Carbon dots-enhanced pH-responsive lubricating hydrogel based on reversible dynamic covalent bondings

Due to the various pH liquid environment in nature,the pH-responsive lubricating hydrogel is widely investigated and developed for tissue interface substitute.However,the applied liquid environment will lead to poor mechanical property and weaken the pH-responsive capability.In this work,a carbon dotsenhanced pH-responsive lubricating hydrogel is developed by combining a pH-responsive section of dynamic PVA-borax network into a PAAm covalent polymer network.The formed hydrogel presents a partial gel-sol transition under controlled pH environments.At low pH environments(<6.0),the formed lubricating layer originated from dynamic disassembly of PVA-borax hydrogel,and brings the lubricating properties on the hydrogel surface.Moreover,the mechanical strength and lubrication properties are well promoted by introducing the carbon dots into the hydrogel,the blue sol layer can be observed more visually under the fluorescence microscope.The pH-response also exhibits well reversibility.The prepared hydrogel broadens the idea for designing pH-responsive soft materials for soft lubricating actuator or robot.

A Dynamic Covalent Bonding-based Nanoplatform for Intracellular Co-Delivery of Protein Drugs and Chemotherapeutics with Enhanced Anti-Cancer Effect

Efficient intracellular delivery of protein drugs is critical for protein therapy.The combination of protein drugs with chemotherapeutics represents a promising strategy in enhancing anti-cancer effect.However,co-delivery systems for efficient delivery of these two kinds of drugs are still lacking because of their different properties.Herein,we show a well-designed delivery system based on dynamic covalent bond for efficient intracellular co-delivery of ribonuclease A(RNase A)and doxorubicin(DOX).Two polymers,PEG-b-P(Asp-co-AspDA)and PAE-b-P(Asp-co-AspPBA),and two 2-acetylphenylboronic acid(2-APBA)-functionalized drugs,2-APBA-RNase A and 2-APBA-DOX,self-assemble into mixed-shell nanoparticles(RNase A/DOX@MNPs)via dynamic phenylboronic acid(PBA)-catechol bond between PBA and dopamine(DA)moieties.The PBA-catechol bond endows the nanoparticles with high stability and excellent stimulus-responsive drug release behavior.Under the slight acidic environment at tumor tissue,RNase A/DOX@MNPs are positively charged,promoting their endocytosis.Upon cellular uptake into endosome,further protonation of PAE chains leads to the rupture of endosomes because of the proton sponge effect and the cleavage of PBA-catechol bond promotes the release of two drugs.In cytoplasm,the high level of GSH removed the modification of 2-APBA on drugs.The restored RNase A and DOX show a synergistic and enhanced antic-cancer effect.This system may be a promising platform for intracellular co-delivery of protein drugs and chemotherapeutics.

Self-assembly of supra-amphiphile of azobenzene-galactopyranoside based on dynamic covalent bond and its dual responses

In this paper, dynamic covalent bond has been employed to construct supra-amphiphile of carbohydrate for the first time. In neutral environment, the molecule was fabricated by reacting a hydrophobic building block bearing benzoic aldehyde with a hydrophilic building block bearing hydrazine to form a sugar-containing supra-amphiphile based on acylhydrazone bond, The obtained azobenzene- galactopyranoside （Azo-Gal） supra-amphiphile self-assembled to fibrillar structure in water, which showed dual responses to UV light and pH.

Cancer Therapy by Targeting Thioredoxin Reductase Based on Selenium-Containing Dynamic Covalent Bond

Thioredoxin Reductase(TrxR)plays a pivotal role in defending cells against reactive oxygen species(ROS)and maintaining a reduced intracellular environment.It has been discovered that TrxR is elevated significantly in human cancer,evidenced by its association with the promotion of tumor cell proliferation,inhibiting tumor cell apoptosis,as well as enhancing tumor drug resistance.Hence,finding highly selective inhibitors of TrxR is urgently needed.Herein,we developed a selenium-containing small molecule(EbD),which had two Se–N bonds.Under reduction conditions,the two Se–N bonds reacted with Se–H bond and S–H bond in TrxR to form new Se–Se bond and Se–S bonds,respectively.Subsequently,the newly formed bonds were able to disrupt the thioredoxin(Trx)reduction catalytic cycle,and thus,inhibited the TrxR activity irreversibly,which resulted in the collapse of the antioxidant system.As a consequence,ROS levels elevated that triggered cancer cell apoptosis.This strategy,based on selenium-containing dynamic covalent bonds,provides a new avenue for cancer therapy via targeting TrxR.

