The development of enantioselective C-H macrocyclizations to efficiently access structurally diversified macrocycles is highly desirable,but remain a big challenge.Herein,we reported the first rhodium(Ⅲ)-catalyzed as...The development of enantioselective C-H macrocyclizations to efficiently access structurally diversified macrocycles is highly desirable,but remain a big challenge.Herein,we reported the first rhodium(Ⅲ)-catalyzed asymmetric intramolecular C-H macrocyclization,enabling the efficient synthesis of structurally diverse enantioenriched macrocycles.This robust enantioselective C-H macrocyclization has a broad functional group tolerance,excellent enantioselectivities(up to 98.5:1.5 e.r.)and a mild reaction condition,releasing CO_(2)as the single by-product.More significantly,the resulting unique enantioenriched19-membered macrocycle 2f was found to demonstrate a potent in vitro anti-Zika virus(ZIKV)activity without obvious cytotoxicity.Further investigation revealed that the anti-ZIKV activity is presumably attributed to an autophagy inhibition in the early stage of viral infection by down-regulating the expression of autophagy related gene Atg12.展开更多
The development of innovative strategies and methods to provide natural product-like macrocycles not accessible by biosynthesis, but endowed with novel bioactivities and simplified structure, is highly desirable. Insp...The development of innovative strategies and methods to provide natural product-like macrocycles not accessible by biosynthesis, but endowed with novel bioactivities and simplified structure, is highly desirable. Inspired by the key scaffolds of rapamycin and FR252921, herein, we report a Rh(III)-catalyzed C–H alkylation macrocyclization, which enables access to CF_(3)-substituted macrolides. DFT calculations reveal that the chemoselectivity between C–H alkylation and olefination macrocyclization was highly controllable. Moreover, the unique CF_(3)-substituted macrolides showed potent anti-inflammation activities against TNF-α, IL-6 and CCL2 m RNA expression.展开更多
Influenza virus poses a significant threat to global public health,causing serious repercussions on human life and social well-being.Over the past decades,various antiviral drugs targeting either the virus itself or i...Influenza virus poses a significant threat to global public health,causing serious repercussions on human life and social well-being.Over the past decades,various antiviral drugs targeting either the virus itself or its host were identified.However,the emergence of drug-resistant influenza virus strains has posed a critical challenge to the effectiveness of these existing anti-influenza agents .Consequently,there is an urgent need to develop novel molecules with new chemical frameworks.Macrocyclic natural products serve as a crucial resource for validating targets and discovering lead compounds.However,the number of naturlly crring macrocyclic natural products is limited due to inherent biosynthetic pathways,which restricts the development of macrocyclic drugs.In contrast,artificially synthesized pseudonatural products show enhanced availability and greater structural diversity,while possessing similar biological functions[5]and have attracted significant interest from medicinal chemists.Hence,it is valuable to develop effective synthetic methods to expedite the discovery of macrocyclic lead compounds.展开更多
Thermally activated delayed fluorescence(TADF)depends on reverse intersystem crossing(RISC)from the lowest triplet to the singlet excited state.Here,a macrocyclization strategy is developed to achieve TADF emission by...Thermally activated delayed fluorescence(TADF)depends on reverse intersystem crossing(RISC)from the lowest triplet to the singlet excited state.Here,a macrocyclization strategy is developed to achieve TADF emission by promoting RISC.5-(9Hcarbazol-9-yl)isophthalonitrile,a fluorescent molecule,is coupled with 1,4-dimethoxybenzene by methylene bridges to form a macrocycle with TADF emission.Experimental results and theoretical calculation indicate that the macrocyclization strategy contributes to RISC promotion and suppression of nonradiative decay,resulting in effective TADF emission transformed from prompt fluorescence.Three TADF luminophores are cyclized with the same strategy,and an enhanced TADF emission of up to3.8 folds is observed.The marriage of macrocycle chemistry and luminescent materials will provide new guidelines for designing efficient TADF materials.展开更多
Macrocyclic hosts play a crucial role in supramolecular chemistry and the development of supramolecular functional materials.Their well-defined cavities and diverse host-vip interactions endow macrocycles with excel...Macrocyclic hosts play a crucial role in supramolecular chemistry and the development of supramolecular functional materials.Their well-defined cavities and diverse host-vip interactions endow macrocycles with excellent stimuli responsiveness,facilitating efficient assembly construction.However,the limited availability of functional groups in conventional macrocycles restricts their ability to meet the demand for fabricating materials with multiple functionalities.To address this limitation,several research groups have introduced tetraphenylethylene(TPE),a well-known building block renowned for its remarkable aggregation-induced emission(AIE)effect,into the macrocycle framework.Herein,this paper summarizes the combination strategies and synergistic approaches that achieve multi-functionality by integrating TPE and macrocyclic architectures.The emission characteristics of TPE-embedded macrocycles are elucidated,and it is anticipated that more AIE-type macrocycles with innovative backbones and broad applications will emerge.展开更多
