Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of lum...Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of luminescent materials.In recent years,the novel macrocyclic arenes characterized by unique electron-rich structures,ease of derivatization,tunable conformations and even inherent luminescence properties afford much opportunities to create such dynamic smart luminescent materials.The incorporation of macrocyclic arenes into SLMs leads to simple preparation process,diverse photophysical phenomena and sophisticated regulatory mechanisms,which is also currently one of the most frontier and hot topics in macrocyclic and supramolecular chemistry and even luminescent materials.In this review,the research advances in construction and applications of SLMs based on macrocyclic arenes in the last several years will be presented from the different assembly strategies,including host-vip complexes,supramolecular polymers,nanoparticles,and other assemblies.Moreover,some insights into future directions for this research area will also be offered.展开更多
A renewable fluorescent material(GСCP5L)has been constructed via supramolecular assembly between a new derivative of pillararene,namely leggero pillar[5]arene,as the host molecule(CP5L)and a tetraphenylethylene(TPE)-...A renewable fluorescent material(GСCP5L)has been constructed via supramolecular assembly between a new derivative of pillararene,namely leggero pillar[5]arene,as the host molecule(CP5L)and a tetraphenylethylene(TPE)-based ditopic vip(G).This new material can simultaneously perform efficient detection and separation of silver(I)from aqueous environments.Possessing an electron-rich cavity and two cytosine groups modified on both rims,CP5L functions as the host-vip binding site for G and offers exclusive coordination sites for further interaction with Ag+.Adding Ag+to the system undergoes dramatic fluorescence enhancement due to the mechanism of supramolecular assembly-induced enhanced emission(SAIEE).This fluorescence enhancement allows for efficient and visualized detection following a“light-up”pattern,achieving a limit of detection(LOD)of 1.3×10^(-7)mol/L,which is fully in line with the World Health Organization's drinking water standard of 9×10^(-7)mol/L.In addition,GСCP5L also shows strong anti-interference capability against other cationic species.For the separation of Ag+from aqueous systems,GСCP5L displays exceptional adsorption efficiency(97%)and reliable recovery performance,demonstrating excellent recyclability after five experimental cycles without compromising its adsorption activity.展开更多
The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycl...The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.展开更多
Circularly polarized luminescence(CPL)-active materials have a wide range of technological applications.Traditionally,creating CPL-active materials relies on the use of chiral luminophores.In contrast,supramolecular a...Circularly polarized luminescence(CPL)-active materials have a wide range of technological applications.Traditionally,creating CPL-active materials relies on the use of chiral luminophores.In contrast,supramolecular assembly introduces an innovative and promising strategy for developing CPL-active materials not only from chiral luminophores but also from achiral species.This approach significantly enriches the diversity of CPL-active materials.It also offers an effective means to optimize the performance of CPL-active materials,such as enhancing the asymmetry factor|glum|.Compared to polymers,the assembly of small molecules is generally easier to control.This review systematically summarizes the recent progress and developments in CPL from small-molecule assemblies,particularly focusing on differences,merits,and demerits of three typical assembly modes.The aim is to provide valuable insights for the future development of chiroptical materials.展开更多
The convergence of materials science and biotechnology has catalyzed the development of innovative platforms,including nanotechnology,smart sensors,and supramolecular materials,significantly advancing the progress in ...The convergence of materials science and biotechnology has catalyzed the development of innovative platforms,including nanotechnology,smart sensors,and supramolecular materials,significantly advancing the progress in the field of life sciences[1−7].Among them,supramolecular materials have garnered increasing attention in life sciences owing to their distinctive self-assembly capabilities and intelligent responsiveness[8−12].展开更多
Osteoarthritis(OA)is the most prevalent joint disease and icariin is a promising drug for its treatment.However,the clinical use of icariin is hindered by poor water solubility,low bioavailability,and nonspecific rele...Osteoarthritis(OA)is the most prevalent joint disease and icariin is a promising drug for its treatment.However,the clinical use of icariin is hindered by poor water solubility,low bioavailability,and nonspecific release and biological distribution.Herein,sulfonated azocalix[4]arene(SAC4A)with enhanced water solubility,recognition capacity,and designed responsiveness was used to improve the efficiency of icariin for OA therapy.SAC4A,a macrocycle with well-defined molecular weight and structure,could encapsulate and enhance water solubility of various drugs.In addition,SAC4A enables hypoxia-responsive release of loaded drug.Compared with icariin treatment,supramolecular complex icariin@SAC4A significantly relieved OA symptoms of rats,including more regular bone morphology and structure,and lower degree of cartilage damage.Moreover,the supramolecular formulation demonstrated various advantages,including easy preparation,hypoxia-triggered release,and small size that conducive to drug penetration.展开更多
Background:Enzyme fragility remains a major challenge in research and applications.Free enzymes are highly unstable,inactivated by heat,acid,alkali,or organic solvents,and often lose activity even under optimal storag...Background:Enzyme fragility remains a major challenge in research and applications.Free enzymes are highly unstable,inactivated by heat,acid,alkali,or organic solvents,and often lose activity even under optimal storage conditions.Limiting their use in cosmetics.Few commercial products combine acids and enzymes effectively.Objective:To investigate the physicochemical properties,in vitro exfoliation efficacy,and effects on facial skin parameters of a supramolecular acid-enzyme complex(SAE)composed of mandelic acid(MAN),betaine(BET),and composite enzymes(CE;papain and bromelain),thereby establishing a theoretical foundation for cosmetic applications.Methods:The supramolecular structure was characterized using Fourier transform infrared(FTIR)spectroscopy and proton nuclear magnetic resonance(1H NMR)spectroscopy.Dissolution experiments were conducted to compare the solubility of SAE and CE in aqueous solutions.Enzymatic activity assays evaluated the stabilizing effect of supramolecular deep eutectic technology on enzymes.In vitro exfoliation tests assessed acid-enzyme synergy in keratin removal.A 4-week clinical trial evaluated the efficacy of a 2%SAE