Solvent-Free Synthesis of Self-Healable and Recyclable Crosslinked Polyurethane Based on Dynamic Oxime-Urethane Bonds

Polyurethane is widely used for its versatility in design and range of performance.Self-healing and recyclable dynamic polyurethane networks have attracted extensive attention due to their potential to extend service life and ensure safety in use,as well as to promote sustainable use of resources.Developing green and environment-friendly methods to obtain this material is an interesting and challenging task,as the majority of current dynamic polyurethane networks utilize the solution polymerization method.The use of solvents makes the processes complicated,harmful to environment,and increase the cost.Poly(oxime-urethanes)(POUs)are emerging dynamic polyurethanes and show great potential in diverse fields,such as biomaterials,hot melt adhesives,and flexible electronics.In this study,we utilized the solubility properties of dimethylglyoxime in raw material poly(ethylene glycol)to prepare POUs through bulk polymerization for the first time.This method is simple,convenient and cost-efficient.Simultaneously,copper ion coordination improves POUs strength and dynamic properties,with mechanical strength up from 0.54 MPa to 1.03 MPa and self-healing recovery rate up from 85.5%to 91.8%,and activation energy down from 119.6 k J/mol to 95.4 k J/mol.To demonstrate the application of this technology,self-healing and stretchable circuits are constructed from this dynamic polyurethane network.

Dynamic covalent nano-networks comprising antibiotics and polyphenols orchestrate bacterial drug resistance reversal and inflammation alleviation

New antimicrobial strategies are urgently needed to meet the challenges posed by the emergence of drug-resistant bacteria and bacterial biofilms.This work reports the facile synthesis of antimicrobial dynamic covalent nano-networks(aDCNs)composing antibiotics bearing multiple primary amines,polyphenols,and a cross-linker acylphenylboronic acid.Mechanistically,the iminoboronate bond drives the formation of aDCNs,facilitates their stability,and renders them highly responsive to stimuli,such as low pH and high H2O2 levels.Besides,the representative A1B1C1 networks,composed of polymyxin B1(A1),2-formylphenylboronic acid(B1),and quercetin(C1),inhibit biofilm formation of drug-resistant Escherichia coli,eliminate the mature biofilms,alleviate macrophage inflammation,and minimize the side effects of free polymyxins.Excellent bacterial eradication and inflammation amelioration efficiency of A1B1C1 networks are also observed in a peritoneal infection model.The facile synthesis,excellent antimicrobial performance,and biocompatibility of these aDCNs potentiate them as a much-needed alternative in current antimicrobial pipelines.

Aggregates of fluorescent gels assembled by interfacial dynamic bonds

Life,defined as the specific form of substance,is an integration of aggregates at various scales,ranging from single molecules to tissues.However,these building blocks of common aggregates are usually recognized as confining at the microscopic level,while there are few studies focusing on macroscopic building blocks for aggregates.Fluorescent gels,as the important macroscopic building blocks,are drawing researchers’attention on account of their extraordinary fluorescence as well as soft material properties.Inspired by nature,fluorescent gels can be aggregated through interfacial adhesion.According to the driving forces for interfacial adhesion,a series of aggregates of fluorescent gels(AFGs)was summarized,including H-bond,metal coordinations,host-guest interactions,hydrophobic interactions,electrostatic interactions,dynamic covalent bonds as well as multiple driving forces.These AFGs own dynamic assembled behaviors and rich stimuli responsiveness,which could be applied to information storage,sensing,biomedical systems,and so on.The authors anticipate this review can accelerate the development of aggregate science,especially based on macroscopic building blocks.

