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
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
Macroscopic supramolecular assembly(MSA)has been a recent progress in supramolecular chemistry.MSA mainly focuses on studies of the building blocks with a size beyond ten micrometers and the non-covalent interactions ...Macroscopic supramolecular assembly(MSA)has been a recent progress in supramolecular chemistry.MSA mainly focuses on studies of the building blocks with a size beyond ten micrometers and the non-covalent interactions between these interactive building blocks to form ordered structures.MSA is essential to realize the concept of"self-assembly at all scales"by bridging most supramolecular researches at molecular level and at macroscopic scale.This review summaries the development of MSA,the basic design principle and related strategies to achieve MSA and potential applications.Correspondingly,we try to elucidate the correlations and differences between"macroscopic assembly"and MSA based on intermolecular interactions;the design principle and the underlying assembly mechanism of MSA are proposed to understand the reported MSA behaviors;to demonstrate further applications of MSA,we introduce some methods to improve the ordered degree of the assembled structures from the point of precise assembly and thus envision some possible fields for the use of MSA.展开更多
Conformational regulation among two or more distant sites is not only one of the main pathways to accomplish multiple tasks in complex biological systems but also represents a powerful strategy to obtain stimuli-respo...Conformational regulation among two or more distant sites is not only one of the main pathways to accomplish multiple tasks in complex biological systems but also represents a powerful strategy to obtain stimuli-responsive supramolecular nanoconstructs with tailored physicochemical performance.We herein report the fabrication of a photochromic supramolecular assembly,which can be synergistically activated by the conformational regulation with bis(4,8-disulfonato-1,5-naphtho)-32-crown-8 and then reversibly switched by the through-space communication between restricted stilbazolium salt and photochromic dithienylethene.This work demonstrates that the synergistic conformational modulation via intra-and intermolecular interactions can be developed as a generalizable approach to construct more advanced biomimetic nanomaterials.展开更多
Triterpenoids exhibit remarkable pharmacological characteristics and have garnered significant research attention,owing to their unique backbone structures and numerous modification sites.Recent advancements in supram...Triterpenoids exhibit remarkable pharmacological characteristics and have garnered significant research attention,owing to their unique backbone structures and numerous modification sites.Recent advancements in supramolecular chemistry have highlighted the potential of triterpenoids to form organized assemblies through noncovalent interactions,affording versatile functional properties.By leveraging their unique structural characteristics and biological activities,innovative strategies can be developed to enhance the efficacy and safety of biomedical therapies.This review describes the recent advances in triterpenoids serving as(i)functional groups for aggregation-induced emission,(ii)building blocks for self-transportation and drug delivery,(iii)potential gelators for rational hydrogel design,and(iv)cholesterol alternatives for optimizing lipid-based nanoparticles.The biomedical perspectives of triterpenoid-based supramolecular assemblies and potential bottlenecks in clinical translation are also discussed,with the hope of offering insights into future research and biomedical applications.展开更多
Aggregation-induced emission(AIE)and thermally activated delayed fluorescence(TADF)are two optoelectronic properties with great potential for applications.However,metal nanoclusters exhibiting both AIE and TADF charac...Aggregation-induced emission(AIE)and thermally activated delayed fluorescence(TADF)are two optoelectronic properties with great potential for applications.However,metal nanoclusters exhibiting both AIE and TADF characteristics have not been extensively studied.This study investigates a binary cocrystal system based on silver nanoclusters—Ag_(6)(Et_(2)NCS_(2))6·[Ag_(11)(AdmS)_(3)(Et_(2)NCS_(2))6]_(2)(1-Ag_(6)·(Ag_(11))_(2)),aiming to explore the synergistic effects between flexible-alkyl dithiol and rigid monothiol ligands.Due to the introduction of Ag_(6)structures,the system exhibits enhanced stability and modulated optical properties.The binary tricluster 1-Ag_(6)·(Ag_(11))_(2)demonstrates significant AIE behavior,with an approximately 15-fold increase in intensity when the water volume fraction(fw)is 60%.Single-crystal X-ray diffraction analysis indicates that the enhanced AIE effect originates from intercluster hydrogen bonding interactions,which drive the self-assembly of sub-clusters and form hierarchical structures,thereby suppressing ligand rotation.In addition,the system exhibits the TADF phenomenon in the temperature range of 100−175 K.In order to further investigate the effect of ligand variations on optical properties,two unitary clusters,Ag_(11)(AdmS)_(3)(Et_(2)NCS_(2))6(2-Ag_(11)-AS)and Ag_(11)(tBuS)_(3)(Et_(2)NCS_(2))6(3-Ag_(11)-BS),are synthesized,and their roles in regulating optoelectronic properties are explored through ligand exchange reactions.This study provides important insights for the development of efficient luminescent materials with AIE and TADF properties,highlighting the critical roles of ligand exchange and structural configuration.展开更多