essence aqueous solution on facial skin parameters.Results:Dissolution experiments confirmed that supramolecular deep eutectic technology significantly improved enzyme solubility.Enzymatic activity tests demonstrated that this technology effectively preserved protease activity,substantially enhancing its practical applicability.Furthermore,in vitro exfoliation efficacy tests revealed that this technology strengthened the synergistic interaction between acids and enzymes and exhibited superior stratum corneum-removing capability of the SAE.In clinical evaluations of efficacy,after 7 days of using the essence containing SAE,the formulation significantly enhanced cheek gloss(+8.08%),while reducing comedones volume(-16.25%).after 28 days,significantly enhanced cheek hydration(+25.0%,SCH),gloss(+15.93%),and smoothness(−7.78%SEsm),while reducing TEWL(−6.86%),sebum(−15.54%),roughness(+16.24%SEr),and pore metrics(volume:−39.98%;count:−30.64%),and decreased comedones(blackheads:−70.33%;Whiteheads:−52.42%;all p<0.05).Conclusion:The supramolecular acid-enzyme complex demonstrates enhanced stability,improved solubility,and superior exfoliation efficacy compared to free enzymes.Clinical results further confirm its multifunctional benefits,including enhancing skin hydration,sebum regulation,barrier repair,pore refinement,and comedolytic effects.This study provides both theoretical and practical foundations for developing stable acid-enzyme combinations in dermatological applications.展开更多
Sustained inflammatory responses are closely related to various severe diseases,and inhibiting the excessive activation of inflammasomes and pyroptosis has significant implications for clinical treatment.Natural produ...Sustained inflammatory responses are closely related to various severe diseases,and inhibiting the excessive activation of inflammasomes and pyroptosis has significant implications for clinical treatment.Natural products have garnered considerable concern for the treatment of inflammation.Huanglian-Wumei decoction(HLWMD)is a classic prescription used for treating inflammatory diseases,but the necessity of their combination and the exact underlying anti-inflammatory mechanism have not yet been elucidated.Inspired by the supramolecular self-assembly strategy and natural drug compatibility theory,we successfully obtained berberine(BBR)-chlorogenic acid(CGA)supramolecular(BCS),which is an herbal pair from HLWMD.Using a series of characterization methods,we confirmed the self-assembly mechanism of BCS.BBR and CGA were self-assembled and stacked into amphiphilic spherical supramolecules in a 2:1 molar ratio,driven by electrostatic interactions,hydrophobic interactions,andπ–πstacking;the hydrophilic fragments of CGA were outside,and the hydrophobic fragments of BBR were inside.This stacking pattern significantly improved the anti-inflammatory performance of BCS compared with that of single free molecules.Compared with free molecules,BCS significantly attenuated the release of multiple inflammatory mediators and lipopolysaccharide(LPS)-induced pyroptosis.Its anti-inflammatory mechanism is closely related to the inhibition of intracellular nuclear factor-kappaB(NF-κB)p65 phosphorylation and the noncanonical pyroptosis signalling pathway mediated by caspase-11.展开更多
Supramolecular materials,characterized by dynamic reversibility and responsiveness to environmental stimuli,have found widespread applications in numerous fields.Unlike traditional materials,supramolecular materials t...Supramolecular materials,characterized by dynamic reversibility and responsiveness to environmental stimuli,have found widespread applications in numerous fields.Unlike traditional materials,supramolecular materials that rely on non-covalent interactions can allow spontaneous reorganization and self-healing at room temperature.However,these materials typically exhibit low strength due to the weak bonding energies of non-covalent interactions.This study presents the development of a high-strength self-healing supramolecular material that combines multiple interactions including ionic bonding,hydrogen bonding,and coordination bonding.The material,formed by the aggregation of the negatively charged picolinate-grafted copolymer(PCM)with positively charged hyperbranched molecules(HP),is further enhanced by Eu^(3+)ion complexation.The resulting film exhibits a high modulus of 427 MPa,tensile strength of 10.5 MPa,and toughness of 14.7 MJ m^(−3).Meanwhile,the non-covalent interaction of this supramolecular material endows it with a self-healing efficiency of 92%within 24 h at room temperature,as well as multiple remolding properties.The incorporation of lanthanide ions also imparts tunable fluorescence.This study not only provides insights into the development of high-strength self-healing materials but also offers new possibilities for the functionalization of supramolecular materials.展开更多
Three monomers,namely A2,B2,and GH,were designed and synthesized.By utilizing double host-vip interactions,the monomers A2+B2+GH underwent self-assembly to form a supramolecular linear polymer(SLP)at high concentrat...Three monomers,namely A2,B2,and GH,were designed and synthesized.By utilizing double host-vip interactions,the monomers A2+B2+GH underwent self-assembly to form a supramolecular linear polymer(SLP)at high concentrations.Long fibers could be pulled from the concentrated SLP solution.Upon the addition of PdCl_(2)(PhCN)_(2)into the SLP solution,a structural transformation occurred from SLP to a supramolecular crosslinked polymer(SCP)through metal coordination interaction.This transformation induced fluorescence quenching,test paper strips for ion detection experiment confirmed that the SLP had good detection ability for Pd^(2+).Furthermore,the SCP underwent a transformation into a gel when the concentration exceeded 145 mmol/L.The SCP gel demonstrated sensitivity to different stimuli,such as K^(+)ions and changes in temperature,accompanied by a reversible transition between sol and gel states.Additionally,rheological analyses indicated that the gel possessed favorable self-healing properties.展开更多
Mechanically robust transparent materials that can be repaired have many advantages for practical applications.In this study,a supramolecular strategy is used to introduce healing capacity and mechanical toughness int...Mechanically robust transparent materials that can be repaired have many advantages for practical applications.In this study,a supramolecular strategy is used to introduce healing capacity and mechanical toughness into artificial glass.Non-covalent/dynamic covalent polymerization of thioctic acid(TA)and(±)-trans-1,2-diaminocyclohexane(DC)generates supramolecular glass with versatile attractive properties,including high optical transmittance(>90%),strong impact resistance(2.47 k J/m^(2)),good mechanical strength(21.6 MPa),and high rigidity(65 HD on Shore hardness).The adhesive bonding of poly[TA],along with its photopolymerization behavior,enables damaged areas in poly[DC/TA]to be rebuilt in-situ.Subsequent solidification and hardening of the repaired areas are notably accelerated by hydrogen bonding between poly[TA]and DC.The newly healed poly[DC/TA]exhibits considerable optical and mechanical properties compared to those of untreated poly[DC/TA].This study presents a new design concept for constructing the high-performance glass from low-molecular-weight organic compounds.展开更多