Dynamic Oxime-Urethane Bonds, a Versatile Unit of High Performance Self-healing Polymers for Diverse Applications

Oxime-urethane bond featuring with high reversibility even at room temperature and multiple reactivity is an emerging dynamic covalent bond,and has shown great potential for self-healing polymers,which are one of the most attractive development directions for next generation of polymeric materials.In this review,recent progresses on the oxime-urethane-based self-healing polymers,including their designs and applications in diverse fields such as biomedicine,flexible electronics,soft robots,3D printing,protective materials,and adhesives,are summarized,and outlooks on the future development of this field are discussed.

Design of Tough, yet Strong, Heat-resistant PLA/PBAT Blends with Reconfigurable Shape Memory Behavior by Engineering Exchangeable Covalent Crosslinks

Polylactide(PLA)has often been blended with biodegradable poly(butylene adipate-co-terephthalate)(PBAT)to improve its toughness.However,the strength and heat resistance of PLA are always sacrificed.Herein,exchangeable hydroxyl-ester crosslinks are constructed in PLA/PBAT blends by successively introducing a tertiary amine-containing polyol,bis-(2-hydroxyethyl)amino-tris(hydroxymethyl)methane(BTM)and 4,4’-diphenylmethane diisocyanate(MDI)via reactive blending.BTM can react with both PLA and PBAT by transesterification,generating PLA or PBAT chains with terminal or pendant hydroxyl groups,which can then react with MDI to form networks.With internal catalysis of tertiary amine moiety in BTM,transesterification between the residual hydroxyl groups and ester bonds can occur at high temperatures,endowing the PLA/PBAT network with vitrimeric properties.Owning to the transesterification and chain extension reactions with MDI between PLA and PBAT,the interfacial adhesion is greatly improved.As a result of the excellent interfacial adhesion and the network structure,the prepared PLA/PBAT blends show greatly enhanced heat resistance and toughness(more than 40 times that of PLA)while maintaining high stiffness comparable to PLA.Furthermore,the prepared PLA/PBAT blends exhibit promising reconfigurable shape memory behavior.The present work provides a new and facile way to achieve high-performance and functional biodegradable polymeric materials.

Synergistic Dual Dynamic Bonds in Covalent Adaptable Networks

Covalent adaptable networks(CANs),comprising polymer networks crosslinked by dynamic covalent bonds(DCBs),have garnered considerable attention as sustainable materials.Mastering the stress relaxation of CANs is essential for controlling their viscoelastic properties.An unexpected acceleration of stress relaxation has been observed in CANs containing dual dynamic bonds.The dynamic behavior of the second dynamic bonds can accelerate stress relaxation and lower the relaxation activation energy of dual dynamic CANs compared to analogous CANs that rely on only one type of DCB.These findings complement current approaches that utilize catalysts or adjust network parameters.In this minireview,we summarize the synergistic acceleration effects in various CANs containing dual dynamic bonds.We classify these effects based on the second dynamic bonds,including noncovalent bonds,mechanical bonds,and the second DCBs.We also discuss the mechanisms behind this synergy.Finally,we highlight the challenges and offer perspectives on harnessing the synergistic effects of these dual dynamic systems to expand the chemistry and applications of CANs.

An interfacial robust and entire self-healing ionogel-elastomer hybrid for elastic electronics enables discretionary assembly and reconfiguration

Inspired by the multi-layer architecture of mammal skins,interfacial robust,stretchable,and entirely healable gel-elastomer hybrids hold great potential in diverse fields including biomedical devices,wearable electrical devices,and soft robotics.However,existing gel-elastomer hybrids have numerous limitations including low interfacial bonding toughness,complex and time-consuming preparation process,unhealable,and non-reconfiguration.Herein,we propose a simple and general chemical strategy through the interfacial dynamic bonding between gel and elastomer to simultaneously address the abovementioned obstacles.Dynamic covalent bonds readily and repeatably covalent bonding ionogel and elastomer(interfacial toughness:390 J m^(-2)),endowed the hybrids with entire self-healing features like skin and enabled discretionary assembly and reconfiguration.Moreover,this strategy resolved the troublesome contradiction between interfacial stability and reconfiguration.Taking advantage of the aforementioned features,we readily constructed a multi-module,self-healing,self-powered,and realtime monitoring of personal status integrated elastic electronics,which could simply reconfigure the output signal of elastic electronics into an input signal of the devices-braille keyboard.