Multidimensional supramolecular assembly(CB[6]-PA)based on cucurbit[6]uril(CB[6])was constructed via the outer-surface interactions of CB[6]with a structure-directing agent of pamoic acid(H_2PA).Most impressively,crys...Multidimensional supramolecular assembly(CB[6]-PA)based on cucurbit[6]uril(CB[6])was constructed via the outer-surface interactions of CB[6]with a structure-directing agent of pamoic acid(H_2PA).Most impressively,crystal CB[6]-PA exhibited satisfactory selectivity for the capture of Cd^(2+)and Hg^(2+)cations,and released Cd^(2+)and Hg^(2+)cations under acidic condition.This reversible process allows for capturing applications of Cd^(2+)and Hg^(2+)cations.Furthermore,crystalline CB[6]-PA-Cd demonstrated enhanced fluorescence properties compared with H_2PA ligands.CB[6]-PA-Cd could be employed for the precise detection of methylmalonic acid(EA or MMA)as a biomarker of septicemia.The introduction of EA resulted in the fluorescence quenching of CB[6]-PA-Cd,the mechanism of sensing EAwas clearly elucidated.A portable detection platform was designed to augment the efficiency of EA detection.To promote biological applications,the exceptional probe capable of exactly detecting EA in serum samples had been substantiated.CB[6]-PA-Cd exhibited a negligible cytotoxicity,favorable cytocompatibility,and good hemocompatibility.Thus,these results will bring about new enlightenment for the fabrication of light-emitting materials and high-resolution bio-imaging probes based on cucurbit[n]urils.展开更多
Luminescent carbon nanoparticles （CNPs） are newcomers to the world of nanomaterials and have shown great impact in health and environmental applications as well as being promising building blocks for future nanodevi...Luminescent carbon nanoparticles （CNPs） are newcomers to the world of nanomaterials and have shown great impact in health and environmental applications as well as being promising building blocks for future nanodevices because of their fascinating photoluminescence and potential to serve as nontoxic replacements for traditional heavy-metals-based quantum dots. Herein, fluorescent CNPs have been prepared from candle soot by re fluxing with HNO3 and subsequently separated by a single centrifugation. The CNPs can be represented by the empirical formula C1Ho.677Oo.586No.o15Nao.069, and have a size of 20-100 nm, height of 3.0 nm, lifetime of 7.31 ns ＋ 0.06 ns and quantum yield of -1.7%. Further studies demonstrate that： （1）the as-prepared CNPs exhibit excellent stability in biological media and their luminescence intensity does not change with ionic strength or pH in the physiological and pathological range of pH 4.5-8.8; （2） CNPs can act as electron donors and transporters and porphyrin can assemble onto CNPs through electrostatic and ^-stacking interactions to form porphyrin-CNPs supramolecular composites; （3）CNPs have strong intrinsic peroxidase-like activity. Based on this intrinsic peroxidase activity, a simple, cheap, and highly selective and sensitive colorimetric and quantitative assay has been developed for the detection of glucose levels. This assay has been used to analyze real samples, such as diluted blood and fruit juice.展开更多
The dynamic regulation of circularly polarized luminescence(CPL)holds profound significance in various fields,such as highlevel information storage and encryption.Here we developed a chiral amphiphilic molecule,CPSB-G...The dynamic regulation of circularly polarized luminescence(CPL)holds profound significance in various fields,such as highlevel information storage and encryption.Here we developed a chiral amphiphilic molecule,CPSB-GLU-PEG350(CGP),composed of aggregation-induced emission(AIE)chromophores(Z)-4-(1-cyano-2-phenylvinyl)benzoic acid(CPSB),a chiral linker Glutamic acid and polyethylene glycol(PEG)thermoresponsive segments.Within the self-assembled supramolecular system formed by CGP,we have achieved in-situ temperature-responsive chiral structures,facilitating the thermal control switch of the CPL signal.Molecular dynamics simulations demonstrate the distinct behaviors of AIE and PEG units during the temperature-variable assembly process.Furthermore,by co-assembling achiral dye molecules with CGP,we have expanded the color range of the temperature-responsive CPL assembly system in situ and confirmed the occurrence of circularly polarizedF?rster resonance energy transfer(C-FRET)phenomenon in this process,which successfully enriched the strategies for in-situ CPL control in aqueous phases.In addition,the contactless radiative energy transfer of CPL can also be realized in this system,exhibiting more flexible temperature regulation of the CPL signal.This study provides a convenient and universal strategy for the construction of dynamically smart chiroptical materials.展开更多