Black phosphorus(BP),as a rising star of 2D nanomaterials has drawn considerable attention in cancer therapy.However,the poor stability under ambient conditions limits their practical applications.Herein,a multiple su...Black phosphorus(BP),as a rising star of 2D nanomaterials has drawn considerable attention in cancer therapy.However,the poor stability under ambient conditions limits their practical applications.Herein,a multiple supramolecular assembly composed of adamantane-modified hyaluronic acid(HAADA),ferrocene-modified cinnamaldehyde(Fc-CA),guanidinium-functionalizedβ-cyclodextrin(Guano-CD),and black phosphorus(BP)nanosheets was successfully fabricated through cooperative host-vip and electrostatic interactions.Owing to the cooperative contribution of these building blocks,the obtained supramolecular assembly simultaneously possesses multiple functions including excellent stability,good biocompatibility and targeting property,and a high inhibition effect toward cancer cells.We believe that this work might provide new insights into designing a new generation of cancer theranostic protocols for potential clinical applications.展开更多
Surface-adhering biofilms contribute significantly to irreversible biofouling and corrosion,presenting a multi-trillion-dollar annual problem in public health and industry.Strategies employing antibacterial elements a...Surface-adhering biofilms contribute significantly to irreversible biofouling and corrosion,presenting a multi-trillion-dollar annual problem in public health and industry.Strategies employing antibacterial elements are emerging to fabricate multifunctional coatings that effectively combat such microbially produced damage.However,rapid,reliable,and robust surface engineering remains challenging due to stability limitations and intricate anti-biofilm additive dynamics.Herein,a silver-capsule-conjugated polyurethane coating with high stability and antimicrobial efficacy in a cooperative manner is developed through controlled supramolecular self-assembly.Polyvinylpyrrolidone(PVP)-mediated molecule entanglement breaks through the incompatibility between polymeric components and nanomaterials,strengthening the dispersion and fixation of encapsulated silver nanoparticles.The facilitation and control of the nanoscale interfacial binding significantly suppresses the aggregation of inorganic nanoparticles and consequent microcracks development,giving rise to mechanical robustness and thermal stability of the hybrid coating under extreme conditions.A synergistic combination of exposed residues,electrostatic,and coordination interactions could readily integrate the resultant coating on virtually arbitrary material sur-faces.This composite coating exhibits broad-spectrum and high bactericidal efficiencies of 99.99% against Staphylococcus aureus and Escherichia coli,as well as excellent biofilm formation suppression.Moreover,our coating has robust resistance to microbial-influenced corrosion(MIC)and can even endure 720 h of salt spray.This study deciphers a general code for creating stable and durable nanohybrid coatings to mitigate microbially related risks.展开更多
Herein,a ternary supramolecular assembly(BPP-BQ?CB[8]-SCD)is successfully constructed by a bromophenylpyridine-tethered-bromoisoquinoline(BPP-BQ),cucurbit[8]uril(CB[8])and sulfonatedβ-cyclodextrin(SCD)via successive ...Herein,a ternary supramolecular assembly(BPP-BQ?CB[8]-SCD)is successfully constructed by a bromophenylpyridine-tethered-bromoisoquinoline(BPP-BQ),cucurbit[8]uril(CB[8])and sulfonatedβ-cyclodextrin(SCD)via successive assembling way,exhibiting progressively enhanced green roomtemperature phosphorescence(RTP).The self-aggregates of BPP-BQ?CB[8]-SCD accommodate an energy acceptor rhodamine B(Rh B)to form a light-harvesting system(BPP-BQ?CB[8]-SCD@Rh B)with further enhanced yellow long-lifetime luminescence with large Stokes shift based on triplet-singlet F?rster resonance energy transfer(TS-FRET).Crucially,the introduction of a photoactive diarylethene achieves the long-lived photoluminescence of BPP-BQ?CB[8]-SCD@Rh B to be switched with the efficiency of up to98%through logically ordered lowering/enhancing RTP performance of the energy donor and intercepting/restoring TS-FRET pathway,when stimulated by host-vip competition and light illumination in sequence.Moreover,BPP-BQ?CB[8]-SCD@Rh B is evenly doped into polyvinyl alcohol or polyacrylamide to obtain high-performance luminescent films with long afterglow.The abovementioned logically ordered stimulus-switched long-lived emission enables the light-harvesting system in both solution and solid state to be applied in high-security-level information encryption and transformation,and anticounterfeiting.展开更多
Rational tuning of chiral nanostructures of supramolecular assemblies as catalysts and investigating their chiral morphology-enantioselectivity dependence is rarely reported. Herein, we report a series of supramolecul...Rational tuning of chiral nanostructures of supramolecular assemblies as catalysts and investigating their chiral morphology-enantioselectivity dependence is rarely reported. Herein, we report a series of supramolecular M/P-helical nanoribbons(HNs) assembled from the chiral L/D-glutamate-based amphiphiles(L/D-Glu C16) and Cu(Ⅱ) ions, with their helical screw pitches adjusted from 217 nm to 104 nm through the facile regulation of their water/organic solvent assembly environment. They were then used as ideal models to reveal the chiral morphology-enantioselectivity relationship by catalyzing the asymmetric Diels-Alder reaction. Better enantioselectivity was achieved with more twist morphology. Experimental evidences of stronger chiral transfer effect from the supramolecular HNs with more twist to the aza-chalcone as reactant were obtained to understand such dependence. Our study demonstrates a new perspective for designing supramolecular catalysts with higher enantioselectivity.展开更多
Supramolecular prodrug vesicles(H-4⊃B-2@MB)with selective antibacterial activity have been successfully constructed.Specifically,a natural antibiotic prodrug(B-2)with glutathione(GSH)-responsiveness was synthesized.Th...Supramolecular prodrug vesicles(H-4⊃B-2@MB)with selective antibacterial activity have been successfully constructed.Specifically,a natural antibiotic prodrug(B-2)with glutathione(GSH)-responsiveness was synthesized.The hydrophobic interaction between B-2 and a novel water-soluble cavitand with deep cavity(H-4)resulted in the formation of a host-vip complex,which further self-assembled into supramolecular vesicles.The formed vesicles could effectively encapsulate the photosensitizer methylene blue(MB),enabling co-delivery of antibiotics and photosensitizers in the presence of GSH.Moreover,upon excitation at 630 nm,the photosensitizers generate reactive oxygen species(ROS),effectively eradicating E.coli through combined chemo-photodynamic therapy.Considering that GSH is predominantly present in Gram-negative bacteria such as E.coli,this strategy exhibits substantial potential for selectively inhibiting bacteria characterized by high GSH levels to regulate bacterial colony equilibrium.展开更多