The preparation,functionalization,and investigations in host-vip properties of high-level pillararene macrocycles have long been a big challenge because of the lack of efficient synthetic methods.Herein,a novel type...The preparation,functionalization,and investigations in host-vip properties of high-level pillararene macrocycles have long been a big challenge because of the lack of efficient synthetic methods.Herein,a novel type of pillararene derivative,namely desymmetrized pillar[8]arene(DP[8]A),has been successfully synthesized via a facile two-step strategy with high yield.Compared with its pillar[8]arene counterpart,DP[8]A is composed of four alkoxy-substituted benzene units and four bare benzene rings.Single crystal analysis has been performed in order to unveil the molecular conformation and packing mode of DP[8]A,which indicated that DP[8]A possesses a unique chair-like structure and much smaller steric hindrance.Density functional theory(DFT)calculations and electrostatic potential map suggested the inhomogeneous electronic distribution in the DP[8]A cavity.Water-soluble carboxylate-modified DP[8]A,that is,CDP[8]A,was also prepared to investigate the host-vip properties in aqueous solution with methyl viologen(MV),where the binding constant and morphologies of the formed host-vip complexes have been studied.In all,this new version of eight-membered pillararene derivative might potentially serve as a powerful macrocycle candidate for further applications in supramolecular chemistry.展开更多
Many azo compounds and their intermediates are toxic and have been linked to various health issues,representing a growing global problem.Molecular engineering for selective encapsulation of azobenzene compounds is cri...Many azo compounds and their intermediates are toxic and have been linked to various health issues,representing a growing global problem.Molecular engineering for selective encapsulation of azobenzene compounds is critical,given their significant use in smart materials and prevalence as environmental micropollutants released from the food and dye industries.However,the current host molecules catering to azobenzene compounds are mainly limited to cyclodextrins,pillar[n]arenes and cucurbit[n]urils,demonstrating a moderate affinity.This report describes that a novel 3,3'-bipyridinium-based cyclophane was capable of encapsulating anionic azobenzene compounds in water with high binding affinity and pH stability through electrostatic attraction-enhanced mechanism,surpassing the extensively reported supramolecular systems.1D&2D NMR experiments,UV-vis spectrum,X-ray crystallography and computational modeling were carried out to understand the host-vip complexation.It's worth noting that the tetracationic cyclophane exhibited good selective and anti-interference encapsulation properties in binary,ternary and seawater systems.Furthermore,upon UV/white light irradiation,the reversible conversion between(E)-4,4'-azobisbenzoate and(Z)-4,4'-azobisbenzoate triggers the dissociation/recomplexation of the host-vip complex within 3 min.This reversible photo-switchable(E)-disodium 4,4'-azobisbenzoateBPy-Box^(4+)supramolecular system holds promise for designing novel materials for extraction/release of azo compounds and other small smart materials.展开更多
Preparing free-base porphyrinoid radicals that can function as coordination ligands is a challenging task.Here we report the synthesis of a stable,free-base benzocorrole(BC)radical containing only two inner NH protons...Preparing free-base porphyrinoid radicals that can function as coordination ligands is a challenging task.Here we report the synthesis of a stable,free-base benzocorrole(BC)radical containing only two inner NH protons via a retro-Diels-Alder conversion.The radical character of BC was fully supported by crystallographic analysis,spectroscopic evidence,and theoretical calculations.This neutral radical ligand allowed easy insertion of Zn(Ⅱ),Ga(Ⅲ),and Pd(Ⅱ)ions to produce radical complexes.All these radicals exhibited luminescence-on responses under weak reducing atmosphere,corresponding to the conversion to their aromatic anions.The red fluorescence was observed for BC and its Zn(Ⅱ)and Ga(Ⅲ)complexes,and the near-infrared phosphorescence(>900 nm)was detected for Pd(Ⅱ)complex at room temperature.Furthermore,Ga(Ⅲ)corrole exhibited a variation in fluorescence in response to axial coordination.Our findings provide a promising radical platform for coordination and developing novel functional materials with switchable spin and emission.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