Molecular design of recyclable thermosetting polyimide and its composite with excellent mechanical and tribological properties

Recyclability of thermosetting polymers and their composites is a challenge for alleviating environmental pollution and resource waste.In this study,solvent-recyclable thermosetting polyimide(PI)and its composite were successfully synthesized.The tensile strength,elongation at break,and Young’s modulus of PI are 108.70±7.29 MPa,19.35%±3.89%,and 2336.42±128.00 MPa,respectively.The addition of reduced graphene oxide(RGO)not only enhances the mechanical properties of PI but also endows it with excellent tribological properties.The PI illustrates a high recycling efficiency of 94.15%,but the recycled composite exhibits inferior mechanical properties.The recycling and utilization of PI and its composite are realized through imine bonds(-C=N),which provides new guidance for solving the problem of environmental pollution and resource waste and is potential application in the field of sustainable tribology.

Light-controlled switchable underwater adhesive

Despite extensive efforts in designing and preparing switchable underwater adhesives,it is not easy to regulate the underwater adhesion strength locally and remotely.Here,we design and synthesize photoreversible copolymer of poly[dopamine methacrylamide-co-methoxyethyl-acrylate-co-7-(2-methacryloyloxyethoxy)-4-methylcoumarin].Due to the dynamic formation and breaking of chemical crosslinking networks within the smart adhesives,the material shows widely tunable adhesion strength from∼150 to∼450 kPa and long-range reversible maneuverability under orthogonal 254 and 365 nm ultraviolet light stimulation via the coumarin dimerization and cycloreversion.Moreover,the adhesive exhibits good circulation performance and stability in an acid–base environment.It also demonstrated that the bolt can be coated with the smart adhesive material for on-demand bonding.This design principle opens the door to the development of remotely controllable high-performance smart underwater adhesives.

"Solid-Liquid" Vitrimers Based on Dynamic Boronic Ester Networks

The"solid-liquid"behavior of vitrimers have not been systematically investigated.Herein,a series of"solid-liquid"vitrimers bearing varying contents of dynamic boronic ester bonds were synthesized via thiol-ene click reactions.These vitrimers allow for flexibile modulation of their network structures and thus show a range of intriguing properties including high stretchability,flexible transition from elasticity to plasticity,strong strain rate dependence,and solid-liquid performance.The dynamic association rate of boronic ester bonds within these vitrimers could be apparently accelerated via increasing the content of boronic ester,which could be used to shape-program the flat vitrimer films into various complex 3D structures just with external force.Materials with such versatile dynamic behavior may open up a range of new applications.

Configurational Selectivity Study of Two-dimensional Covalent Organic Frameworks Isomers Containing D2h and C2 Building Blocks

The isomerization of covalent organic frameworks(COFs) materials is still a mysterious and attractive topic. Diversified monomer structures are still urgently needed to explore the in-depth mechanism of isomerization in these special COFs. This work provides a new D2h monomer for the construction of [D2h+C2] 2D COFs isomers. A new D2h monomer adopted here was proven to tend to form a single pore framework structure.

Highly Conductive Poly(Imide–Imine)Hybrid Vitrimer-Graphene Aerogel Composites

Comprehensive Summary,Although polyimides(PIs)have shown great potential for a broad range of applications,it remains very challenging to achieve the malleability,rehealability and recyclability for PIs and their composites targeting various applications,particularly for the rapidly emerging flexible and stretchable electronics.Herein,malleable conductive poly(imide-imine)hybrid(PIIH)vitrimer-graphene aerogel(GA)composites have been prepared,for the first time,via simple sol-gel film formation followed by heat-press.The resulting PIIH-GA composites exhibit not only the highly desired properties of thermosetting(strong mechanical strength)and thermoplastic(reprocessability)polymers,but also good conductivity enabled by the GA filler.PIIH3-GA-10(with 10 wt%GA)showed one of the highest electrical conductivities(26.7 S/m)for PI-based composites,as well as good electromagnetic interference(EMI)shielding performance.Moreover,the PIIH-GA films could maintain good performance during stretching and even after chemical recycling,which opens new opportunities for flexible and sustainable electronics development.

