Excipients are important components of pharmaceutical preparations that affect their quality, safety, and efficacy. Macrocyclic receptors are a family of supramolecular excipients with several advantages, including mo...Excipients are important components of pharmaceutical preparations that affect their quality, safety, and efficacy. Macrocyclic receptors are a family of supramolecular excipients with several advantages, including molecular-level protection, small sizes,fast kinetics of host-guest recognition, and modular construction. With the continuous advances in the medical field, personalized and precision medicine requires the development of excipients with low dosages, integrated modifying effects, universality,and controlled release. To meet these requirements, we have developed a new family of macrocyclic excipients based on calixarenes by integrating their covalent(broad chemical design space) and noncovalent(wide range of substrates) advantages.Accordingly, azocalixarenes(Azo CAs) were designed, showing high binding affinities to a broad spectrum of active pharmaceutical ingredients(APIs), selectivity to interferents, and responsiveness to hypoxic microenvironments. Due to their highly efficient and controllable recognition, Azo CAs serve as low-dose excipients for 30 APIs. Molecular encapsulation by Azo CAs results in the integrated modification of the physicochemical properties of APIs, including solubility, stability, bioavailability,and biocompatibility. Moreover, Azo CAs can be reduced by azoreductases overexpressed in hypoxic microenvironments,leading to the controlled release of APIs. Collectively, Azo CA excipients have broad application prospects for a series of diseases such as enteritis, arthritis, stroke, cancer, bacterial infection and kidney injury, with diverse therapeutic modalities,including chemotherapy, photodynamic therapy, photothermal therapy, immunotherapy, boron neutron capture therapy, radiotherapy, fluorescence imaging, and their combinations.展开更多
Comprehensive Summary Intramolecular interactions are fundamental for the unique structures and outstanding properties of metallofullerenes.However,how the internal metal species interplay with the cluster configurati...Comprehensive Summary Intramolecular interactions are fundamental for the unique structures and outstanding properties of metallofullerenes.However,how the internal metal species interplay with the cluster configuration inside oxide clusterfullerenes remains poorly understood.Herein,we successfully captured two oxide clusterfullerenes with different metals,namely,Lu_(2)O@C_(82)and Er_(2)O@C_(82),to elucidate the role of metal species in tuning cluster configuration.The two molecules have been fully characterized by mass spectrometry,Vis-NIR absorption spectroscopy,cyclic voltammetry,and single-crystal X-ray diffraction.展开更多
Artificial light-harvesting systems(LHSs) have drawn increasing research interest in recent times due to the energy crisis worldwide. Concurrently, macrocycle-based host–guest interactions have played an important ro...Artificial light-harvesting systems(LHSs) have drawn increasing research interest in recent times due to the energy crisis worldwide. Concurrently, macrocycle-based host–guest interactions have played an important role in the development of supramolecular chemistry. In recent years, studies towards artificial LHSs driven by macrocycle-based host–guest interactions are gradually being disclosed. In this mini-review, we briefly introduce the burgeoning progress of artificial LHSs driven by host–guest interactions. We believe that an increasing number of reports of artificial LHSs driven by host–guest interactions will appear in the near future and will provide a viable alternative for the future production of renewable energy.展开更多
