Nanoconfined polymerization limits crack propagation in hysteresis-free gels.

Consecutive mechanical loading cycles cause irreversible fatigue damage and residual strain in gels, affecting their service life and application scope. Hysteresis-free hydrogels within a limited deformation range have been created by various strategies. However, large deformation and high elasticity are inherently contradictory attributes. Here we present a nanoconfined polymerization strategy for producing tough and near-zero-hysteresis gels under a large range of deformations. Gels are prepared through in situ polymerization within nanochannels of covalent organic frameworks or molecular sieves. The nanochannel confinement and strong hydrogen bonding interactions with polymer segments are crucial for achieving rapid self-reinforcement. The rigid nanostructures relieve the stress concentration at the crack tips and prevent crack propagation, enhancing the ultimate fracture strain (17,580 ± 308%), toughness (87.7 ± 2.3 MJ m-3) and crack propagation strain (5,800%) of the gels. This approach provides a general strategy for synthesizing gels that overcome the traditional trade-offs of large deformation and high elasticity.

Biocompatible Tough Ionogels with Reversible Supramolecular Adhesion.

Cohesive and interfacial adhesion energies are difficult to balance to obtain reversible adhesives with both high mechanical strength and high adhesion strength, although various methods have been extensively investigated. Here, a biocompatible citric acid/L-(-)-carnitine (CAC)-based ionic liquid was developed as a solvent to prepare tough and high adhesion strength ionogels for reversible engineered and biological adhesives. The prepared ionogels exhibited good mechanical properties, including tensile strength (14.4 MPa), Young's modulus (48.1 MPa), toughness (115.2 MJ m-3), and high adhesion strength on the glass substrate (24.4 MPa). Furthermore, the ionogels can form mechanically matched tough adhesion at the interface of wet biological tissues (interfacial toughness about 191 J m-2) and can be detached by saline solution on demand, thus extending potential applications in various clinical scenarios such as wound adhesion and nondestructive transfer of organs.

Interlayer Polymerization to Construct a Fully Conjugated Covalent Organic Framework as a Metal-Free Oxygen Reduction Reaction Catalyst for Anion Exchange Membrane Fuel Cells.

Two-dimensional (2D) covalent organic frameworks (COFs) have a multilayer skeleton with a periodic π-conjugated molecular array, which can facilitate charge carrier transport within a COF layer. However, the lack of an effective charge carrier transmission pathway between 2D COF layers greatly limits their applications in electrocatalysis. Herein, by employing a side-chain polymerization strategy to form polythiophene along the nanochannels, a conjugated bridge is constructed between the COF layers. The as-synthesized fully conjugated COF (PTh-COF) exhibits high oxygen reduction reaction (ORR) activity with narrowed energy band gaps. Correspondingly, PTh-COF is tested as a metal-free cathode catalyst for anion exchange membrane fuel cells (AEMFCs) which showed a maximum power density of 176 mW cm-2 under a current density of 533 mA cm-2. The density functional theory (DFT) calculation reveals that interlayer conjugated polythiophene optimizes the electron cloud distribution, which therefore enhances the ORR performance. This work not only provides new insight into the construction of a fully conjugated covalent organic framework but also promotes the development of new metal-free ORR catalysts.

Regulation of Hydrophobic Structures of Antibacterial Guanidinium-Based Amphiphilic Polymers for Subcutaneous Implant Applications.

