplinary strategies, one can rationally combine multiple approaches toward the creation of nanocomposite hydrogels with enhanced mechanical properties.

Mimicking Dynamic Adhesiveness and Strain-Stiffening Behavior of Biological Tissues in Tough and Self-Healable Cellulose Nanocomposite Hydrogels.

Although self-healing gels with structural resemblance to biological tissues attract great attention in biomedical fields, it remains a dilemma for combination between fast self-healing properties and high mechanical toughness. On the basis of the design of dynamic reversible cross-links, we incorporate rigid tannic acid-coated cellulose nanocrystal (TA@CNC) motifs into the poly(vinyl alcohol) (PVA)-borax dynamic networks for the fabrication of a high toughness and rapidly self-healing nanocomposite (NC) hydrogel, together with dynamically adhesive and strain-stiffening properties that are particularly indispensable for practical applications in soft tissue substitutes. The results demonstrate that the obtained NC gels present a highly interconnected network, where flexible PVA chains wrap onto the rigid TA@CNC motifs and form the dynamic TA@CNC-PVA clusters associated by hydrogen bonds, affording the critical mechanical toughness. The synergetic interactions between borate-diol bonds and hydrogen bonds impart a typical self-healing behavior into the NC gels, allowing the dynamic cross-linked networks to undergo fast rearrangement in the time scale of seconds. Moreover, the obtained NC hydrogels not only mimic the main feature of biological tissues with the unique strain-stiffening behavior but also display unique dynamic adhesiveness to nonporous and porous substrates. It is expected that this versatile approach opens up a new prospect for the rational design of multifunctional cellulosic hydrogels with remarkable performance to expand their applications.

High-Strength, Tough, and Self-Healing Nanocomposite Physical Hydrogels Based on the Synergistic Effects of Dynamic Hydrogen Bond and Dual Coordination Bonds.

Dynamic noncovalent interactions with reversible nature are critical for the integral synthesis of self-healing biological materials. In this work, we developed a simple one-pot strategy to prepare a fully physically cross-linked nanocomposite hydrogel through the formation of the hydrogen bonds and dual metal-carboxylate coordination bonds within supramolecular networks, in which iron ions (Fe3+) and TEMPO oxidized cellulose nanofibrils (CNFs) acted as cross-linkers and led to the improved mechanical strength, toughness, time-dependent self-recovery capability and self-healing property. The spectroscopic analysis and rheological measurements corroborated the existence of hydrogen bonds and dual coordination bonds. The mechanical tests and microscopic morphology were explored to elucidate the recovery properties and toughening mechanisms. The hydrogen bonds tend to preferentially break prior to the coordination bonds associated complexes that act as skeleton to maintain primary structure integrity, and the survived coordination bonds with dynamic feature also serve as sacrificial bonds to dissipate another amount of energy after the rupture of hydrogen bonds, which collectively maximize the contribution of sacrificial bonds to energy dissipation while affording elasticity. Additionally, the multiple noncovalent interactions in diverse types synergistically serve as dynamic but highly stable associations, leading to the effective self-healing efficiency over 90% after damage. We expect that this facile strategy of incorporating the biocompatible and biodegradable CNFs as building blocks may enrich the avenue in exploration of dynamic and tunable cellulosic hydrogels to expand their potential applications in the biomedical field.