Aggregation-induced emission(AIE),as an exciting photophysical phenomenon,has been regarded as one frontier research topic within both ranges of molecular luminescence and materials science over the last two decades.S...Aggregation-induced emission(AIE),as an exciting photophysical phenomenon,has been regarded as one frontier research topic within both ranges of molecular luminescence and materials science over the last two decades.Since controllable molecular ensembles with particular morphologies and tunable functions can be elegantly constructed in the realm of supramolecular chemistry,the integration of supramolecular assembly and AIE systems can expectedly bring about luminescent materials with tunable emission and tailorable well-ordered architectures.In this review,we will provide a summary of the creation and working mechanisms of AIE systems involving supramolecular systems that are driven by different supramolecular driving forces including hydrogen bonding,host−vip interactions,metal coordination,and π-π interactions.The morphological and photoluminescent features of these AIE-active supramolecular assemblies will be elucidated,and the regulated fluorescence properties of the AIEgens induced by the assembling-disassembling processes will be discussed in detail.展开更多
Biomimetic intelligent polymeric hydrogel actuators with cooperative fluorescence-color switchable behaviors are expected to find great potential applications in soft robotics,visual detection/display,and camouflage a...Biomimetic intelligent polymeric hydrogel actuators with cooperative fluorescence-color switchable behaviors are expected to find great potential applications in soft robotics,visual detection/display,and camouflage applications.However,it remains challenging to realize the spatial manipulation of synergistic shape/color-changing behaviors.Herein,we report an interfacial supramolecular assembly(ISA)approach that enables the construction of robust fluorescent polymeric hydrogel actuators with spatially anisotropic structures.On the basis of this ISA approach,diverse 2D/3D soft fluorescent hydrogel actuators,including chameleon-and octopi-shaped ones with spatially anisotropic structures,were facilely assembled from two different fluorescent hydrogel building blocks sharing the same physically cross-linked agar network.Spatially control over synergistic shape/color-changing behaviors was then realized in one single anisotropic hydrogel actuator.The proposed ISA approach is universal and expected to open promising avenues for developing powerful bioinspired intelligent soft actuators/robotics with selective spatial shape/color-changing behaviors.展开更多
The manipulation of supramolecular assembly enables single-component architectures to possess diverse structures and functions.Here,we report directed phase transitions of dipeptide supramolecular gel to crystals with...The manipulation of supramolecular assembly enables single-component architectures to possess diverse structures and functions.Here,we report directed phase transitions of dipeptide supramolecular gel to crystals with excellent selectivity and tunable mechanical properties.To be specific,lamellar-to-orthorhombic rearrangement of dipeptide molecules in the supramolecular assembly was guided by application of ammonia gas,while lamellar-tohexagonal realignment was generated upon water vapor exposure of the assembly.Importantly,this crystal phase control originated from distinct gas-mediated reconstitution of hydrogen-bonding interactions,which endowed the dipeptide materials with remarkably modulated stiffness.The selective phase transformation offers a simple and effective platform for self-assembling peptide crystals with diverse long-range-ordered structures from a single gel-state aggregation.This work opens up new perspectives on peptide-based biomaterials via gas-directed hydrogen-bonding chemistry.展开更多
The photochemical and photophysical properties of near-infrared(NIR)dyes are significantly influenced by their aggregation state and mesoscopic morphology.However,beyond chemical synthesis,the regulation mechanisms fo...The photochemical and photophysical properties of near-infrared(NIR)dyes are significantly influenced by their aggregation state and mesoscopic morphology.However,beyond chemical synthesis,the regulation mechanisms for the properties of NIR dyes,particularly with respect to photothermal properties of the aggregates,are not yet fully understood.Here,we investigate the photothermal behaviors of croconaine-based(CroA)NIR dyes containing dipeptide or amino acids moieties.The introduction of hydrogen bonding promotesπ-πstacking of croconaine center,which can efficiently regulate aggregation states and assembly structures in isopropanol.Under laser irradiation,CroA aggregates undergo aggregation-dissociation transition,the in-situ monomer generation process regulates two parameters of photothermal performance:heating rates and plateau photothermal temperatures.This study reveals the regulation effect of non-covalent bonding interactions on CroA aggregates,highlighting supramolecular assembly strategy not only facilitates to construct of photothermal nanomaterials with well-defined structures,but also provides an alternative and effective method for regulating photothermal performance of NIR dyes.展开更多
Small interfering RNA(siRNA)technology,which could be able to silence specific targeted mRNAs rapidly and efficiently,has been regarded as a novel and potent gene therapeutic approach for diseases,such as cancers,in-f...Small interfering RNA(siRNA)technology,which could be able to silence specific targeted mRNAs rapidly and efficiently,has been regarded as a novel and potent gene therapeutic approach for diseases,such as cancers,in-fections,inflammations and neurological disorders.However,some conspicuous intrinsic defects of siRNA including the poor cellular uptake,low biological stability,unfavorable pharmacokinetics and bio-distribution properties,have hindered further applications in clinic.Therefore,it is prerequisite to design safe and effective siRNA delivery systems for the successful development of siRNA-based various diseases therapeutics.This review aims to analyze and summarize these supramolecular assembly models in the process of siRNA delivery,namely recent nanotech-nological strategies for carrying siRNA by using diverse non-viral vehicles such as cationic liposomes,stable nucleic acid lipid particles(SNALPs),cationic polymers,cationic dendrimers,inorganic nanoparticles and others.Eventually,it is concluded with future perspectives of siRNA therapeutics in the field of non-viral carriers.展开更多