Antimicrobial peptide mimics have been used to kill bacteria and construct antibacterial materials. Precise design and construction of chemical structure are essential for easy access to highly effective antimicrobial peptide mimics. Herein, cationic guanidinium-based polymers (PGXs) with varying hydrophobic structures were synthesized to explore the structure and antibacterial activity relationship of antimicrobial peptide mimics and to construct antibacterial implants. The effect of the hydrophobic chemical structure, including carbon chain length and configuration, on the antimicrobial activities against both Escherichia coli and Staphylococcus aureus was investigated. The antibacterial activities of PGXs improved with increasing alkyl chain length, and PGXs with a straight-chain hydrophobic structure exhibited better bactericidal activities than those with cyclic alkane and aromatic hydrocarbon. Furthermore, PGXs grafted with poly(dimethylsiloxane) (PDMS-PGXs) showed a similar bactericidal change tendency of PGXs in solution. Additionally, the PDMS-PGXs showed potent antibiofilm performance in vitro, which can inhibit bacterial infection in vivo as subcutaneous implants. This study may propose a basis for the precise design and construction of antibacterial materials and provide a promising way of designing biomedical devices and implants with bacterial infection-combating activities.

Semi-Interpenetrating Network Anion Exchange Membranes by Thiol-Ene Coupling Reaction for Alkaline Fuel Cells and Water Electrolyzers.

In this work, a thiol-ene coupling reaction was employed to prepare the semi-interpenetrating polymer network AEMs. The obtained QP-1/2 membrane exhibits high hydroxide conductivity (162.5 mS cm-1 at 80 °C) with a relatively lower swelling ratio, demonstrating its mechanical strength of 42 MPa. This membrane is noteworthy for its improved alkaline stability, as the semi-interpenetrating network effectively limits the attack of hydroxide. Even after being treated in 2 M NaOH at 80 °C for 600 h, 82.5% of the hydroxide conductivity is maintained. The H2/O2 fuel cell with QP-1/2 membrane displays a peak power density of 521 mW cm-2. Alkaline water electrolyzers based on QP-1/2 membrane demonstrated a current density of 1460 mA cm-2 at a cell voltage of 2.00 V using NiCoFe catalysts in the anode. All the results demonstrate that a semi-interpenetrating structure is a promising way to enhance the mechanical property, ionic conductivity, and alkaline stability of AEMs for the application of alkaline fuel cells and water electrolyzers.

Unsupervised Learning-Guided Accelerated Discovery of Alkaline Anion Exchange Membranes for Fuel Cells.

Without insight into the correlation between the structure and properties, anion exchange membranes (AEMs) for fuel cells are developed usually using the empirical trial and error method or simulation methods. Here, a virtual module compound enumeration screening (V-MCES) approach, which does not require the establishment of expensive training databases and can search the chemical space containing more than 4.2×105 candidates was proposed. The accuracy of the V-MCES model was considerably improved when the model was combined with supervised learning for the feature selection of molecular descriptors. Techniques from V-MCES, correlating the molecular structures of the AEMs with the predicted chemical stability, generated a ranking list of potential high stability AEMs. Under the guidance of V-MCES, highly stable AEMs were synthesized. With understanding of AEM structure and performance by machine learning, AEM science may enter a new era of unprecedented levels of architectural design.

Ultra-Tough and Recyclable Ionogels Constructed by Coordinated Supramolecular Solvents.

The mechanical properties of most hydrogels (ionogels) are considerably affected by covalently cross-linked networks. However, the interactions between solvent/solvent molecules and solvent/polymer chains are usually ignored. Herein, a series of ultra-tough ionogels were prepared via a supramolecular solvent, halometallate ionic liquid, in which cations and coordinating anions form a 3D supramolecular network. The linear polymer chains are physically cross-linked with supramolecular solvents synergistically enhancing the strength (14.3 MPa), toughness (78 MJ m-3 ), and Young's modulus (55 MPa) of ionogels, effectively dispersing the stress concentration under load, and obtaining better fatigue resistance and higher fracture energy (198 kJ m-2 ). Furthermore, the reversible cross-linking enables green recovery and recycling of ionogels, simply by water. This strategy shows broad applicability based on a variety of supramolecular solvents and coordinatable polymers.

A Superstrong and Reversible Ionic Crystal-Based Adhesive Inspired by Ice Adhesion.