Chemotherapy combined with photodynamic therapy has emerged as a promising strategy for cancer treatment.However,simultaneously delivering chemotherapeutic drugs and photosensitizers and precisely adjusting the ratio ...Chemotherapy combined with photodynamic therapy has emerged as a promising strategy for cancer treatment.However,simultaneously delivering chemotherapeutic drugs and photosensitizers and precisely adjusting the ratio of the two components as needed remains a challengeable task.Herein,novel supramolecular nanoparticles(donated as BODIPY-CPT-NPs)for chemo-photodynamic combination cancer therapy are constructed from a glutathione-responsive camptothecin-based prodrug,BODIPY photosensitizer,and dimacrocyclic host molecule through orthogonal host-guest recognitions and co-assembly.With this strategy,the ratio of prodrugs and photosensitizers in nanoparticles can be easily and precisely controlled as needed.Benefiting from the strong host-guest interactions and stable self-assembly,the nanoparticles exhibit excellent stability and photobleaching resistance.Furthermore,camptothecin can be released from nanoparticles for chemotherapy in the presence of reduction agent and single oxygen can be efficiently generated for PDT with light irradiation.The combined effects of the BODIPY-CPT-NPs have been verified in CT26 and HeLa cancer cells.展开更多
The power conversion efficiencies(PCEs)of all-polymer solar cells(all-PSCs),usually processed from low-boiling-point and toxic sol-vents,have reached high values of 18%.However,poor miscibility and uncontrollable crys...The power conversion efficiencies(PCEs)of all-polymer solar cells(all-PSCs),usually processed from low-boiling-point and toxic sol-vents,have reached high values of 18%.However,poor miscibility and uncontrollable crystallinity in polymer blends lead to a nota-ble drop in the PCEs when using green solvents,limiting the practical development of all-PSCs.Herein,a third component(guest)BTO was employed to optimize the miscibility and enhance the crystallinity of PM6/PY2Se-F host film processed from green solvent toluene(TL),which can effectively suppress the excessive aggregation of PY2Se-F and facilitate a nano-scale interpenetrating net-work morphology for exciton dissociation and charge transport.As a result,TL-processed all-polymer hosted solar cells(all-PHSCs)exhibited an impressive PCE of 17.01%.Moreover,the strong molecular interaction between the host and guest molecules also en-hances the thermal stability of the devices.Our host-guest strategy provides a unique approach to developing high-efficiency and stable all-PHSCs processed from green solvents,paving the way for the industrial development of all-PHSCs.展开更多
Programming microscopic assembly mode to control macroscopic property is an attractive research objective.In particular,controlling molecular assembly to control fluorescence is of considerable interest for developing...Programming microscopic assembly mode to control macroscopic property is an attractive research objective.In particular,controlling molecular assembly to control fluorescence is of considerable interest for developing smart fluorescent materials.Herein,a color-tunable supramolecular emissive system was developed based on cucurbit[8]uril mediated host-guest assembly.Chemical designing for the molecular structures with minimized change resulted in different assembly modes and hence generating distinctive fluorescence,including green,yellow and orange with the addition of cucurbit[n]uril.Taking advantage of this feature,the advanced information encryption material(4D code)with multiple encryption levels and time-dependent encryption feature was developed.Such a code was dynamic on time scale,generating a series of 3D codes with time.The encrypted information only can be recognized by integrating time-coursed codes.This work provides a new insight for designing intelligent fluorescent materials for information encryption with high level of security.展开更多
Comprehensive Summary,Organic luminogens with persistent room temperature phosphorescence(RTP)have drawn tremendous attentions due to their promising potentials in optoelectronic devices,information storage,biological...Comprehensive Summary,Organic luminogens with persistent room temperature phosphorescence(RTP)have drawn tremendous attentions due to their promising potentials in optoelectronic devices,information storage,biological imaging,and anti-counterfeiting.In this work,six triazatruxene-based lumiogens with different peripheral substituents and configurations are synthesized and systematically studied.The results show that their fluorescence quantum yields in solid states range from 15.73%to 37.58%.Dispersing the luminogens as guest into the host(PPh_(3))could turn on the persistent RTP,where PPh_(3)acts as not only a rigid matrix to suppress the non-radiative transitions of the guest,but also provides energy transfer channels to the guest.The maximum phosphorescence efficiency and the longest lifetime could reach 29.35%and 0.99 s in co-crystal films of 6-TAT-CN/PPh_(3)and 5-TAT-H/PPh_(3),respectively.Moreover,these host-guest co-crystalline films exhibit great potentials in advanced dynamic data encryption and anti-counterfeiting.This work deepens the insight for low cost,halogen-free,and facile fabrication of all-organic persistent RTP materials.展开更多