A novel[3]rotaxane,featuring two hydrogen-bonded aramide azo-macrocycles mechanically interlocked on a dumbbell with distinct recognition sites,a secondary dialkylammonium(AM)unit and a 4,4'-bipyridinium(BP)unit,h...A novel[3]rotaxane,featuring two hydrogen-bonded aramide azo-macrocycles mechanically interlocked on a dumbbell with distinct recognition sites,a secondary dialkylammonium(AM)unit and a 4,4'-bipyridinium(BP)unit,has been synthesized.This multi-stimuli-responsive[3]rotaxane exhibits unique molecular motion,with the macrocycles shuttling along the axle in response to acid-base reactions,temperature changes,solvent variations,and light irradiation.The molecular shuttle and reversibility were investigated by^(1)H NMR,2D NOESY,HRESI-MS,and UV-vis spectroscopy.This study provides a rare example of a higher order rotaxane with multi-stimuli responsiveness,highlighting its potential for multi-state control over the motion of interlocked rings on an axle.The ability to manipulate the molecular motion of the macrocycles through various external triggers offers insights for future developments in molecular machinery and adaptive materials.展开更多
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
Herein we report an environmentally friendly and energy-efficient method for the adsorptive separation of toluene from toluene-alcohol azeotropes using porous crystalline fluorinated leaning pillar[6]arene(FLP6α),ach...Herein we report an environmentally friendly and energy-efficient method for the adsorptive separation of toluene from toluene-alcohol azeotropes using porous crystalline fluorinated leaning pillar[6]arene(FLP6α),achieving up to 100%purity.Moreover,FLP6αdemonstrates rapid adsorption and excellent recyclability.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
Macrocyclic polyamines are excellent chelating agents with the advantage of forming highly stable complexes.They offer the flexibility to adjust the coordination environment through functionalization.making them valua...Macrocyclic polyamines are excellent chelating agents with the advantage of forming highly stable complexes.They offer the flexibility to adjust the coordination environment through functionalization.making them valuable in numerous applications owing to their unique chemical and biological characteristics.This review summarizes the use of macrocyclic polyamines as carriers and molecular platforms of targeted drugs for medical applications.The significance and innovative design of these original approaches are dissected from the unique perspective of diverse mechanisms,such as iron depletion,metallo-β-lactamases inhibitors,intracellular ATP depletion,non-viral gene vector,DNA/RNA syntheses inhibitors and theranostics agent.Of interest are the metal complex of macrocyclic polyamines,which is usually a double-edged sword as dealing with endogenous macromolecular targets,especially DNA.These excellent cases will help to understand the typical mechanism in drug design based on macrocyclic polyamines,and achieve actual applications in medicine.展开更多
Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active...Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active sites inside the cavity of macrocyclic arenes to better mimic molecular recognition of bioreceptors and enzymes.The editorial aims to enlighten scientists in this field when they develop novel macrocycles for molecular recognition, supramolecular assembly, and applications.展开更多
Recently,stimuli-responsive nanocarriers capable of precision drug release have garnered significant attention in the field of drug delivery.Here,an in-situ dynamic covalent self-assembled(DCS)strategy was utilized to...Recently,stimuli-responsive nanocarriers capable of precision drug release have garnered significant attention in the field of drug delivery.Here,an in-situ dynamic covalent self-assembled(DCS)strategy was utilized to develop a co-delivery system.This assembly was based on a thiol-disulfide-exchange reaction,producing disulfide macrocycles in an oxidizing aerial environment.These macrocycles encapsulated the anti-cancer drug(paclitaxel,PTX)on the surface of gold nanoparticles,which served as photothermal therapy agents during the self-assembly.In the DCS process,the kinetic control over the concentration of each building unit within the reaction system led to the formation of a stable co-delivery nanosystem with optimal drug-loading efficiency.Notably,the high glutathione(GSH)concentrations in tumor cells caused the disulfide macrocycles in nanostructures to break,resulting in drug release.The stimuli-responsive performances of the prepared nanosystems were determined by observing the molecular structures and drug release.The results revealed that the self-assembled nanosystem exhibited GSH-triggered drug release and good photothermal conversion capability under near-infrared light.Moreover,the in vitro and in vivo results revealed that conjugating the targeting molecule of cRGD with co-delivery nanosystem enhanced its biocompatibility,chemo-photothermal anti-cancer effect.Overall,our findings indicated that in-situ DCS strategy enhanced the control over drug loading during the construction of the co-delivery system,paving a way for the development of more functional carriers in nanomedicine.展开更多
In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff...In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff base macrocyclic ligands incorporating the pyridine moiety,and their complexes,were revised,and in 2015 the chemistry of pentaaza macrocycle ligands with rare earth metals was also summarized.Porphyrin and phthalocyanine ligands are not included in this review,which primarily focuses on complexes with Schiff bases and amines without pendant arms or any additional donor other than nitrogen.The synthetic methods,structural characterization,based on single X-ray crystal data,and properties of the lanthanoid complexes,with special attention to magneto-structural correlations,are presented herein.展开更多