In this study, we developed a superstrong and reversible adhesive, which can possess a high bonding strength in the "adhesive" state and detach with the application of heating. An ionic crystal (IC) gel, in which an IC was immobilized within a soft-polymer matrix, were synthesized via in situ photo-crosslinking of a precursor solution composed of N, N-dimethyl acrylamide (DMAA) and a melted IC. The obtained IC gel is homogenous and transparent at melt point. When cooled to the phase transition temperature of the IC, the gel turns into the adhesive with the adhesion strength of 5.82 MPa (on glasses), due to the excellent wetting of melted gel and a thin layer of crystalline IC with high cohesive strength formed on the substrates. The synergistic effects between IC, polymer networks and substrates were investigated by solid state 1 H NMR and molecular dynamics simulation. Such an adhesive layer is reversable and can be detached by heating and subsequent re-adhesion via cooling. This study proposed the new design of removable adhesives, which can be used in dynamic and complex environments.

High-Toughness and High-Strength Solvent-Free Linear Poly(ionic liquid) Elastomers.

Solvent-free elastomers, unlike gels, do not suffer from solvent evaporation and leakage in practical applications. However, it is challenging to realize the preparation of high-toughness (with both high stress and strain) ionic elastomers. Herein, high-toughness linear poly(ionic liquid) (PIL) elastomers are constructed via supramolecular ionic networks formed by the polymerization of halometallate ionic liquid (IL) monomers, without any chemical crosslinking. The obtained linear PIL elastomers exhibit high strength (16.5 MPa), Young's modulus (157.49 MPa), toughness (130.31 MJ m-3 ), and high crack propagation insensitivity (fracture energy 243.37 kJ m-2 ), owing to the enhanced intermolecular noncovalent interactions of PIL chains. Furthermore, PIL elastomer-based strain, pressure, and touch sensors have shown high sensitivity. The linear noncovalent crosslinked network endows the PIL elastomers with self-healing and recyclable properties, and broad application prospects in the fields of flexible sensor devices, health monitoring, and human-machine interaction.

Nitric oxide-releasing poly(ionic liquid)-based microneedle for subcutaneous fungal infection treatment.

Poor permeation of therapeutic agents and similar eukaryotic cell metabolic and physiological properties of fungi and human cells are two major challenges that lead to the failure of current therapy for fungi-induced skin and soft tissue infections. Herein, a nitric oxide (NO)-releasing poly(ionic liquid)-based microneedle (PILMN-NO) with the capacity of deep persistent NO toward subcutaneous fungal bed is presented as a synergistic antifungal treatment strategy to treat subcutaneous fungal infection. Upon the insertion of PILMN-NO into skin, the contact fungicidal activities induced by electrostatic and hydrophobic effects of poly(ionic liquid) and the released NO sterilization resulting from the peroxidation and nitrification effect of NO achieved enhanced antifungal efficacy against fungi (Candida albicans) both in vitro and in vivo. Simultaneously, PILMN-NO showed biofilm ablation ability and efficiently eliminated mature biofilms. In vivo fungal-induced subcutaneous abscess studies revealed that PILMN-NO could effectively sterilize fungi while suppressing the inflammatory reaction, facilitating collagen deposition and angiogenesis, and promoting wound healing. This work provides a new strategy to overcome the difficulties in deep skin fungal infection treatment and has potential for further exploitation of NO-releasing microbicidal therapy.

Recyclable, Healable, and Tough Ionogels Insensitive to Crack Propagation.