Buckybowl structures as non-uniform electrostatic potential distributions of poly-cyclic aromatic materials show a unique photoelectric performance.In this work,OTC was utilized for dynamic modulation of triplet excit...Buckybowl structures as non-uniform electrostatic potential distributions of poly-cyclic aromatic materials show a unique photoelectric performance.In this work,OTC was utilized for dynamic modulation of triplet exciton transition processes.Five host molecules with different functional units were selected,thus providing dif-ferent intermolecular interactions in the host/guest systems.Therefore,the delayed emissions were regulated from 536 to 624 nm via the tuning of the triplet exciton transition processes of OTC in different hosts.Experimental data and theoretical calculations revealed that the varied triplet transition behaviors resulted from the competition between the intersystem crossing(ISC)process of OTC-monomer and the reverse intersystem crossing(RISC)process of OTC-aggregates.This work proves the superior structure of buckybowl-based luminophore for controlling triplet exciton transition processes and supplies a new perspective for persistent afterglow luminophore design.展开更多
Comprehensive Summary In this work,we have successfully obtained a series of novel copper(I)–iodide clusters(CuI NCs)based assembly materials by combining supramolecular pseudorotaxane ligands{[Mebpe^(+)]PF_(6)^(–)@...Comprehensive Summary In this work,we have successfully obtained a series of novel copper(I)–iodide clusters(CuI NCs)based assembly materials by combining supramolecular pseudorotaxane ligands{[Mebpe^(+)]PF_(6)^(–)@CB[6](CB[6]=cucurbit[6]uril),L’·PF_(6)}and linkers{BPHF@CB[6],[BPHF=C_(14)H_(20)N_(4)(PF_(6))_(2)],L·PF_(6)},including discrete cluster CuI 1 and extended cluster organic frameworks MORF 1 and MORF 2.CuI 1 can be described as a dumbbell-shaped molecule with its body-centered site and two vertexes respectively occupied by one[Cu_(5)I_(6)]^(–)cluster and two CB[6]held together by two L’·PF_(6) ligands.The crystal structures of MORF 1 and MORF 2 are 1D anionic chain and four-fold interpenetrated 3D cationic diamondoid structure,respectively,which all featured intriguing alternating CB[6]and CuI NCs.展开更多
Coordination cages with intrinsic enzyme-like activity are a class of promising catalysts for improving the efficiency of organic reactions.We present herein a viable strategy to conveniently construct multimetallic a...Coordination cages with intrinsic enzyme-like activity are a class of promising catalysts for improving the efficiency of organic reactions.We present herein a viable strategy to conveniently construct multimetallic active sites into a coordination cage via self-assembly of a pre-formed sulfonylcalix[4]arene-based tetranuclear copper(II)precursor and an amino-functionalized dicarboxylate linker.The cage exhibits a“defective”,partially open cylindrical structure and features coordinatively labile dimetallic Cu(II)sites.Modulated by this unique inner cavity environment,promising catalytic activity toward selective oxidation of primary alcohols to carboxylic acids at room temperature is achieved.Mechanistic studies reveal that the coordinatively labile dimetallic Cu(II)sites can efficiently capture and activate the substrate and oxidant to catalyze the reaction,while the confined nano-cavity environment modulates substrate binding and enhances the catalytic turnover.This study provides a new approach to designing biomimetic multifunctional coordination cages and environmentally friendly supramolecular catalysts.展开更多