Tryptophan(Trp)is an essential amino acid that plays a critical role in human physiology.The increasing demand for Trp has created a highly promising market,underscoring the urgent necessity for the development of eff...Tryptophan(Trp)is an essential amino acid that plays a critical role in human physiology.The increasing demand for Trp has created a highly promising market,underscoring the urgent necessity for the development of efficient strategies for the simultaneous detection and uptake of tryptophan.Herein,we report an expanded“Texas-sized”molecular box(An-TxSB),which incorporates luminescent anthracene bridging subunits and molecular recognition motifs.This luminescent molecular box demonstrates exceptional sensitivity to Trp in water,permitting its precise quantification with a notably low limit of detection(LOD)of 0.42μmol/L.Moreover,An-TxSB facilitates the proficient uptake of Trp from simulated water samples,thereby revealing an impressive Trp adsorption capacity of up to 226.0μmol/g.展开更多
On account of the complicated magnetic exchange interactions between lanthanide ions,binuclear lanthanide complexes have broad application prospect in the field of single-molecule magnets.Therefore,it is necessary to ...On account of the complicated magnetic exchange interactions between lanthanide ions,binuclear lanthanide complexes have broad application prospect in the field of single-molecule magnets.Therefore,it is necessary to develop reasonable bridging ligands to manipulate the directional assembly of binuclear lanthanide complexes.Herein,we selected the macrocyclic ligand L^(N_(8)O_(2))to build up two new dilanthanide complexes[Ln_(2)(LN_(8)O_(2))(OpyO)_(2)(H_(2)O)2](NO_(3))_(2)(1-Ln,Ln=Dy,Tb;LN_(8)O_(2)=hexamethyl-tetraaza-dioxe-dipyrazolacycloicosaphane-2,9,12,19-tetraene;OpyOH=2-pyridinol-1-oxide).Dynamic magnetic studies show that 1-Dy exhibits slow relaxation behavior under a 1 kOe applied field.Further fitting analysis of relaxation times gives the effective energy barrier of 38.2 cm^(−1),and reveals that the slow magnetic relaxation behavior is dominated by the Orbach and Raman processes.High-resolution luminescence emission spectrum indicates the energy gap of 36.8 cm^(−1)between the ground state and the first excited state,consistent with the magnetic measurement results.1-Tb exhibits brilliant characteristic green light emission under UV light excitation.The absolute quantum yield of 1-Tb is 44.8%,and its first-order fitted decay lifetime is 779.21μs at room temperature.This study provides the way for directional construction of high-performance molecular materials with magnetic and optical dual-function.展开更多
Host-vip recognition-based macrocycle in macrocycle to form"Russian doll"assemblies remains an interesting topic in supramolecular chemistry.Herein,a macrocycle-in-macrocycle assembly was studied using cuc...Host-vip recognition-based macrocycle in macrocycle to form"Russian doll"assemblies remains an interesting topic in supramolecular chemistry.Herein,a macrocycle-in-macrocycle assembly was studied using cucurbit[10]uril(Q[10])and the smallest cucurbituril-like macrocycle(TD[4]).X-ray crystal structure analysis revealed that TD[4]was encapsulated in the cavity of Q[10]to form a 1:1 complex.Importantly,competitive vip studies suggested that TD[4]had the highest binding constant with the Q[10]host among the vips used,including Q[5],Me_(8)TD[4],and amantadine molecules in water.Our results provided a new cucurbituril-based Russian-doll structure containing both the largest and smallest cavities of the cucurbiturils,which expanded the family of molecular Russian dolls.展开更多
基金supported by National Natural Science Foundation of China(No.81973166)Science and Technology Commission of Shanghai Municipality(No.22XD1424600)+4 种基金Natural Science Foundation of Shanghai Municipality(No.22ZR1474100)Taishan Scholar Foundation of Shandong Province(No.tsqn202306322)National Key R&D Program of China(No.2021YFC2300700)Shandong Laboratory Program(No.SYS202205)Shandong Provincial Natural Science Foundation(Nos.ZR2023LSW003 and ZR2023JQ028)。
文摘The development of enantioselective C-H macrocyclizations to efficiently access structurally diversified macrocycles is highly desirable,but remain a big challenge.Herein,we reported the first rhodium(Ⅲ)-catalyzed asymmetric intramolecular C-H macrocyclization,enabling the efficient synthesis of structurally diverse enantioenriched macrocycles.This robust enantioselective C-H macrocyclization has a broad functional group tolerance,excellent enantioselectivities(up to 98.5:1.5 e.r.)and a mild reaction condition,releasing CO_(2)as the single by-product.More significantly,the resulting unique enantioenriched19-membered macrocycle 2f was found to demonstrate a potent in vitro anti-Zika virus(ZIKV)activity without obvious cytotoxicity.Further investigation revealed that the anti-ZIKV activity is presumably attributed to an autophagy inhibition in the early stage of viral infection by down-regulating the expression of autophagy related gene Atg12.