The supramolecular assembly of bis[3, 4, 12, 13, 21, 22, 30, 31-octa(dodecylthio)-2, 3-naphthalocyaninato] erbium complex (Er[Nc(SC12H25)8]2) was fabricated at the air/water interface by Langmuir monolayer technique. ...The supramolecular assembly of bis[3, 4, 12, 13, 21, 22, 30, 31-octa(dodecylthio)-2, 3-naphthalocyaninato] erbium complex (Er[Nc(SC12H25)8]2) was fabricated at the air/water interface by Langmuir monolayer technique. Surface pressure-area isotherm indicates that stable monolayer is formed. The monolayer morphology on mica was investigated by atomic force microscopy (AFM). Columnar domains of ca. 100 nm X (20–30) nm appearing in the micrograph have ordered orientation. Polarized UV-vis spectra and small-angle X-ray diffraction pattern show that the macrocycles tilt in the monolayer. The orientation angle of the naphthalocyanine ring with respect to the substrate was found to be ca. 54°. Each monolayer is ca. 3.53 nm thick. The columnar domain comprises 4–6 rows of columnar supramolecular assemblies where the molecules stack face-to-face.展开更多
Supramolecular chemistry during the synthesis of carbon-nitrogen-based materials has recently experienced a renaissance in the arena of photocatalysis and electrocatalysis.In this review,we start with the discussion o...Supramolecular chemistry during the synthesis of carbon-nitrogen-based materials has recently experienced a renaissance in the arena of photocatalysis and electrocatalysis.In this review,we start with the discussion of supramolecular assemblies-derived carbon-nitrogen-based materials’regulation from the aspect of morphology,chemical composition,and micro/nanostructural control.Afterwards the recent advances of these materials in energy and environment related applications,including degradation of pollutants,water splitting,oxygen reduction reactions,CO_(2) reduction reactions along with organic synthesis are summarized.The correlations between the structural features and physicochemical properties of the carbonnitrogen-based materials and the specific catalytic activity are discussed in depth.By highlighting the opportunities and challenges of supramolecular assembly strategies,we attempt an outlook on possible future developments for highly efficient carbon-based photo/electrocatalysts.展开更多
Supramolecular assemblies constructed through the encapsulation of conductive polymers(CPs)by macrocyclic molecules have attracted increasing interest in the fields of supramolecular chemistry and electrochemistry.In ...Supramolecular assemblies constructed through the encapsulation of conductive polymers(CPs)by macrocyclic molecules have attracted increasing interest in the fields of supramolecular chemistry and electrochemistry.In this work,an effective strategy was reported to improve the stability and conductivity of CPs by electrochemically constructing different supramolecular assemblies composed of macrocycles and CPs.Typically,we uploaded zinc-based MOF(ZIF-8)onto carbon nanotube film(CNTF)and further electrically deposited macrocycles and CPs to gain the flexible conductive electrodes.Herein,five different supramolecular macrocycles,includingα-cyclodextrin(α-CD),sulfato-β-cyclodextrin(SCD),sulfonatocalix[4]arene(SC[4]),cucurbit[6]uril(CB[6])and cucurbit[7]uril(CB[7])were utilized and the electrochemical performances of the assembly electrodes increased in an order ofα-CD<SCD<SC[4]<CB[6]<CB[7],significantly improving the areal capacitance up to 1533 mF/cm^(2).This strategy may provide a new way for the application of macrocyclic supramolecules in electrochemical systems.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
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 interracial assembly of photo-induced dimerization of atypical anthracene-containing amphiphilic dendron and host-vip interaction with γ-cyclodextrin has been investigated. It has been proved that even without ...The interracial assembly of photo-induced dimerization of atypical anthracene-containing amphiphilic dendron and host-vip interaction with γ-cyclodextrin has been investigated. It has been proved that even without long alkyl chain the amphiphilic dendron could still form stable Langmuir monolayer at the air/water interface. Through the host-vip interaction,γ-cyclodextrin can be used to encapsulate two headgroups of amphiphilic dendron in the antiparallel direction. However, the formed host-vip complex was sensitive to the surface pressure. Slight compression of surface pressure led amphiphilic dendron to reassemble into nanofibers through the strong π-π stacking between headgroups. On the other hand, under in situ irradiation, the amphiphilic dendron was stabilized in the cavity of γ- cyclodextrin through headgroup dimerization and the host-vip complex further irregularly aggregated to nanoparticles. Meanwhile, γ-cyclodextrin, as a silencer, blocked the supramolecular chirality transfer. Our conclusion was demonstrated through UV/vis, FT-IR, CD spectrum and AFM images, respectively.展开更多
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.