Redox responsive vesicles were constructed based on guest interaction between fl-cyclodextrin and a ferrocene self-assembly of a supra-amphiphile built by the host- derivative. The structure and destruction-reconstruc...Redox responsive vesicles were constructed based on guest interaction between fl-cyclodextrin and a ferrocene self-assembly of a supra-amphiphile built by the host- derivative. The structure and destruction-reconstruction reversibility of the ＂smart＂ vesicles were clearly characterized by electron microscopy and dynamic light scattering. Notably, these vesicles were proved to be capable of controlled release function and bringing protease resistance to the enzyme, showing great biocompatibility and promising applications.展开更多
Excellent electro-optical （E-O） performances are essential for high-quality reflective cholesteric liquid crystal （LC） displays, but are often limited by the high driving voltages required by these displays. Dispe...Excellent electro-optical （E-O） performances are essential for high-quality reflective cholesteric liquid crystal （LC） displays, but are often limited by the high driving voltages required by these displays. Dispersing functional nanomaterials into the LCs has emerged as a promising approach to achieve outstanding E-O properties. In this work, we report the facet-controlled E-O properties of a chiral nematic LC （N＊LC） doped with cubic, octahedral, and rhornbic dodecahedral Cu20. The outstanding E-O properties of the doped systems are related to the interaction between the liquid crystals and Cu20 dopants with different exposed crystal planes. Doping with octahedral and rhombic dodecahedral Cu20 reduces the stability of the planar state, as a result of both the surface abundance of active Cu atoms that interact with the polarized LC molecules, and the large amounts of vertexes and edges on the crystal surfaces, which accelerate the transition from the planar to the focal conic state under an applied electric field. Rhombic Cu20 is the most effective dopant for improving the E-O properties of the present LCs, resulting in a 65.31% reduction of the threshold voltage. The facet and morphology effects highlighted in this work provide a new pathway to develop excellent energy-saving meso-materials with exposed high-reactivity facets, improving their potential applications in electro-optical technologies and information displays.展开更多
Recent advances in non-fullerene acceptors(NFAs)like Y6 have pushed the power conversion efficiencies(PCEs)of organic solar cells(OSCs)above 19%.However,the harsh fabrication conditions,such as the use of the highly v...Recent advances in non-fullerene acceptors(NFAs)like Y6 have pushed the power conversion efficiencies(PCEs)of organic solar cells(OSCs)above 19%.However,the harsh fabrication conditions,such as the use of the highly volatile chloroform(CF)solvent and the thermal annealing process,are not suitable for large-area printing technologies and environmental standards.Here,a series of guest molecules,BT2O,BTO,and BT4O,are designed and synthesized with different numbers of oligo ethylene glycol(OEG)repeating units in side chains.All these guest molecules could tune the crystallization kinetics of the annealing-free host-guest active layers by inducing the self-assembly of Y6 in non-halogenated paraxylene(PX)solution.The increasing number of OEG repeating units in guest molecules could enhance the molecular assembly ability but molecular stacking steric hindrance simultaneously.Therefore,BTO with three OEG repeating units blended with PM6:PM7:Y6 delivers the highest PCE of 17.78%.Our results demonstrate controlling the crystallization kinetics via delicate side-chain engineering of guest molecules is an effective way to achieve efficient OSCs in non-halogenated solution.展开更多
The clinical translation of nanomedicines has been strongly hampered by the limitations of delivery vehicles,promoting scientists to search for novel nanocarriers.Although cell membrane-based delivery systems have att...The clinical translation of nanomedicines has been strongly hampered by the limitations of delivery vehicles,promoting scientists to search for novel nanocarriers.Although cell membrane-based delivery systems have attracted extensive attention,further functionalizations are urgently desired to augment their theranostic functions.We propose a cell-friendly supramolecular strategy to engineer cell membranes utilizing cyclodextrin-based host–guest molecular recognitions to fix the defects