基金the"100 Talent Program of Chinese Academy of Sciences""1000-Youth Talents Plan"+3 种基金ShanghaiYouth Talent,National Science&Technology Major Project"Key New Drug Creation and Manufacturing Program"China(No. 2018ZX09711002–006)Science and Technology Commission of Shanghai Municipality (No. 18431907100)ShanghaiTechnology Innovation Action Plan (No. 18JC1415300)the Research Grants Council of Hong Kong (No. HKUST 16302418) for financial support of this research。
文摘The development of innovative strategies and methods to provide natural product-like macrocycles not accessible by biosynthesis, but endowed with novel bioactivities and simplified structure, is highly desirable. Inspired by the key scaffolds of rapamycin and FR252921, herein, we report a Rh(III)-catalyzed C–H alkylation macrocyclization, which enables access to CF_(3)-substituted macrolides. DFT calculations reveal that the chemoselectivity between C–H alkylation and olefination macrocyclization was highly controllable. Moreover, the unique CF_(3)-substituted macrolides showed potent anti-inflammation activities against TNF-α, IL-6 and CCL2 m RNA expression.
基金supported by the Natural Science Foundation of Jiangsu Province(No.BK20201332).
文摘Influenza virus poses a significant threat to global public health,causing serious repercussions on human life and social well-being.Over the past decades,various antiviral drugs targeting either the virus itself or its host were identified.However,the emergence of drug-resistant influenza virus strains has posed a critical challenge to the effectiveness of these existing anti-influenza agents .Consequently,there is an urgent need to develop novel molecules with new chemical frameworks.Macrocyclic natural products serve as a crucial resource for validating targets and discovering lead compounds.However,the number of naturlly crring macrocyclic natural products is limited due to inherent biosynthetic pathways,which restricts the development of macrocyclic drugs.In contrast,artificially synthesized pseudonatural products show enhanced availability and greater structural diversity,while possessing similar biological functions[5]and have attracted significant interest from medicinal chemists.Hence,it is valuable to develop effective synthetic methods to expedite the discovery of macrocyclic lead compounds.
基金supported by the Zhejiang Provincial Natural Science Foundation of China(LQ24B020003,LR24B020003)the National Natural Science Foundation of China(21921003,22205040,22401210)。
文摘Thermally activated delayed fluorescence(TADF)depends on reverse intersystem crossing(RISC)from the lowest triplet to the singlet excited state.Here,a macrocyclization strategy is developed to achieve TADF emission by promoting RISC.5-(9Hcarbazol-9-yl)isophthalonitrile,a fluorescent molecule,is coupled with 1,4-dimethoxybenzene by methylene bridges to form a macrocycle with TADF emission.Experimental results and theoretical calculation indicate that the macrocyclization strategy contributes to RISC promotion and suppression of nonradiative decay,resulting in effective TADF emission transformed from prompt fluorescence.Three TADF luminophores are cyclized with the same strategy,and an enhanced TADF emission of up to3.8 folds is observed.The marriage of macrocycle chemistry and luminescent materials will provide new guidelines for designing efficient TADF materials.
基金the National Natural Science Foundation of China(No.22271154)the Science Fund for Distinguished Young Scholars of Jiangsu Province(No.BK20240078).
文摘Macrocyclic hosts play a crucial role in supramolecular chemistry and the development of supramolecular functional materials.Their well-defined cavities and diverse host-vip interactions endow macrocycles with excellent stimuli responsiveness,facilitating efficient assembly construction.However,the limited availability of functional groups in conventional macrocycles restricts their ability to meet the demand for fabricating materials with multiple functionalities.To address this limitation,several research groups have introduced tetraphenylethylene(TPE),a well-known building block renowned for its remarkable aggregation-induced emission(AIE)effect,into the macrocycle framework.Herein,this paper summarizes the combination strategies and synergistic approaches that achieve multi-functionality by integrating TPE and macrocyclic architectures.The emission characteristics of TPE-embedded macrocycles are elucidated,and it is anticipated that more AIE-type macrocycles with innovative backbones and broad applications will emerge.