Metal ions trigger Fenton/Fenton-like reactions,generating highly toxic hydroxyl radicals(•OH)for chemodynamic therapy(CDT),which is crucial in inducing lethal oxidative DNA damage and subsequent cell apoptosis.Howeve...Metal ions trigger Fenton/Fenton-like reactions,generating highly toxic hydroxyl radicals(•OH)for chemodynamic therapy(CDT),which is crucial in inducing lethal oxidative DNA damage and subsequent cell apoptosis.However,tumor cells can counteract this damage through repair pathways,particularly MutT homolog 1(MTH1)protein attenuation of oxidative DNA damage.Suppression of MTH1 can enhance CDT efficacy,therefore,orderly integrating Fenton/Fenton-like agents with an MTH1 inhibitor is expected to significantly augment CDT effectiveness.Carrier-free CuTH@CD,self-assembled through the supramolecular orchestration ofγ-cyclodextrin(γ-CD)with Cu^(2+)and the MTH1 inhibitor TH588,effectively overcoming tumor resistance by greatly amplifying oxidative damage capability.Without additional carriers and mediated by multiple supramolecular regulatory effects,CuTH@CD enables high drug loading content,stability,and uniform size distribution.Upon internalization by tumor cells,CuTH@CD invalidates repair pathways through Cu^(2+)-mediated glutathione(GSH)depletion and TH588-mediated MTH1 inhibition.Meanwhile,both generated Cu^(+)ions and existing ones within the nanoassembly initiate a Fentonlike reaction,leading to the accumulation of•OH.This strategy enhances CDT efficiency with minimal side effects,improving oxidative damage potency and advancing self-delivery nanoplatforms for developing effective chemodynamic tumor therapies.展开更多
Nanoscale drug delivery systems(nano-DDSs)have attracted intense interest in tumor chemotherapy in the last decades,to improve antitumor efficacy and minimize toxic and side effects.As a versatile supramolecular build...Nanoscale drug delivery systems(nano-DDSs)have attracted intense interest in tumor chemotherapy in the last decades,to improve antitumor efficacy and minimize toxic and side effects.As a versatile supramolecular building block,cyclodextrins(CDs)have been widely used in the fabrication of the smart nano-DDSs.Besides their multifunctionality,which makes them versatile core in the star(co)polymers for micellar nanomedicines,specific host-vip inclusion complexation via their hydrophobic cavities endows them diversified functions:(i)design of amphiphilic copolymers for micellar nanomedicines,(ii)supramolecular hydrogels and poly(pseudo)rotaxane nano-hydrogels as drug carriers,and(iii)recipient for direct and indirect drug-loading.In the present work,the recent progress of CDs in nano-DDSs for tumor chemotherapy was reviewed,classified by the crucial roles of CD units.Based on the structureperformance relationship,the future perspective was also proposed.展开更多
Developing advanced polymer electrolytes in lithium metal batteries(LMBs)has gained significant attention because of their inherent safety advantages over liquid electrolytes,while still encountering great challenges ...Developing advanced polymer electrolytes in lithium metal batteries(LMBs)has gained significant attention because of their inherent safety advantages over liquid electrolytes,while still encountering great challenges in mitigating uneven lithium plating/stripping and dendrite growth.Previous efforts primarily focused on passive approaches to mechanically constrain lithium dendrite growth.Recent studies have revealed the significance and effectiveness of regulating supramolecular interactions between polymer chains and other electrolyte components for homogenizing lithium deposition and enhancing the interfacial stability.This report provides a timely critical review to cover recent inspiring advancements in this direction.We first summarize the origins of supramolecular interaction origins,strength-determining factors,and structure–property relationships to establish quantitative correlations between polymer composition and supramolecular interaction properties.Then the recent advances in regulating supramolecular interaction chemistry are comprehensively discussed,focusing on those towards accelerated mass transport and stabilized anode-electrolyte interface.Finally,the remaining challenges are highlighted,and potential future directions in supramolecular interaction regulation of polymer electrolytes are prospected for the practical application of LMBs.展开更多
Although supramolecular transformations have been emerged as a potent strategy for transitioning between various topologies,post-modification induced topological transformations have never been explored in the context...Although supramolecular transformations have been emerged as a potent strategy for transitioning between various topologies,post-modification induced topological transformations have never been explored in the context of[2]catenane topologies.In this study,we present a novel supramolecular transformation between a Hopf link and a macrocycle,induced by the Diels–Alder click reaction.By strategically selecting the half-sandwich ruthenium binuclear fragment B as a rigid capping agent,we successfully integrated tetrazine moieties into the metalla[2]catenane structure.We demonstrated that the introduction of 2,5-norbornadiene(NBD)as an external stimulus allows for the transformation of the novel metalla[2]catenane,featuring reactive tetrazine sites,into the corresponding monomeric ring through postmodification for the first time.The synthetic results are corroborated by single-crystal X-ray diffraction analysis,ESI-TOF/MS,elemental analysis,and detailed solution-state NMR techniques.展开更多
基金the National Natural Science Foundation of China(Nos.22171272,22031010)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0520302)the Youth Innovation Promotion Association CAS(No.2021035)for financial support。
文摘Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of luminescent materials.In recent years,the novel macrocyclic arenes characterized by unique electron-rich structures,ease of derivatization,tunable conformations and even inherent luminescence properties afford much opportunities to create such dynamic smart luminescent materials.The incorporation of macrocyclic arenes into SLMs leads to simple preparation process,diverse photophysical phenomena and sophisticated regulatory mechanisms,which is also currently one of the most frontier and hot topics in macrocyclic and supramolecular chemistry and even luminescent materials.In this review,the research advances in construction and applications of SLMs based on macrocyclic arenes in the last several years will be presented from the different assembly strategies,including host-vip complexes,supramolecular polymers,nanoparticles,and other assemblies.Moreover,some insights into future directions for this research area will also be offered.