arising from chemical and genetic modifcations.In this study,the supramolecular cell membrane vesicles(SCMVs)specifcally accumulate in tumors,benefting from tumor-homing capability and the enhanced permeability and retention effect.SCMVs co-delivering indocyanine green and an indoleamine 2,3-dioxygenase inhibitor effectively ablate tumors combining photodynamic therapy and immunotherapy.Driven by host–guest inclusion complexation,SCMVs successfully encapsulate resiquimod to repolarize tumor-associated macrophages into M1 phenotype,synergizing with immune checkpoint blockade therapy.This supramolecular engineering methodology based on noncovalent interactions presents a generalizable and cell-friendly tactic to develop living cell–originated nanomaterials for precise cancer therapy.展开更多
In the presence of cucurbit[7]uril （CB[7]）, the CB[7] could react with palmatine, which served as a sensitive fluorescence probe, to form host-guest stable complexes and the fluorescence intensity of the complexes w...In the presence of cucurbit[7]uril （CB[7]）, the CB[7] could react with palmatine, which served as a sensitive fluorescence probe, to form host-guest stable complexes and the fluorescence intensity of the complexes was greatly enhanced. The fluorescence intensity decreased linearly with an increasing number of L-cystine in the inclusion system. The experimental results show that there exists a competition between L-cystine and palmatine for the CB[7] hydrophobic cavity and L-cystine occupies the space of CB[7] cavity, leading palmatine molecules to be forced to reside in the aqueous environment. Based on the fluorescence quenching of the CB[7]/palmatine complexes resulting from complex formation between CB[7] and L-cystine, a spectrofluorimetric method for the determination of L-cystine in aqueous solution in the presence of CB[7] was developed. The linear relationship between the corresponding values of the fluorescence quenching AF and L-cystine concentration was obtained in the range of 6.0 to 1.5 × 10^3 ngomL l, with a correlation coefficient （r） of 0.9996. The detection limit was 2.0 ng·mL -1. The application of the present method to the determination of L-cystine in tablets gave satisfactory results. This paper also discussed the mechanism of the fluorescence indicator probe.展开更多
Aromatic carboxylic acid self-assembly has been a hot research field for many scientists due to its strong coordination ability and flexible coordination mode.The hydrogen bond formed between aromatic carboxylic acids...Aromatic carboxylic acid self-assembly has been a hot research field for many scientists due to its strong coordination ability and flexible coordination mode.The hydrogen bond formed between aromatic carboxylic acids is a strong intermolecular force and has directionality and saturation,which plays a very important role in the self-assembly and regulation of aromatic carboxylic acids.In this review,we introduce surface organization formed by aromatic carboxylic acids with the aid of scanning tunneling microscopy(STM).These two-dimensional structures include molecular templates,host-guest systems,and photo-isomerization structures.We also emphasize the thermodynamics and dynamics,which are important research topics of current and future study.展开更多
The production of high-purity n-hexane under mild conditions is of great significance in both the petrochemical industry and synthetic chemistry.Here,we report an easy-to-operate and energy-efficient n-hexane purifica...The production of high-purity n-hexane under mild conditions is of great significance in both the petrochemical industry and synthetic chemistry.Here,we report an easy-to-operate and energy-efficient n-hexane purification strategy using nonporous adaptive crystals of perethylated leaning pillar[6]arene(EtLP6).Adaptive EtLP6 crystals preferentially absorb n-hexane over other branched or cyclic C6 alkanes with similar boiling points.This selectivity arises from the different thermodynamic stabilities and variabilities of EtLP6 crystalloids loaded with n-hexane and other C6 alkanes.Moreover,the reversible transformations between the nonporous guest-free and n-hexane-containing structures make the EtLP6 crystals highly recyclable.展开更多