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.
文摘Macroscopic supramolecular assembly(MSA)has been a recent progress in supramolecular chemistry.MSA mainly focuses on studies of the building blocks with a size beyond ten micrometers and the non-covalent interactions between these interactive building blocks to form ordered structures.MSA is essential to realize the concept of"self-assembly at all scales"by bridging most supramolecular researches at molecular level and at macroscopic scale.This review summaries the development of MSA,the basic design principle and related strategies to achieve MSA and potential applications.Correspondingly,we try to elucidate the correlations and differences between"macroscopic assembly"and MSA based on intermolecular interactions;the design principle and the underlying assembly mechanism of MSA are proposed to understand the reported MSA behaviors;to demonstrate further applications of MSA,we introduce some methods to improve the ordered degree of the assembled structures from the point of precise assembly and thus envision some possible fields for the use of MSA.
基金supported by the National Natural Science Foundation of China(Nos.21871154,21772099,21861132001,and 21873051)the Fundamental Research Funds for the Central Universities,Nankai University。
文摘Conformational regulation among two or more distant sites is not only one of the main pathways to accomplish multiple tasks in complex biological systems but also represents a powerful strategy to obtain stimuli-responsive supramolecular nanoconstructs with tailored physicochemical performance.We herein report the fabrication of a photochromic supramolecular assembly,which can be synergistically activated by the conformational regulation with bis(4,8-disulfonato-1,5-naphtho)-32-crown-8 and then reversibly switched by the through-space communication between restricted stilbazolium salt and photochromic dithienylethene.This work demonstrates that the synergistic conformational modulation via intra-and intermolecular interactions can be developed as a generalizable approach to construct more advanced biomimetic nanomaterials.
基金supported by the National Natural Science Foundation of China(NSFC)project(32301133),the University of Hong Kong Seed Fund for Basic Research(104006533)the R&D Program of Beijing Municipal Education Commission(KM202310025022).
文摘Triterpenoids exhibit remarkable pharmacological characteristics and have garnered significant research attention,owing to their unique backbone structures and numerous modification sites.Recent advancements in supramolecular chemistry have highlighted the potential of triterpenoids to form organized assemblies through noncovalent interactions,affording versatile functional properties.By leveraging their unique structural characteristics and biological activities,innovative strategies can be developed to enhance the efficacy and safety of biomedical therapies.This review describes the recent advances in triterpenoids serving as(i)functional groups for aggregation-induced emission,(ii)building blocks for self-transportation and drug delivery,(iii)potential gelators for rational hydrogel design,and(iv)cholesterol alternatives for optimizing lipid-based nanoparticles.The biomedical perspectives of triterpenoid-based supramolecular assemblies and potential bottlenecks in clinical translation are also discussed,with the hope of offering insights into future research and biomedical applications.
基金supported by the National Natural Science Foundation of China(Nos.22488101 and 22071274).
文摘Aggregation-induced emission(AIE)and thermally activated delayed fluorescence(TADF)are two optoelectronic properties with great potential for applications.However,metal nanoclusters exhibiting both AIE and TADF characteristics have not been extensively studied.This study investigates a binary cocrystal system based on silver nanoclusters—Ag_(6)(Et_(2)NCS_(2))6·[Ag_(11)(AdmS)_(3)(Et_(2)NCS_(2))6]_(2)(1-Ag_(6)·(Ag_(11))_(2)),aiming to explore the synergistic effects between flexible-alkyl dithiol and rigid monothiol ligands.Due to the introduction of Ag_(6)structures,the system exhibits enhanced stability and modulated optical properties.The binary tricluster 1-Ag_(6)·(Ag_(11))_(2)demonstrates significant AIE behavior,with an approximately 15-fold increase in intensity when the water volume fraction(fw)is 60%.Single-crystal X-ray diffraction analysis indicates that the enhanced AIE effect originates from intercluster hydrogen bonding interactions,which drive the self-assembly of sub-clusters and form hierarchical structures,thereby suppressing ligand rotation.In addition,the system exhibits the TADF phenomenon in the temperature range of 100−175 K.In order to further investigate the effect of ligand variations on optical properties,two unitary clusters,Ag_(11)(AdmS)_(3)(Et_(2)NCS_(2))6(2-Ag_(11)-AS)and Ag_(11)(tBuS)_(3)(Et_(2)NCS_(2))6(3-Ag_(11)-BS),are synthesized,and their roles in regulating optoelectronic properties are explored through ligand exchange reactions.This study provides important insights for the development of efficient luminescent materials with AIE and TADF properties,highlighting the critical roles of ligand exchange and structural configuration.