基金the Natural Science Foundation of Jilin Province(No.20230101052JC)the National Natural Science Foundation of China(No.52173200)Hangzhou Jingshi Technology Co.,Ltd.,and Hangzhou Xuhui Technology Co.,Ltd.for financial support。
文摘A renewable fluorescent material(GСCP5L)has been constructed via supramolecular assembly between a new derivative of pillararene,namely leggero pillar[5]arene,as the host molecule(CP5L)and a tetraphenylethylene(TPE)-based ditopic vip(G).This new material can simultaneously perform efficient detection and separation of silver(I)from aqueous environments.Possessing an electron-rich cavity and two cytosine groups modified on both rims,CP5L functions as the host-vip binding site for G and offers exclusive coordination sites for further interaction with Ag+.Adding Ag+to the system undergoes dramatic fluorescence enhancement due to the mechanism of supramolecular assembly-induced enhanced emission(SAIEE).This fluorescence enhancement allows for efficient and visualized detection following a“light-up”pattern,achieving a limit of detection(LOD)of 1.3×10^(-7)mol/L,which is fully in line with the World Health Organization's drinking water standard of 9×10^(-7)mol/L.In addition,GСCP5L also shows strong anti-interference capability against other cationic species.For the separation of Ag+from aqueous systems,GСCP5L displays exceptional adsorption efficiency(97%)and reliable recovery performance,demonstrating excellent recyclability after five experimental cycles without compromising its adsorption activity.
文摘The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.
基金support from the National Natural Science Foundation of China(52473192)。
文摘Circularly polarized luminescence(CPL)-active materials have a wide range of technological applications.Traditionally,creating CPL-active materials relies on the use of chiral luminophores.In contrast,supramolecular assembly introduces an innovative and promising strategy for developing CPL-active materials not only from chiral luminophores but also from achiral species.This approach significantly enriches the diversity of CPL-active materials.It also offers an effective means to optimize the performance of CPL-active materials,such as enhancing the asymmetry factor|glum|.Compared to polymers,the assembly of small molecules is generally easier to control.This review systematically summarizes the recent progress and developments in CPL from small-molecule assemblies,particularly focusing on differences,merits,and demerits of three typical assembly modes.The aim is to provide valuable insights for the future development of chiroptical materials.
基金supported by the National Natural Science Foundation of China(22101043)the Fundamental Research Funds for the Central Universities(N2205013,N232410019,N2405013)+3 种基金Natural Science Foundation of Liaoning Province(2023-MSBA-068)the Opening Fund of State Key Laboratory of Heavy Oil Processing(SKLHOP202203006)the Key Laboratory of Functional Molecular Solids,Ministry of Education(FMS2023005)Northeastern University。
文摘The convergence of materials science and biotechnology has catalyzed the development of innovative platforms,including nanotechnology,smart sensors,and supramolecular materials,significantly advancing the progress in the field of life sciences[1−7].Among them,supramolecular materials have garnered increasing attention in life sciences owing to their distinctive self-assembly capabilities and intelligent responsiveness[8−12].
基金supported by grants from the National Natural Science Foundation of China(Nos.82374489,U20A20259 and 22201299)the Scientific Research Program of the Tianjin Municipal Education Commission(No.2021ZD013)。
文摘Osteoarthritis(OA)is the most prevalent joint disease and icariin is a promising drug for its treatment.However,the clinical use of icariin is hindered by poor water solubility,low bioavailability,and nonspecific release and biological distribution.Herein,sulfonated azocalix[4]arene(SAC4A)with enhanced water solubility,recognition capacity,and designed responsiveness was used to improve the efficiency of icariin for OA therapy.SAC4A,a macrocycle with well-defined molecular weight and structure,could encapsulate and enhance water solubility of various drugs.In addition,SAC4A enables hypoxia-responsive release of loaded drug.Compared with icariin treatment,supramolecular complex icariin@SAC4A significantly relieved OA symptoms of rats,including more regular bone morphology and structure,and lower degree of cartilage damage.Moreover,the supramolecular formulation demonstrated various advantages,including easy preparation,hypoxia-triggered release,and small size that conducive to drug penetration.
文摘Background:Enzyme fragility remains a major challenge in research and applications.Free enzymes are highly unstable,inactivated by heat,acid,alkali,or organic solvents,and often lose activity even under optimal storage conditions.Limiting their use in cosmetics.Few commercial products combine acids and enzymes effectively.Objective:To investigate the physicochemical properties,in vitro exfoliation efficacy,and effects on facial skin parameters of a supramolecular acid-enzyme complex(SAE)composed of mandelic acid(MAN),betaine(BET),and composite enzymes(CE;papain and bromelain),thereby establishing a theoretical foundation for cosmetic applications.Methods:The supramolecular structure was characterized using Fourier transform infrared(FTIR)spectroscopy and proton nuclear magnetic resonance(1H NMR)spectroscopy.Dissolution experiments were conducted to compare the solubility of SAE and CE in aqueous solutions.Enzymatic activity assays evaluated the stabilizing effect of supramolecular deep eutectic technology on enzymes.In vitro exfoliation tests assessed acid-enzyme synergy in keratin removal.A 4-week clinical trial evaluated the efficacy of a 2%SAE essence aqueous solution on facial skin parameters.Results:Dissolution experiments confirmed that supramolecular deep eutectic technology significantly improved enzyme solubility.Enzymatic activity tests demonstrated that this technology effectively preserved protease activity,substantially enhancing its practical applicability.Furthermore,in vitro exfoliation efficacy tests revealed that this technology strengthened the synergistic interaction between acids and enzymes and exhibited superior stratum corneum-removing capability of the SAE.In clinical evaluations of efficacy,after 7 days of using the essence containing SAE,the formulation significantly enhanced cheek gloss(+8.08%),while reducing comedones volume(-16.25%).after 28 days,significantly enhanced cheek hydration(+25.0%,SCH),gloss(+15.93%),and smoothness(−7.78%SEsm),while reducing TEWL(−6.86%),sebum(−15.54%),roughness(+16.24%SEr),and pore metrics(volume:−39.98%;count:−30.64%),and decreased comedones(blackheads:−70.33%;Whiteheads:−52.42%;all p<0.05).Conclusion:The supramolecular acid-enzyme complex demonstrates enhanced stability,improved solubility,and superior exfoliation efficacy compared to free enzymes.Clinical results further confirm its multifunctional benefits,including enhancing skin hydration,sebum regulation,barrier repair,pore refinement,and comedolytic effects.This study provides both theoretical and practical foundations for developing stable acid-enzyme combinations in dermatological applications.