Most gels and elastomers introduce sacrificial bonds in the covalent network to dissipate energy. However, long-term cyclic loading caused irreversible fatigue damage and crack propagation cannot be prevented. Furthermore, because of the irreversible covalent crosslinked networks, it is a huge challenge to implement reversible mechanical interlocking and reorganize the polymer segments to realize the recycling and reuse of ionogels. Here, covalent crosslinking of host materials is replaced with entanglement. The entangled microdomains are used as physical crosslinking while introducing reversible bond interactions. The interpenetrating, entangled, and elastic microdomains of linear segments and covalent-network microspheres provide mechanical stability, eliminate stress concentration at the crack tip under load, and achieve unprecedented tear and fatigue resistance of ionogels in any load direction. Moreover, reversible entanglements and noncovalent interactions can be disentangled and recombined to achieve recycling and mechanical regeneration, and the recyclability of covalent-network microdomains is realized.

Enhanced photocatalytic and antibacterial activity of acridinium-grafted g-C3N4 with broad-spectrum light absorption for antimicrobial photocatalytic therapy.

As a metal-free polymeric photocatalyst, graphitic carbon nitride (g-C3N4) has attracted great attention owing to its high stability and low toxicity. However, g-C3N4 suffers from low light harvesting ability which limits its applications in antimicrobial photocatalytic therapy (APCT). Herein, acridinium (ADN)-grafted g-C3N4 (ADN@g-C3N4) nanosheets are prepared via covalent grafting of ADN to g-C3N4. The obtained ADN@g-C3N4 exhibits a narrow optical band gap (2.12 eV) and a wide optical absorption spectrum (intensity a.u. > 0.30) ranging from ultraviolet to near-infrared region. Moreover, ADN@g-C3N4 would produce reactive oxygen species (ROS) under light irradiation to exert effective sterilization and biofilm elimination activities against both gram-negative and gram-positive bacteria. Molecular dynamics simulation reveals that the ADN@g-C3N4 may move toward, tile and insert the bacterial lipid bilayer membrane through strong van der Waals and electrostatic interaction, decreasing the order parameter of the lipid while increasing the conducive of ROS migration, inducing ADN@g-C3N4 with improved antimicrobial and antibiofilm performance. Moreover, ADN@g-C3N4 could efficiently eradicate oral biofilm on artificial teeth surfaces. This work may provide a broad-spectrum light-induced photocatalytic therapy for preventing and treating dental plaque diseases and artificial teeth-related infections, showing potential applications for intractable biofilm treatment applications. An acridinium-grafted g-C3N4 (ADN@g-C3N4) with a narrow band gap and broad-spectrum light absorption was synthesized. The narrow optical band gap and improved electrostatic interaction with bacterial lipid bilayer membrane of ADN@g-C3N4 strengthened the ROS generation and facilitated the diffusion of ROS to bacteria surface, leading to enhanced photocatalytic and antibacterial activity against bacteria and corresponding biofilm under light irradiation. STATEMENT OF SIGNIFICANCE: An acridinium-grafted g-C3N4 (ADN@g-C3N4) with a narrow band gap and broad-spectrum light absorption was developed as an antimicrobial photocatalytic therapy agent. The ADN@g-C3N4 exhibited enhanced photocatalytic and antibacterial activity against bacteria and corresponding biofilm under light irradiation, showing potential applications for intractable biofilm treatment.

Metal-organic framework (MOF) facilitated highly stretchable and fatigue-resistant ionogels for recyclable sensors.

Ionogel-based flexible sensors are widely applied in wearable biomedical devices and soft robots. However, the abandoned ionic sensors are rapidly turning into e-waste. Here, we harness the porosity and the coordination of metal sites of metal-organic frameworks (MOFs) to develop physically crosslinked ionogels, which are composed of polymer chains that coordinate with the MOF metal sites. The covalent crosslinking of the host material transformed into reversible bond interactions that significantly enhance the mechanical properties of the MOF-ionogels. The obtained ionogels can endure an 11 000% stretch and exhibit Young's modulus and toughness of 58 MPa and 25 MJ m-3, respectively. In addition, the fracture energy is as high as 125 kJ m-2, outperforming most reported ionogels. Furthermore, the UiO-66-ionogels are fully recyclable and both the mechanical and electrical properties can be restored. The results of this work provide a new vision for the development of future "green" sensors.