基金supported by the Natural Science Foundation of Inner Mongoliathe National Natural Science Foundation of China (2021MS02012,21761024,22161032)。
文摘Multidimensional supramolecular assembly(CB[6]-PA)based on cucurbit[6]uril(CB[6])was constructed via the outer-surface interactions of CB[6]with a structure-directing agent of pamoic acid(H_2PA).Most impressively,crystal CB[6]-PA exhibited satisfactory selectivity for the capture of Cd^(2+)and Hg^(2+)cations,and released Cd^(2+)and Hg^(2+)cations under acidic condition.This reversible process allows for capturing applications of Cd^(2+)and Hg^(2+)cations.Furthermore,crystalline CB[6]-PA-Cd demonstrated enhanced fluorescence properties compared with H_2PA ligands.CB[6]-PA-Cd could be employed for the precise detection of methylmalonic acid(EA or MMA)as a biomarker of septicemia.The introduction of EA resulted in the fluorescence quenching of CB[6]-PA-Cd,the mechanism of sensing EAwas clearly elucidated.A portable detection platform was designed to augment the efficiency of EA detection.To promote biological applications,the exceptional probe capable of exactly detecting EA in serum samples had been substantiated.CB[6]-PA-Cd exhibited a negligible cytotoxicity,favorable cytocompatibility,and good hemocompatibility.Thus,these results will bring about new enlightenment for the fabrication of light-emitting materials and high-resolution bio-imaging probes based on cucurbit[n]urils.
基金This project was supported by the 973 Project （No. 2011CB936004）, the National Natural Science Foundation of China （NSFC） （Nos. 20831003, 90813001, 20833006, and 90913007） and Funds from the Chinese Academy of Sciences.
文摘Luminescent carbon nanoparticles （CNPs） are newcomers to the world of nanomaterials and have shown great impact in health and environmental applications as well as being promising building blocks for future nanodevices because of their fascinating photoluminescence and potential to serve as nontoxic replacements for traditional heavy-metals-based quantum dots. Herein, fluorescent CNPs have been prepared from candle soot by re fluxing with HNO3 and subsequently separated by a single centrifugation. The CNPs can be represented by the empirical formula C1Ho.677Oo.586No.o15Nao.069, and have a size of 20-100 nm, height of 3.0 nm, lifetime of 7.31 ns ＋ 0.06 ns and quantum yield of -1.7%. Further studies demonstrate that： （1）the as-prepared CNPs exhibit excellent stability in biological media and their luminescence intensity does not change with ionic strength or pH in the physiological and pathological range of pH 4.5-8.8; （2） CNPs can act as electron donors and transporters and porphyrin can assemble onto CNPs through electrostatic and ^-stacking interactions to form porphyrin-CNPs supramolecular composites; （3）CNPs have strong intrinsic peroxidase-like activity. Based on this intrinsic peroxidase activity, a simple, cheap, and highly selective and sensitive colorimetric and quantitative assay has been developed for the detection of glucose levels. This assay has been used to analyze real samples, such as diluted blood and fruit juice.
基金supported by the National Natural Science Foundation of China(22301206,22301208 and 92356305)the Natural Science Foundation of Anhui Province(2308085J15)+3 种基金the China Postdoctoral Science Foundation(2022M722312)the Jiangsu Natural Science Foundation(BK20230505)the Jiangsu Funding Program for Excellent Postdoctoral Talentthe Natural Science Foundation of Anhui Provincial Higher Education Institutions(2023AH010012)。
文摘The dynamic regulation of circularly polarized luminescence(CPL)holds profound significance in various fields,such as highlevel information storage and encryption.Here we developed a chiral amphiphilic molecule,CPSB-GLU-PEG350(CGP),composed of aggregation-induced emission(AIE)chromophores(Z)-4-(1-cyano-2-phenylvinyl)benzoic acid(CPSB),a chiral linker Glutamic acid and polyethylene glycol(PEG)thermoresponsive segments.Within the self-assembled supramolecular system formed by CGP,we have achieved in-situ temperature-responsive chiral structures,facilitating the thermal control switch of the CPL signal.Molecular dynamics simulations demonstrate the distinct behaviors of AIE and PEG units during the temperature-variable assembly process.Furthermore,by co-assembling achiral dye molecules with CGP,we have expanded the color range of the temperature-responsive CPL assembly system in situ and confirmed the occurrence of circularly polarizedF?rster resonance energy transfer(C-FRET)phenomenon in this process,which successfully enriched the strategies for in-situ CPL control in aqueous phases.In addition,the contactless radiative energy transfer of CPL can also be realized in this system,exhibiting more flexible temperature regulation of the CPL signal.This study provides a convenient and universal strategy for the construction of dynamically smart chiroptical materials.