基金supported by the Project of National Natural Science Foundation of China(Grant No.:82274219 and 81930117)the Key Project of Traditional Chinese Medicine Technology Development Plan of Jiangsu Province,China(Grant No.:ZD202201)Jiangsu Province Postgraduate Scientific Research Practice and Innovation Plan Project,China(Grant Nos.:KYCX21_1735 and SJCX21_0679).
文摘Sustained inflammatory responses are closely related to various severe diseases,and inhibiting the excessive activation of inflammasomes and pyroptosis has significant implications for clinical treatment.Natural products have garnered considerable concern for the treatment of inflammation.Huanglian-Wumei decoction(HLWMD)is a classic prescription used for treating inflammatory diseases,but the necessity of their combination and the exact underlying anti-inflammatory mechanism have not yet been elucidated.Inspired by the supramolecular self-assembly strategy and natural drug compatibility theory,we successfully obtained berberine(BBR)-chlorogenic acid(CGA)supramolecular(BCS),which is an herbal pair from HLWMD.Using a series of characterization methods,we confirmed the self-assembly mechanism of BCS.BBR and CGA were self-assembled and stacked into amphiphilic spherical supramolecules in a 2:1 molar ratio,driven by electrostatic interactions,hydrophobic interactions,andπ–πstacking;the hydrophilic fragments of CGA were outside,and the hydrophobic fragments of BBR were inside.This stacking pattern significantly improved the anti-inflammatory performance of BCS compared with that of single free molecules.Compared with free molecules,BCS significantly attenuated the release of multiple inflammatory mediators and lipopolysaccharide(LPS)-induced pyroptosis.Its anti-inflammatory mechanism is closely related to the inhibition of intracellular nuclear factor-kappaB(NF-κB)p65 phosphorylation and the noncanonical pyroptosis signalling pathway mediated by caspase-11.
基金supported by Zhejiang Provincial Natural Science Foundation of China under(LD22A020002)National Natural Science Foundation of China(52473116,22322508)+1 种基金International Cooperation Project of Ningbo City(2023H019)the Sino-German mobility program(M-0424).
文摘Supramolecular materials,characterized by dynamic reversibility and responsiveness to environmental stimuli,have found widespread applications in numerous fields.Unlike traditional materials,supramolecular materials that rely on non-covalent interactions can allow spontaneous reorganization and self-healing at room temperature.However,these materials typically exhibit low strength due to the weak bonding energies of non-covalent interactions.This study presents the development of a high-strength self-healing supramolecular material that combines multiple interactions including ionic bonding,hydrogen bonding,and coordination bonding.The material,formed by the aggregation of the negatively charged picolinate-grafted copolymer(PCM)with positively charged hyperbranched molecules(HP),is further enhanced by Eu^(3+)ion complexation.The resulting film exhibits a high modulus of 427 MPa,tensile strength of 10.5 MPa,and toughness of 14.7 MJ m^(−3).Meanwhile,the non-covalent interaction of this supramolecular material endows it with a self-healing efficiency of 92%within 24 h at room temperature,as well as multiple remolding properties.The incorporation of lanthanide ions also imparts tunable fluorescence.This study not only provides insights into the development of high-strength self-healing materials but also offers new possibilities for the functionalization of supramolecular materials.
基金supported by the National Natural Science Foundation of China(Nos.22161020,22022107,21801100)the Natural Science Foundation of Jiangxi Province(No.20212BAB203014)the Program of Qingjiang Excellent Young Talents,Jiangxi University of Science and Technology。
文摘Three monomers,namely A2,B2,and GH,were designed and synthesized.By utilizing double host-vip interactions,the monomers A2+B2+GH underwent self-assembly to form a supramolecular linear polymer(SLP)at high concentrations.Long fibers could be pulled from the concentrated SLP solution.Upon the addition of PdCl_(2)(PhCN)_(2)into the SLP solution,a structural transformation occurred from SLP to a supramolecular crosslinked polymer(SCP)through metal coordination interaction.This transformation induced fluorescence quenching,test paper strips for ion detection experiment confirmed that the SLP had good detection ability for Pd^(2+).Furthermore,the SCP underwent a transformation into a gel when the concentration exceeded 145 mmol/L.The SCP gel demonstrated sensitivity to different stimuli,such as K^(+)ions and changes in temperature,accompanied by a reversible transition between sol and gel states.Additionally,rheological analyses indicated that the gel possessed favorable self-healing properties.
基金the Natural Science Foundation of Hunan Province(No.2024JJ6202)the National Natural Science Foundation of China(No.22271087)+1 种基金the Outstanding Youth Scientist Foundation of Hunan Province(No.2021JJ10010)the Huxiang Young Talent Program from Hunan Province(No.2018RS3036)。
文摘Mechanically robust transparent materials that can be repaired have many advantages for practical applications.In this study,a supramolecular strategy is used to introduce healing capacity and mechanical toughness into artificial glass.Non-covalent/dynamic covalent polymerization of thioctic acid(TA)and(±)-trans-1,2-diaminocyclohexane(DC)generates supramolecular glass with versatile attractive properties,including high optical transmittance(>90%),strong impact resistance(2.47 k J/m^(2)),good mechanical strength(21.6 MPa),and high rigidity(65 HD on Shore hardness).The adhesive bonding of poly[TA],along with its photopolymerization behavior,enables damaged areas in poly[DC/TA]to be rebuilt in-situ.Subsequent solidification and hardening of the repaired areas are notably accelerated by hydrogen bonding between poly[TA]and DC.The newly healed poly[DC/TA]exhibits considerable optical and mechanical properties compared to those of untreated poly[DC/TA].This study presents a new design concept for constructing the high-performance glass from low-molecular-weight organic compounds.