Polycyclic aromatic hydrocarbons(PAHs)are promising nanocarbon materials with diverse optoelectronic properties,yet they also pose concerning environmental and health risks.Despite the ubiquity of PAHs in the environm...Polycyclic aromatic hydrocarbons(PAHs)are promising nanocarbon materials with diverse optoelectronic properties,yet they also pose concerning environmental and health risks.Despite the ubiquity of PAHs in the environment(crude oil,emissions,and biomass),most supermolecules rely on heteroatoms for stability.We discovered and characterized a family of all-hydrocarbon,all-π-conjugated[n]cycloparaphenylene-PAH host–guest complexes.We built a theoretical framework to rapidly select these complexes and predict their stabilities,driven exclusively by CH–πinteractions.More than a dozen complexes were confirmed experimentally and assembled directly from commercially available compounds.This motif offers a versatile way to combine the advantageous properties of organic semiconductors with the rich dynamic,stereochemical,stimulus-responsive,and stressdissipative behavior of host–guest complexes,while creating new opportunities for bespoke PAH separation or remediation materials.展开更多
Via the bottom-up synthetic strategy,we synthesized a pair of dodecanuclear metal clusters of Eu_(12)(C_(2)O_(4))_(9)(R/S-BNP)_(18)(EtOH)_(6)-(H_(2)0)_(6)·8EtOH-7H_(2)0(complex 2),which represent the largest axia...Via the bottom-up synthetic strategy,we synthesized a pair of dodecanuclear metal clusters of Eu_(12)(C_(2)O_(4))_(9)(R/S-BNP)_(18)(EtOH)_(6)-(H_(2)0)_(6)·8EtOH-7H_(2)0(complex 2),which represent the largest axial chiral lanthanide metal clusters.In the structure,rare four-pointed star coordination mode of oxalic acid is reported by this work.In addition,as a fluorescence sensor,the complex 2 exhibits high enantioselectivity for R-/S-BINOL-TF_(2)(EF=2.87)and other chiral binaphthyl derivatives.展开更多
基金supported by the National Natural Science Foundation of China (U20A20259, 22201141)the Fundamental Research Funds for the Central Universities+1 种基金the NCC Fund(NCC2020FH04)the China Postdoctoral Science Foundation(2022M711697)。
文摘Excipients are important components of pharmaceutical preparations that affect their quality, safety, and efficacy. Macrocyclic receptors are a family of supramolecular excipients with several advantages, including molecular-level protection, small sizes,fast kinetics of host-guest recognition, and modular construction. With the continuous advances in the medical field, personalized and precision medicine requires the development of excipients with low dosages, integrated modifying effects, universality,and controlled release. To meet these requirements, we have developed a new family of macrocyclic excipients based on calixarenes by integrating their covalent(broad chemical design space) and noncovalent(wide range of substrates) advantages.Accordingly, azocalixarenes(Azo CAs) were designed, showing high binding affinities to a broad spectrum of active pharmaceutical ingredients(APIs), selectivity to interferents, and responsiveness to hypoxic microenvironments. Due to their highly efficient and controllable recognition, Azo CAs serve as low-dose excipients for 30 APIs. Molecular encapsulation by Azo CAs results in the integrated modification of the physicochemical properties of APIs, including solubility, stability, bioavailability,and biocompatibility. Moreover, Azo CAs can be reduced by azoreductases overexpressed in hypoxic microenvironments,leading to the controlled release of APIs. Collectively, Azo CA excipients have broad application prospects for a series of diseases such as enteritis, arthritis, stroke, cancer, bacterial infection and kidney injury, with diverse therapeutic modalities,including chemotherapy, photodynamic therapy, photothermal therapy, immunotherapy, boron neutron capture therapy, radiotherapy, fluorescence imaging, and their combinations.
基金Financial support from NSFC(Nos.21925104,22171094,22201086,92261204,219010190,and 22001084)the Hubei Pro-vincial Natural Science Foundation of China(No.2021CFA020)+1 种基金the Natural Science Foundation of Jiangxi Province(No.20212BAB214029)Jiangxi“Double Thousand Plan”is grate-fully acknowledged.We thank the staff in BL17B beamline of National Center for Protein Sciences Shanghai(NCPSS)at Shanghai Synchrotron Radiation Facility for the assistance with data collection.