Moisture-Wicking, Breathable, and Intrinsically Antibacterial Electronic Skin Based on Dual-Gradient Poly(ionic liquid) Nanofiber Membranes.

Electronic skin can detect minute electrical potential changes in the human skin and represent the body's state, which is critical for medical diagnostics and human-computer interface development. On the other hand, sweat has a significant effect on the signal stability, comfort, and safety of electronic skin in a real-world application. In this study, by modifying the cation and anion of a poly(ionic liquid) (PIL) and employing a spinning process, a PIL-based multilayer nanofiber membrane (PIL membrane) electronic skin with a dual gradient is created. The PIL electronic skin is moisture-wicking and breathable due to the hydrophilicity and pore size-gradients. The intrinsically antimicrobial activities of PILs allow the safe collection of bioelectrical signals from the human body, such as electrocardiography (ECG) and electromyography (EMG). In addition, a robotic hand may be operated in real-time, and a preliminary human-computer interface can be accomplished by simple processing of the collected EMG signal. This study establishes a novel practical approach for monitoring and using bioelectrical signals in real-world circumstances via the multifunctional electronic skin.

Ionic Liquid-Type Additive for Lithium Metal Batteries Operated in LiPF6 Based-Electrolyte Containing 2500 ppm H2O.

The presence of trace amounts of moisture in the electrolyte can cause hydrolysis of LiPF6 and deteriorate the stability of lithium metal batteries. Herein, we propose a multifunctional ionic liquid-type additive constituting a 1-methyl-1-butyl pyrrolidium cation (Py14+) and an acetate anion (CH3COO-) (denoted as IL-AC in this study), which can effectively adsorb the trace moisture and thus prevent the hydrolysis of LiPF6 via intermolecular interactions. The prepared IL-AC can also remove HF to suppress the dissolution of transition metal ions from cathode materials through the reaction CH3COO- + HF → CH3COOH + F-. Compared with the baseline electrolyte, the contents of HF and transition metal ions are significantly lower in the electrolyte with 0.5% IL-AC. Upon the addition of 0.5% IL-AC additive and 2500 ppm H2O, the Li||NCM811 battery shows a capacity of 153.7 mAh g-1 after 300 cycles, while the Li||LNMO battery possesses stable capacity retention of 93.22% after 500 cycles at 1C and a Coulombic efficiency greater than 99%. Thus, this work provides a convenient and effective method to absorb trace amounts of water and remove HF in the electrolyte and provides a new path for the expensive and tedious process of water removal from the electrolyte in industry.

Acridine-Based Covalent Organic Framework Photosensitizer with Broad-Spectrum Light Absorption for Antibacterial Photocatalytic Therapy.

Antibiotic resistance is considered as one of the serious public health issues. Antibacterial photocatalytic therapy, a clinically proven antibacterial therapy, is gaining increasing attention in recent years owing to its high efficacy. Here, an acridine-based covalent organic framework (COF) photosensitizer, named TPDA, with multiple active sites is synthesized via Schiff base condensation between 2,4,6-triformylphloroglucinol (TFP) and 3,6-diaminoacridine (DAA). Owing to the increased conjugation effect of the COF skeleton and outstanding light harvesting ability of DAA, TPDA exhibits a narrow optical band gap (1.6 eV), enhancing light energy transformation and conferring a wide optical absorption spectrum (intensity arbitrary unit > 0.8) ranging from the UV to near-infrared region. Moreover, TPDA shows high antibacterial activities against both gram-negative and gram-positive bacteria within a short time (10 min) of light irradiation and is found to efficiently protect fish from skin infections. Molecular dynamics simulation data show that the introduction of DAA and TFP facilitates the interaction between TPDA and bacteria and is conducive to reactive oxygen species migration, which further improves the antimicrobial performance. These findings indicate the potential of TPDA as a novel photosensitive material for photodynamic therapy.