基金the Natural Science Foundation of Jilin Province(No.20230101052JC)he National Natural Science Foundation of China(Nos.52173200 and 52203138)the Jilin Province Science and Technology Development Plan Project(No.#YDZJ202201ZYTS523)for financial support。
文摘The preparation,functionalization,and investigations in host-vip properties of high-level pillararene macrocycles have long been a big challenge because of the lack of efficient synthetic methods.Herein,a novel type of pillararene derivative,namely desymmetrized pillar[8]arene(DP[8]A),has been successfully synthesized via a facile two-step strategy with high yield.Compared with its pillar[8]arene counterpart,DP[8]A is composed of four alkoxy-substituted benzene units and four bare benzene rings.Single crystal analysis has been performed in order to unveil the molecular conformation and packing mode of DP[8]A,which indicated that DP[8]A possesses a unique chair-like structure and much smaller steric hindrance.Density functional theory(DFT)calculations and electrostatic potential map suggested the inhomogeneous electronic distribution in the DP[8]A cavity.Water-soluble carboxylate-modified DP[8]A,that is,CDP[8]A,was also prepared to investigate the host-vip properties in aqueous solution with methyl viologen(MV),where the binding constant and morphologies of the formed host-vip complexes have been studied.In all,this new version of eight-membered pillararene derivative might potentially serve as a powerful macrocycle candidate for further applications in supramolecular chemistry.
基金support by the National Natural Science Foundation of China(No.52473225)the Guangdong Basic and Applied Basic Research Foundation(No.2023A1515110262)。
文摘Many azo compounds and their intermediates are toxic and have been linked to various health issues,representing a growing global problem.Molecular engineering for selective encapsulation of azobenzene compounds is critical,given their significant use in smart materials and prevalence as environmental micropollutants released from the food and dye industries.However,the current host molecules catering to azobenzene compounds are mainly limited to cyclodextrins,pillar[n]arenes and cucurbit[n]urils,demonstrating a moderate affinity.This report describes that a novel 3,3'-bipyridinium-based cyclophane was capable of encapsulating anionic azobenzene compounds in water with high binding affinity and pH stability through electrostatic attraction-enhanced mechanism,surpassing the extensively reported supramolecular systems.1D&2D NMR experiments,UV-vis spectrum,X-ray crystallography and computational modeling were carried out to understand the host-vip complexation.It's worth noting that the tetracationic cyclophane exhibited good selective and anti-interference encapsulation properties in binary,ternary and seawater systems.Furthermore,upon UV/white light irradiation,the reversible conversion between(E)-4,4'-azobisbenzoate and(Z)-4,4'-azobisbenzoate triggers the dissociation/recomplexation of the host-vip complex within 3 min.This reversible photo-switchable(E)-disodium 4,4'-azobisbenzoateBPy-Box^(4+)supramolecular system holds promise for designing novel materials for extraction/release of azo compounds and other small smart materials.
基金supported by the National Natural Science Foundation of China(Nos.22271140,22071103,and 22371118)。
文摘Preparing free-base porphyrinoid radicals that can function as coordination ligands is a challenging task.Here we report the synthesis of a stable,free-base benzocorrole(BC)radical containing only two inner NH protons via a retro-Diels-Alder conversion.The radical character of BC was fully supported by crystallographic analysis,spectroscopic evidence,and theoretical calculations.This neutral radical ligand allowed easy insertion of Zn(Ⅱ),Ga(Ⅲ),and Pd(Ⅱ)ions to produce radical complexes.All these radicals exhibited luminescence-on responses under weak reducing atmosphere,corresponding to the conversion to their aromatic anions.The red fluorescence was observed for BC and its Zn(Ⅱ)and Ga(Ⅲ)complexes,and the near-infrared phosphorescence(>900 nm)was detected for Pd(Ⅱ)complex at room temperature.Furthermore,Ga(Ⅲ)corrole exhibited a variation in fluorescence in response to axial coordination.Our findings provide a promising radical platform for coordination and developing novel functional materials with switchable spin and emission.