文摘Comprehensive Summary Intramolecular interactions are fundamental for the unique structures and outstanding properties of metallofullerenes.However,how the internal metal species interplay with the cluster configuration inside oxide clusterfullerenes remains poorly understood.Herein,we successfully captured two oxide clusterfullerenes with different metals,namely,Lu_(2)O@C_(82)and Er_(2)O@C_(82),to elucidate the role of metal species in tuning cluster configuration.The two molecules have been fully characterized by mass spectrometry,Vis-NIR absorption spectroscopy,cyclic voltammetry,and single-crystal X-ray diffraction.
基金financial support of the National Natural Science Foundation of China (No. 21702020)
文摘Artificial light-harvesting systems(LHSs) have drawn increasing research interest in recent times due to the energy crisis worldwide. Concurrently, macrocycle-based host–guest interactions have played an important role in the development of supramolecular chemistry. In recent years, studies towards artificial LHSs driven by macrocycle-based host–guest interactions are gradually being disclosed. In this mini-review, we briefly introduce the burgeoning progress of artificial LHSs driven by host–guest interactions. We believe that an increasing number of reports of artificial LHSs driven by host–guest interactions will appear in the near future and will provide a viable alternative for the future production of renewable energy.
基金supported by National Natural Science Foundation of China(Nos.21702153 and 21801194)Wuhan Science and Technology Bureau(No.whkxjsj009)the support of the Core Facility of Wuhan University and the Large-scale Instrument and Equipment Sharing Foundation of Wuhan University.
文摘Chemotherapy combined with photodynamic therapy has emerged as a promising strategy for cancer treatment.However,simultaneously delivering chemotherapeutic drugs and photosensitizers and precisely adjusting the ratio of the two components as needed remains a challengeable task.Herein,novel supramolecular nanoparticles(donated as BODIPY-CPT-NPs)for chemo-photodynamic combination cancer therapy are constructed from a glutathione-responsive camptothecin-based prodrug,BODIPY photosensitizer,and dimacrocyclic host molecule through orthogonal host-guest recognitions and co-assembly.With this strategy,the ratio of prodrugs and photosensitizers in nanoparticles can be easily and precisely controlled as needed.Benefiting from the strong host-guest interactions and stable self-assembly,the nanoparticles exhibit excellent stability and photobleaching resistance.Furthermore,camptothecin can be released from nanoparticles for chemotherapy in the presence of reduction agent and single oxygen can be efficiently generated for PDT with light irradiation.The combined effects of the BODIPY-CPT-NPs have been verified in CT26 and HeLa cancer cells.
基金supported by the National Natural Science Foundation of China(Grant Nos.52273188,22075194,51820105003,52203233)the National Key Research and Development Program of China(Grant No.2020YFB1506400)+3 种基金the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(Grant No.20KJA430010)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD),the National Postdoctoral Program forInnovative Talents(Grant Nos.BX2021205,BX20220221)project funded by China Postdoctoral Science Foundation(Grant No.2022M710102)Collaborative Innovation Center of Suzhou Nano Science and Technology,and the Key Laboratory of Polymeric Materials Design and Synthesis for Biomedical Function,Soochow University.
文摘The power conversion efficiencies(PCEs)of all-polymer solar cells(all-PSCs),usually processed from low-boiling-point and toxic sol-vents,have reached high values of 18%.However,poor miscibility and uncontrollable crystallinity in polymer blends lead to a nota-ble drop in the PCEs when using green solvents,limiting the practical development of all-PSCs.Herein,a third component(guest)BTO was employed to optimize the miscibility and enhance the crystallinity of PM6/PY2Se-F host film processed from green solvent toluene(TL),which can effectively suppress the excessive aggregation of PY2Se-F and facilitate a nano-scale interpenetrating net-work morphology for exciton dissociation and charge transport.As a result,TL-processed all-polymer hosted solar cells(all-PHSCs)exhibited an impressive PCE of 17.01%.Moreover,the strong molecular interaction between the host and guest molecules also en-hances the thermal stability of the devices.Our host-guest strategy provides a unique approach to developing high-efficiency and stable all-PHSCs processed from green solvents,paving the way for the industrial development of all-PHSCs.