基金National Natural Science Foundation of China,Grant/Award Numbers:51673084,21871108Jilin Province-University Cooperative Construction Project--Special Funds for New Materials,Grant/Award Number:SXGJSF2017-3。
文摘Aggregation-induced emission(AIE),as an exciting photophysical phenomenon,has been regarded as one frontier research topic within both ranges of molecular luminescence and materials science over the last two decades.Since controllable molecular ensembles with particular morphologies and tunable functions can be elegantly constructed in the realm of supramolecular chemistry,the integration of supramolecular assembly and AIE systems can expectedly bring about luminescent materials with tunable emission and tailorable well-ordered architectures.In this review,we will provide a summary of the creation and working mechanisms of AIE systems involving supramolecular systems that are driven by different supramolecular driving forces including hydrogen bonding,host−vip interactions,metal coordination,and π-π interactions.The morphological and photoluminescent features of these AIE-active supramolecular assemblies will be elucidated,and the regulated fluorescence properties of the AIEgens induced by the assembling-disassembling processes will be discussed in detail.
基金supported financially by the National Natural Science Foundation of China (No.52073297)the Sino-German Mobility Programme (No.M-0424)+2 种基金Zhejiang Provincial Natural Science Foundation of China (No.LR23E030001)the Youth Innovation Promotion Association of Chinese Academy of Sciences (No.2019297)K.C.Wong Education Foundation (No.GJTD-2019-13).
文摘Biomimetic intelligent polymeric hydrogel actuators with cooperative fluorescence-color switchable behaviors are expected to find great potential applications in soft robotics,visual detection/display,and camouflage applications.However,it remains challenging to realize the spatial manipulation of synergistic shape/color-changing behaviors.Herein,we report an interfacial supramolecular assembly(ISA)approach that enables the construction of robust fluorescent polymeric hydrogel actuators with spatially anisotropic structures.On the basis of this ISA approach,diverse 2D/3D soft fluorescent hydrogel actuators,including chameleon-and octopi-shaped ones with spatially anisotropic structures,were facilely assembled from two different fluorescent hydrogel building blocks sharing the same physically cross-linked agar network.Spatially control over synergistic shape/color-changing behaviors was then realized in one single anisotropic hydrogel actuator.The proposed ISA approach is universal and expected to open promising avenues for developing powerful bioinspired intelligent soft actuators/robotics with selective spatial shape/color-changing behaviors.
基金The authors gratefully acknowledge the financial support for this research from the National Nature Science Foundation of China(nos.21961142022,21872150,and 22072160)J.F.particularly thanks to the Youth Innovation Promotion Association of CAS(no.2016032)Institute of Chemistry,CAS(no.Y6290512B1).
文摘The manipulation of supramolecular assembly enables single-component architectures to possess diverse structures and functions.Here,we report directed phase transitions of dipeptide supramolecular gel to crystals with excellent selectivity and tunable mechanical properties.To be specific,lamellar-to-orthorhombic rearrangement of dipeptide molecules in the supramolecular assembly was guided by application of ammonia gas,while lamellar-tohexagonal realignment was generated upon water vapor exposure of the assembly.Importantly,this crystal phase control originated from distinct gas-mediated reconstitution of hydrogen-bonding interactions,which endowed the dipeptide materials with remarkably modulated stiffness.The selective phase transformation offers a simple and effective platform for self-assembling peptide crystals with diverse long-range-ordered structures from a single gel-state aggregation.This work opens up new perspectives on peptide-based biomaterials via gas-directed hydrogen-bonding chemistry.
基金supported by the National Natural Science Foundation of China(No.21871176).
文摘The photochemical and photophysical properties of near-infrared(NIR)dyes are significantly influenced by their aggregation state and mesoscopic morphology.However,beyond chemical synthesis,the regulation mechanisms for the properties of NIR dyes,particularly with respect to photothermal properties of the aggregates,are not yet fully understood.Here,we investigate the photothermal behaviors of croconaine-based(CroA)NIR dyes containing dipeptide or amino acids moieties.The introduction of hydrogen bonding promotesπ-πstacking of croconaine center,which can efficiently regulate aggregation states and assembly structures in isopropanol.Under laser irradiation,CroA aggregates undergo aggregation-dissociation transition,the in-situ monomer generation process regulates two parameters of photothermal performance:heating rates and plateau photothermal temperatures.This study reveals the regulation effect of non-covalent bonding interactions on CroA aggregates,highlighting supramolecular assembly strategy not only facilitates to construct of photothermal nanomaterials with well-defined structures,but also provides an alternative and effective method for regulating photothermal performance of NIR dyes.
基金supported by the Ministry of Science and Technology of China (No.2012CB720604,2012AA022501)the National Natural Science Foundation of China (No.20932001).
文摘Small interfering RNA(siRNA)technology,which could be able to silence specific targeted mRNAs rapidly and efficiently,has been regarded as a novel and potent gene therapeutic approach for diseases,such as cancers,in-fections,inflammations and neurological disorders.However,some conspicuous intrinsic defects of siRNA including the poor cellular uptake,low biological stability,unfavorable pharmacokinetics and bio-distribution properties,have hindered further applications in clinic.Therefore,it is prerequisite to design safe and effective siRNA delivery systems for the successful development of siRNA-based various diseases therapeutics.This review aims to analyze and summarize these supramolecular assembly models in the process of siRNA delivery,namely recent nanotech-nological strategies for carrying siRNA by using diverse non-viral vehicles such as cationic liposomes,stable nucleic acid lipid particles(SNALPs),cationic polymers,cationic dendrimers,inorganic nanoparticles and others.Eventually,it is concluded with future perspectives of siRNA therapeutics in the field of non-viral carriers.