基金supported by the Program for improving the Scientific Research Ability of Youth Teachers of Inner Mongolia Agricultural University(No.BR220140)the National Natural Science Foundation of China(No.52263013)+2 种基金the Natural Science Foundation of Inner Mongolia Autonomous Region(No.2021MS02023)the Grassland Talents program of Inner Mongolia Autonomous Regionthe Program of Higher-level Talents of Inner Mongolia Agricultural University(No.NDGCC2016-21)。
文摘Black phosphorus(BP),as a rising star of 2D nanomaterials has drawn considerable attention in cancer therapy.However,the poor stability under ambient conditions limits their practical applications.Herein,a multiple supramolecular assembly composed of adamantane-modified hyaluronic acid(HAADA),ferrocene-modified cinnamaldehyde(Fc-CA),guanidinium-functionalizedβ-cyclodextrin(Guano-CD),and black phosphorus(BP)nanosheets was successfully fabricated through cooperative host-vip and electrostatic interactions.Owing to the cooperative contribution of these building blocks,the obtained supramolecular assembly simultaneously possesses multiple functions including excellent stability,good biocompatibility and targeting property,and a high inhibition effect toward cancer cells.We believe that this work might provide new insights into designing a new generation of cancer theranostic protocols for potential clinical applications.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFB3808800,Dake Xu)the National Natural Science Foundation of China(Grant Nos.U2006219(Dake Xu),52301081(Xiangyu Li))+4 种基金the National Postdoctoral Program for Innovative Talents(Grant No.BX20220059,Xiangyu Li)the China Postdoctoral Science Foundation(Grant No.2022M720677,Xiangyu Li)the Liaoning Provincial Natural Science Foundation of China(Grant No.2023-BS-052,Xiangyu Li)the Fundamental Research Funds for the Central Universities(Grant No.N2302015,Xiangyu Li)the State Key Laboratory of Marine Coatings Funded Project(Grant No.2024020800027,Xiangyu Li).
文摘Surface-adhering biofilms contribute significantly to irreversible biofouling and corrosion,presenting a multi-trillion-dollar annual problem in public health and industry.Strategies employing antibacterial elements are emerging to fabricate multifunctional coatings that effectively combat such microbially produced damage.However,rapid,reliable,and robust surface engineering remains challenging due to stability limitations and intricate anti-biofilm additive dynamics.Herein,a silver-capsule-conjugated polyurethane coating with high stability and antimicrobial efficacy in a cooperative manner is developed through controlled supramolecular self-assembly.Polyvinylpyrrolidone(PVP)-mediated molecule entanglement breaks through the incompatibility between polymeric components and nanomaterials,strengthening the dispersion and fixation of encapsulated silver nanoparticles.The facilitation and control of the nanoscale interfacial binding significantly suppresses the aggregation of inorganic nanoparticles and consequent microcracks development,giving rise to mechanical robustness and thermal stability of the hybrid coating under extreme conditions.A synergistic combination of exposed residues,electrostatic,and coordination interactions could readily integrate the resultant coating on virtually arbitrary material sur-faces.This composite coating exhibits broad-spectrum and high bactericidal efficiencies of 99.99% against Staphylococcus aureus and Escherichia coli,as well as excellent biofilm formation suppression.Moreover,our coating has robust resistance to microbial-influenced corrosion(MIC)and can even endure 720 h of salt spray.This study deciphers a general code for creating stable and durable nanohybrid coatings to mitigate microbially related risks.
基金the National Natural Science Foundation of China(Nos.21801063,22305070 and U20041101)the Top-Notch Talents Program of Henan Agricultural University(Nos.30501049 and 30501032)for financial support。
文摘Herein,a ternary supramolecular assembly(BPP-BQ?CB[8]-SCD)is successfully constructed by a bromophenylpyridine-tethered-bromoisoquinoline(BPP-BQ),cucurbit[8]uril(CB[8])and sulfonatedβ-cyclodextrin(SCD)via successive assembling way,exhibiting progressively enhanced green roomtemperature phosphorescence(RTP).The self-aggregates of BPP-BQ?CB[8]-SCD accommodate an energy acceptor rhodamine B(Rh B)to form a light-harvesting system(BPP-BQ?CB[8]-SCD@Rh B)with further enhanced yellow long-lifetime luminescence with large Stokes shift based on triplet-singlet F?rster resonance energy transfer(TS-FRET).Crucially,the introduction of a photoactive diarylethene achieves the long-lived photoluminescence of BPP-BQ?CB[8]-SCD@Rh B to be switched with the efficiency of up to98%through logically ordered lowering/enhancing RTP performance of the energy donor and intercepting/restoring TS-FRET pathway,when stimulated by host-vip competition and light illumination in sequence.Moreover,BPP-BQ?CB[8]-SCD@Rh B is evenly doped into polyvinyl alcohol or polyacrylamide to obtain high-performance luminescent films with long afterglow.The abovementioned logically ordered stimulus-switched long-lived emission enables the light-harvesting system in both solution and solid state to be applied in high-security-level information encryption and transformation,and anticounterfeiting.
基金support of this research by the National Natural Science Foundation of China(Nos.22202171,21922202,and 22272146)the Natural Science Foundation of Jiangsu Basic Research Program(No.BK20220559)+1 种基金the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province(No.22KJD150009)the Jiangsu Specially-Appointed Professor Plan(Z.Xi)from the Jiangsu Education Department。
文摘Rational tuning of chiral nanostructures of supramolecular assemblies as catalysts and investigating their chiral morphology-enantioselectivity dependence is rarely reported. Herein, we report a series of supramolecular M/P-helical nanoribbons(HNs) assembled from the chiral L/D-glutamate-based amphiphiles(L/D-Glu C16) and Cu(Ⅱ) ions, with their helical screw pitches adjusted from 217 nm to 104 nm through the facile regulation of their water/organic solvent assembly environment. They were then used as ideal models to reveal the chiral morphology-enantioselectivity relationship by catalyzing the asymmetric Diels-Alder reaction. Better enantioselectivity was achieved with more twist morphology. Experimental evidences of stronger chiral transfer effect from the supramolecular HNs with more twist to the aza-chalcone as reactant were obtained to understand such dependence. Our study demonstrates a new perspective for designing supramolecular catalysts with higher enantioselectivity.