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supported by the National Natural Science Foundation of China(No.22271202 to L.Yuan,No.22201193 to X.Li)the Sichuan Science and Technology Program(No.2023NSFSC0109 to X.Li)+2 种基金the Fundamental Research Funds for the Central Universities and the Hundred Talent Program of Sichuan University(No.YJ2021158 to X.Li)Sichuan University Interdisciplinary Innovation Fund(X.Li)Open Project of State Key Laboratory of Supramolecular Structure and Materials(No.SKLSSM2024037)。
文摘A novel[3]rotaxane,featuring two hydrogen-bonded aramide azo-macrocycles mechanically interlocked on a dumbbell with distinct recognition sites,a secondary dialkylammonium(AM)unit and a 4,4'-bipyridinium(BP)unit,has been synthesized.This multi-stimuli-responsive[3]rotaxane exhibits unique molecular motion,with the macrocycles shuttling along the axle in response to acid-base reactions,temperature changes,solvent variations,and light irradiation.The molecular shuttle and reversibility were investigated by^(1)H NMR,2D NOESY,HRESI-MS,and UV-vis spectroscopy.This study provides a rare example of a higher order rotaxane with multi-stimuli responsiveness,highlighting its potential for multi-state control over the motion of interlocked rings on an axle.The ability to manipulate the molecular motion of the macrocycles through various external triggers offers insights for future developments in molecular machinery and adaptive materials.
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financially supported by the National Natural Science Foundation of China(Nos.22001214,21662031,21661028 and 22061039)the Science Fund for Distinguished Young Scholars of Gansu Province(No.22JR5RA131)+4 种基金the Longyuan Innovation and Entrepreneurship Talent Project of Gansu Provincethe Major Project Cultivation Program of Northwest Normal Universitythe Top Leading Talents Project of Gansu Provincethe Key R&D program of Gansu Province(No.21YF5GA066)College Industry Support Plan Project of Gansu Province(No.2022CYZC-18)。
文摘Herein we report an environmentally friendly and energy-efficient method for the adsorptive separation of toluene from toluene-alcohol azeotropes using porous crystalline fluorinated leaning pillar[6]arene(FLP6α),achieving up to 100%purity.Moreover,FLP6αdemonstrates rapid adsorption and excellent recyclability.
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National Natural Science Foundation of China(Nos.22177011,21977012,and 21672021)the Joint Project of BRCBC(Biomedical Translational Engineering Research Center of BUCT-CJFH)(No.XK2020-06).
文摘Macrocyclic polyamines are excellent chelating agents with the advantage of forming highly stable complexes.They offer the flexibility to adjust the coordination environment through functionalization.making them valuable in numerous applications owing to their unique chemical and biological characteristics.This review summarizes the use of macrocyclic polyamines as carriers and molecular platforms of targeted drugs for medical applications.The significance and innovative design of these original approaches are dissected from the unique perspective of diverse mechanisms,such as iron depletion,metallo-β-lactamases inhibitors,intracellular ATP depletion,non-viral gene vector,DNA/RNA syntheses inhibitors and theranostics agent.Of interest are the metal complex of macrocyclic polyamines,which is usually a double-edged sword as dealing with endogenous macromolecular targets,especially DNA.These excellent cases will help to understand the typical mechanism in drug design based on macrocyclic polyamines,and achieve actual applications in medicine.
文摘Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active sites inside the cavity of macrocyclic arenes to better mimic molecular recognition of bioreceptors and enzymes.The editorial aims to enlighten scientists in this field when they develop novel macrocycles for molecular recognition, supramolecular assembly, and applications.
基金supported by the National Natural Science Foundation of China(Nos.82202274,82072032,22161016,32025021,12374390,52002380 and 31971292),the National Science and Technology Major Project(No.2023ZD0500902)the Fellowship of China Postdoctoral Science Foundation(No.2023M743559)+2 种基金the Member of Youth Innovation Promotion Association Foundation of CAS,China(No.2023310)the Key Scientific and Technological Special Project of Ningbo City(No.2023Z209)the Natural Science Foundation of Zhejiang Province(No.LQ23H180003)。
文摘Recently,stimuli-responsive nanocarriers capable of precision drug release have garnered significant attention in the field of drug delivery.Here,an in-situ dynamic covalent self-assembled(DCS)strategy was utilized to develop a co-delivery system.This assembly was based on a thiol-disulfide-exchange reaction,producing disulfide macrocycles in an oxidizing aerial environment.These macrocycles encapsulated the anti-cancer drug(paclitaxel,PTX)on the surface of gold nanoparticles,which served as photothermal therapy agents during the self-assembly.In the DCS process,the kinetic control over the concentration of each building unit within the reaction system led to the formation of a stable co-delivery nanosystem with optimal drug-loading efficiency.Notably,the high glutathione(GSH)concentrations in tumor cells caused the disulfide macrocycles in nanostructures to break,resulting in drug release.The stimuli-responsive performances of the prepared nanosystems were determined by observing the molecular structures and drug release.The results revealed that the self-assembled nanosystem exhibited GSH-triggered drug release and good photothermal conversion capability under near-infrared light.Moreover,the in vitro and in vivo results revealed that conjugating the targeting molecule of cRGD with co-delivery nanosystem enhanced its biocompatibility,chemo-photothermal anti-cancer effect.Overall,our findings indicated that in-situ DCS strategy enhanced the control over drug loading during the construction of the co-delivery system,paving a way for the development of more functional carriers in nanomedicine.