Self-assembly behavior of disaccharide-containing supra-amphiphiles

In this paper,supra-amphiphilic compounds containing disaccharides and azobenzene ends have been constructed via dynamic covalent bond.It was found that the slight structural difference of the disaccharides made significant difference in the self-assembled morphologies.Namely,three kinds of azodisaccharide supra-amphiphiles were found to assemble into different morphologies,with the only difference in chemical structure from the disaccharides.More importantly,the structural difference between the disaccharides,including lactoside,maltoside and cellobioside was trivial.Molecular simulation revealed the packing of molecules was due to the different contribution from hydrogen bonds.The above results clearly indicated the contribution of saccharide packing,especially the related hydrogen bonding,to the final morphology of the assembled structures.

Detachable and hierarchical assemblies for recyclable and highly efficient oil-fouling removal

Large-scale use of detergents to remove oil-fouling in industry continuously generates tremendous amounts of wastewater and thus leads to both economic and environmental problems.To develop recyclable oil-fouling removal strategy is an appealing solution but a challenging task.Herein,a kind of dynamic imine-based surfactant has been constructed by 2-formylbenzenesulfonic acid sodium salt(FBSS)and linear amines(CnNH_(2),n=6,7,8,10,and 12).Owing to high interfacial activity and strong assembly ability,dynamic FBSS/C8NH_(2)system can remove oil-fouling on multiple substrates for at least 10 cycles,largely reducing the toxicity to ecosystem.At basic pH,the hierarchical assemblies(from vesicle to network and hollow sphere)are formed and boost surfactant molecule enrichment around oil-fouling,leading to highly efficient emulsification.When pH is changed to acidic condition,the surfactant molecules dissociate due to the breaking of imine bonds,and accordingly the emulsion is destroyed and the released oil droplets float to the top layer.After removing the oil-fouling and adjusting the solution back to basic pH,the surfactant assemblies are reconstructed and used for the next oil-fouling cleaning cycle.This study provides a recyclable,efficient and eco-friendly oil-fouling removal approach,satisfying the need of sustainable development.

Self-healing Hydrogelsand Underlying Reversible Intermolecular Interactions

Self-healing hydrogels have attracted growing attention over the past decade due to their biomimetic structure,biocompatibility,as well as enhanced lifespan and reliability,thereby have been widely used in various biomedical,electrical and environmental engineering applications.This feature article has reviewed our recent progress in self-healing hydrogels derived from mussel-inspired interactions,multiple hydrogen-bonding functional groups such as 2-ureido-4[1H]-pyrimidinohe(UPy),dynamic covalent bonds(eg,Schiff base reactions and boronic ester bonds).The underlying molecular basics of these interactions,hydrogel preparation principles,and corresponding performances and applications are introduced.The underlying reversible intermolecular interaction mechanisms in these hydrogels were investigated using nanomechanical techniques such as surface forces apparatus(SFA)and atomic force microscopy(AFM),providing fundamental insights into the self-healing mechanisms of the hydrogels.The remaining challenging issues and perspectives in this rapidly developing research area are also discussed.

Thermal- and Light-driven Metathesis Reactions Between Different Diselenides

Thermal- and light-driven diselenide metathesis reactions with different types of diselenides are investigated systematically. Their exchange reaction rates and equilibrium conversions are compared in the aspects of the different diselenide structures, activation conditions and solvents. As a result, the metathesis reactions between diselenide small molecules are demonstrated with high dynamic and sensitive features, which can be broadly tuned by varying the electron affinity and aromaticity of the diselenide substituents and external conditions(e.g., solvent, stimulus mode). The current work thus will not only advance our understanding on diselenide metathesis chemistry, but also promote concrete and impactful studies in selenium-containing materials.