基金supported by the National Natural Science Foundation of China(No.22271154)Natural Science Foundation of Jiangsu Province(No.BK20211179)+3 种基金Innovation Support Program of Jiangsu Province(No.BZ2023055)Fundamental Research Funds for the Central Universities(No.NS2023033)China Postdoctoral Science Foundation(No.2023M731658)Achievement Transformation Project of Qinghai Province(No.2021-SF-145).
文摘Supramolecular prodrug vesicles(H-4⊃B-2@MB)with selective antibacterial activity have been successfully constructed.Specifically,a natural antibiotic prodrug(B-2)with glutathione(GSH)-responsiveness was synthesized.The hydrophobic interaction between B-2 and a novel water-soluble cavitand with deep cavity(H-4)resulted in the formation of a host-vip complex,which further self-assembled into supramolecular vesicles.The formed vesicles could effectively encapsulate the photosensitizer methylene blue(MB),enabling co-delivery of antibiotics and photosensitizers in the presence of GSH.Moreover,upon excitation at 630 nm,the photosensitizers generate reactive oxygen species(ROS),effectively eradicating E.coli through combined chemo-photodynamic therapy.Considering that GSH is predominantly present in Gram-negative bacteria such as E.coli,this strategy exhibits substantial potential for selectively inhibiting bacteria characterized by high GSH levels to regulate bacterial colony equilibrium.
基金funded by Tongzhou District Health Development Research Reserve Project Foundation(No.KJ2024CX024)Natural Science Foundation of Tianjin City(No.23JCQNJC01640)+1 种基金National Natural Science Foundation of China(Nos.82304393,22404122)Beijing Nova Program(No.Z211100002121127).
文摘Metal ions trigger Fenton/Fenton-like reactions,generating highly toxic hydroxyl radicals(•OH)for chemodynamic therapy(CDT),which is crucial in inducing lethal oxidative DNA damage and subsequent cell apoptosis.However,tumor cells can counteract this damage through repair pathways,particularly MutT homolog 1(MTH1)protein attenuation of oxidative DNA damage.Suppression of MTH1 can enhance CDT efficacy,therefore,orderly integrating Fenton/Fenton-like agents with an MTH1 inhibitor is expected to significantly augment CDT effectiveness.Carrier-free CuTH@CD,self-assembled through the supramolecular orchestration ofγ-cyclodextrin(γ-CD)with Cu^(2+)and the MTH1 inhibitor TH588,effectively overcoming tumor resistance by greatly amplifying oxidative damage capability.Without additional carriers and mediated by multiple supramolecular regulatory effects,CuTH@CD enables high drug loading content,stability,and uniform size distribution.Upon internalization by tumor cells,CuTH@CD invalidates repair pathways through Cu^(2+)-mediated glutathione(GSH)depletion and TH588-mediated MTH1 inhibition.Meanwhile,both generated Cu^(+)ions and existing ones within the nanoassembly initiate a Fentonlike reaction,leading to the accumulation of•OH.This strategy enhances CDT efficiency with minimal side effects,improving oxidative damage potency and advancing self-delivery nanoplatforms for developing effective chemodynamic tumor therapies.
文摘Nanoscale drug delivery systems(nano-DDSs)have attracted intense interest in tumor chemotherapy in the last decades,to improve antitumor efficacy and minimize toxic and side effects.As a versatile supramolecular building block,cyclodextrins(CDs)have been widely used in the fabrication of the smart nano-DDSs.Besides their multifunctionality,which makes them versatile core in the star(co)polymers for micellar nanomedicines,specific host-vip inclusion complexation via their hydrophobic cavities endows them diversified functions:(i)design of amphiphilic copolymers for micellar nanomedicines,(ii)supramolecular hydrogels and poly(pseudo)rotaxane nano-hydrogels as drug carriers,and(iii)recipient for direct and indirect drug-loading.In the present work,the recent progress of CDs in nano-DDSs for tumor chemotherapy was reviewed,classified by the crucial roles of CD units.Based on the structureperformance relationship,the future perspective was also proposed.
基金support from The Hong Kong Polytechnic University(U-CDCA)and Innovation and Technology Fund(ITS-322-23FP)。
文摘Developing advanced polymer electrolytes in lithium metal batteries(LMBs)has gained significant attention because of their inherent safety advantages over liquid electrolytes,while still encountering great challenges in mitigating uneven lithium plating/stripping and dendrite growth.Previous efforts primarily focused on passive approaches to mechanically constrain lithium dendrite growth.Recent studies have revealed the significance and effectiveness of regulating supramolecular interactions between polymer chains and other electrolyte components for homogenizing lithium deposition and enhancing the interfacial stability.This report provides a timely critical review to cover recent inspiring advancements in this direction.We first summarize the origins of supramolecular interaction origins,strength-determining factors,and structure–property relationships to establish quantitative correlations between polymer composition and supramolecular interaction properties.Then the recent advances in regulating supramolecular interaction chemistry are comprehensively discussed,focusing on those towards accelerated mass transport and stabilized anode-electrolyte interface.Finally,the remaining challenges are highlighted,and potential future directions in supramolecular interaction regulation of polymer electrolytes are prospected for the practical application of LMBs.
基金the Shanxi Province Science Foundation for Youth(No.202203021212408)the Shanxi Normal University Quality Curriculum(No.2019YZKC-13)the 1331 Project of Shanxi Province。
文摘Although supramolecular transformations have been emerged as a potent strategy for transitioning between various topologies,post-modification induced topological transformations have never been explored in the context of[2]catenane topologies.In this study,we present a novel supramolecular transformation between a Hopf link and a macrocycle,induced by the Diels–Alder click reaction.By strategically selecting the half-sandwich ruthenium binuclear fragment B as a rigid capping agent,we successfully integrated tetrazine moieties into the metalla[2]catenane structure.We demonstrated that the introduction of 2,5-norbornadiene(NBD)as an external stimulus allows for the transformation of the novel metalla[2]catenane,featuring reactive tetrazine sites,into the corresponding monomeric ring through postmodification for the first time.The synthetic results are corroborated by single-crystal X-ray diffraction analysis,ESI-TOF/MS,elemental analysis,and detailed solution-state NMR techniques.