基金Xunta de Galicia for his postdoctoral fellowship(ED481B-2022-068)the Fundación Segundo Gil Dávila for her PhD fellowship。
文摘In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff base macrocyclic ligands incorporating the pyridine moiety,and their complexes,were revised,and in 2015 the chemistry of pentaaza macrocycle ligands with rare earth metals was also summarized.Porphyrin and phthalocyanine ligands are not included in this review,which primarily focuses on complexes with Schiff bases and amines without pendant arms or any additional donor other than nitrogen.The synthetic methods,structural characterization,based on single X-ray crystal data,and properties of the lanthanoid complexes,with special attention to magneto-structural correlations,are presented herein.
基金supported by the National Natural Science Foundation of China(No.22271110)Shenzhen Science and Technology Program(No.JCYJ20230807143607016)Natural Science Foundation of Hubei Province,China(No.2022CFA031)。
文摘Tryptophan(Trp)is an essential amino acid that plays a critical role in human physiology.The increasing demand for Trp has created a highly promising market,underscoring the urgent necessity for the development of efficient strategies for the simultaneous detection and uptake of tryptophan.Herein,we report an expanded“Texas-sized”molecular box(An-TxSB),which incorporates luminescent anthracene bridging subunits and molecular recognition motifs.This luminescent molecular box demonstrates exceptional sensitivity to Trp in water,permitting its precise quantification with a notably low limit of detection(LOD)of 0.42μmol/L.Moreover,An-TxSB facilitates the proficient uptake of Trp from simulated water samples,thereby revealing an impressive Trp adsorption capacity of up to 226.0μmol/g.
基金Project supported by the National Natural Science Foundation of China(22131011,22071274,21821003)the Pearl River Talent Plan of Guangdong(2017BT01C161)。
文摘On account of the complicated magnetic exchange interactions between lanthanide ions,binuclear lanthanide complexes have broad application prospect in the field of single-molecule magnets.Therefore,it is necessary to develop reasonable bridging ligands to manipulate the directional assembly of binuclear lanthanide complexes.Herein,we selected the macrocyclic ligand L^(N_(8)O_(2))to build up two new dilanthanide complexes[Ln_(2)(LN_(8)O_(2))(OpyO)_(2)(H_(2)O)2](NO_(3))_(2)(1-Ln,Ln=Dy,Tb;LN_(8)O_(2)=hexamethyl-tetraaza-dioxe-dipyrazolacycloicosaphane-2,9,12,19-tetraene;OpyOH=2-pyridinol-1-oxide).Dynamic magnetic studies show that 1-Dy exhibits slow relaxation behavior under a 1 kOe applied field.Further fitting analysis of relaxation times gives the effective energy barrier of 38.2 cm^(−1),and reveals that the slow magnetic relaxation behavior is dominated by the Orbach and Raman processes.High-resolution luminescence emission spectrum indicates the energy gap of 36.8 cm^(−1)between the ground state and the first excited state,consistent with the magnetic measurement results.1-Tb exhibits brilliant characteristic green light emission under UV light excitation.The absolute quantum yield of 1-Tb is 44.8%,and its first-order fitted decay lifetime is 779.21μs at room temperature.This study provides the way for directional construction of high-performance molecular materials with magnetic and optical dual-function.
基金supported by the National Natural Science Foundation of China(No.2271090)。
文摘Host-vip recognition-based macrocycle in macrocycle to form"Russian doll"assemblies remains an interesting topic in supramolecular chemistry.Herein,a macrocycle-in-macrocycle assembly was studied using cucurbit[10]uril(Q[10])and the smallest cucurbituril-like macrocycle(TD[4]).X-ray crystal structure analysis revealed that TD[4]was encapsulated in the cavity of Q[10]to form a 1:1 complex.Importantly,competitive vip studies suggested that TD[4]had the highest binding constant with the Q[10]host among the vips used,including Q[5],Me_(8)TD[4],and amantadine molecules in water.Our results provided a new cucurbituril-based Russian-doll structure containing both the largest and smallest cavities of the cucurbiturils,which expanded the family of molecular Russian dolls.