基金the National Natural Science Foundation of China (Grant No.29701002), the Ministry of Education of China, the Natural Science Foundation of Shandong Province (Grant No. Z99B02), the Science Committee of Shandong Province, Shandong University, and State
文摘The supramolecular assembly of bis[3, 4, 12, 13, 21, 22, 30, 31-octa(dodecylthio)-2, 3-naphthalocyaninato] erbium complex (Er[Nc(SC12H25)8]2) was fabricated at the air/water interface by Langmuir monolayer technique. Surface pressure-area isotherm indicates that stable monolayer is formed. The monolayer morphology on mica was investigated by atomic force microscopy (AFM). Columnar domains of ca. 100 nm X (20–30) nm appearing in the micrograph have ordered orientation. Polarized UV-vis spectra and small-angle X-ray diffraction pattern show that the macrocycles tilt in the monolayer. The orientation angle of the naphthalocyanine ring with respect to the substrate was found to be ca. 54°. Each monolayer is ca. 3.53 nm thick. The columnar domain comprises 4–6 rows of columnar supramolecular assemblies where the molecules stack face-to-face.
基金This work was supported by the National Natural Science Foundation of China(52125202,21908110,U2004209)the Natural Science Foundation of Jiangsu Province(BK20190479)the Fundamental Research Funds for the Central Universities(30922010707).
文摘Supramolecular chemistry during the synthesis of carbon-nitrogen-based materials has recently experienced a renaissance in the arena of photocatalysis and electrocatalysis.In this review,we start with the discussion of supramolecular assemblies-derived carbon-nitrogen-based materials’regulation from the aspect of morphology,chemical composition,and micro/nanostructural control.Afterwards the recent advances of these materials in energy and environment related applications,including degradation of pollutants,water splitting,oxygen reduction reactions,CO_(2) reduction reactions along with organic synthesis are summarized.The correlations between the structural features and physicochemical properties of the carbonnitrogen-based materials and the specific catalytic activity are discussed in depth.By highlighting the opportunities and challenges of supramolecular assembly strategies,we attempt an outlook on possible future developments for highly efficient carbon-based photo/electrocatalysts.
基金National Natural Science Foundation of China(Nos.21971127,21772099 and 21861132001)for financial support。
文摘Supramolecular assemblies constructed through the encapsulation of conductive polymers(CPs)by macrocyclic molecules have attracted increasing interest in the fields of supramolecular chemistry and electrochemistry.In this work,an effective strategy was reported to improve the stability and conductivity of CPs by electrochemically constructing different supramolecular assemblies composed of macrocycles and CPs.Typically,we uploaded zinc-based MOF(ZIF-8)onto carbon nanotube film(CNTF)and further electrically deposited macrocycles and CPs to gain the flexible conductive electrodes.Herein,five different supramolecular macrocycles,includingα-cyclodextrin(α-CD),sulfato-β-cyclodextrin(SCD),sulfonatocalix[4]arene(SC[4]),cucurbit[6]uril(CB[6])and cucurbit[7]uril(CB[7])were utilized and the electrochemical performances of the assembly electrodes increased in an order ofα-CD<SCD<SC[4]<CB[6]<CB[7],significantly improving the areal capacitance up to 1533 mF/cm^(2).This strategy may provide a new way for the application of macrocyclic supramolecules in electrochemical systems.
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(Nos.21021003 and 50673095)the Basic Research Development Program(Nos.2007CB808005 and 2009CB930802)the Fund of the Chinese Academy of Sciences
文摘The interracial assembly of photo-induced dimerization of atypical anthracene-containing amphiphilic dendron and host-vip interaction with γ-cyclodextrin has been investigated. It has been proved that even without long alkyl chain the amphiphilic dendron could still form stable Langmuir monolayer at the air/water interface. Through the host-vip interaction,γ-cyclodextrin can be used to encapsulate two headgroups of amphiphilic dendron in the antiparallel direction. However, the formed host-vip complex was sensitive to the surface pressure. Slight compression of surface pressure led amphiphilic dendron to reassemble into nanofibers through the strong π-π stacking between headgroups. On the other hand, under in situ irradiation, the amphiphilic dendron was stabilized in the cavity of γ- cyclodextrin through headgroup dimerization and the host-vip complex further irregularly aggregated to nanoparticles. Meanwhile, γ-cyclodextrin, as a silencer, blocked the supramolecular chirality transfer. Our conclusion was demonstrated through UV/vis, FT-IR, CD spectrum and AFM images, respectively.