基金supported by the National Natural Science Foundation of China(22025503,22220102004)the Shanghai Municipal Science and Technology Major Project(2018SHZDZX03)+3 种基金the Fundamental Research Funds for the Central Universitiesthe Programme of Introducing Talents of Discipline to Universities(B16017)the Science and Technology Commission of Shanghai Municipality(21JC1401700)the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study(SN-ZJU-SIAS-006)。
文摘Programming microscopic assembly mode to control macroscopic property is an attractive research objective.In particular,controlling molecular assembly to control fluorescence is of considerable interest for developing smart fluorescent materials.Herein,a color-tunable supramolecular emissive system was developed based on cucurbit[8]uril mediated host-guest assembly.Chemical designing for the molecular structures with minimized change resulted in different assembly modes and hence generating distinctive fluorescence,including green,yellow and orange with the addition of cucurbit[n]uril.Taking advantage of this feature,the advanced information encryption material(4D code)with multiple encryption levels and time-dependent encryption feature was developed.Such a code was dynamic on time scale,generating a series of 3D codes with time.The encrypted information only can be recognized by integrating time-coursed codes.This work provides a new insight for designing intelligent fluorescent materials for information encryption with high level of security.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.:22275189,22275193,and 22005307)the Natural Science Foundation of Fujian Province(E131AJ0101)+1 种基金Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZR115)Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences(E055AJ01).
文摘Comprehensive Summary,Organic luminogens with persistent room temperature phosphorescence(RTP)have drawn tremendous attentions due to their promising potentials in optoelectronic devices,information storage,biological imaging,and anti-counterfeiting.In this work,six triazatruxene-based lumiogens with different peripheral substituents and configurations are synthesized and systematically studied.The results show that their fluorescence quantum yields in solid states range from 15.73%to 37.58%.Dispersing the luminogens as guest into the host(PPh_(3))could turn on the persistent RTP,where PPh_(3)acts as not only a rigid matrix to suppress the non-radiative transitions of the guest,but also provides energy transfer channels to the guest.The maximum phosphorescence efficiency and the longest lifetime could reach 29.35%and 0.99 s in co-crystal films of 6-TAT-CN/PPh_(3)and 5-TAT-H/PPh_(3),respectively.Moreover,these host-guest co-crystalline films exhibit great potentials in advanced dynamic data encryption and anti-counterfeiting.This work deepens the insight for low cost,halogen-free,and facile fabrication of all-organic persistent RTP materials.
基金National Natural Scientific Foundation of China,Grant/Award Numbers:21975021,21975020,21875019,21871119,22105019,22175023Beijing National Laboratory for Molecular Sciences,Grant/Award Number:BNLMS192007BIT Research and Innovation Promoting Project,Grant/Award Number:2022YCXZ035。
文摘Buckybowl structures as non-uniform electrostatic potential distributions of poly-cyclic aromatic materials show a unique photoelectric performance.In this work,OTC was utilized for dynamic modulation of triplet exciton transition processes.Five host molecules with different functional units were selected,thus providing dif-ferent intermolecular interactions in the host/guest systems.Therefore,the delayed emissions were regulated from 536 to 624 nm via the tuning of the triplet exciton transition processes of OTC in different hosts.Experimental data and theoretical calculations revealed that the varied triplet transition behaviors resulted from the competition between the intersystem crossing(ISC)process of OTC-monomer and the reverse intersystem crossing(RISC)process of OTC-aggregates.This work proves the superior structure of buckybowl-based luminophore for controlling triplet exciton transition processes and supplies a new perspective for persistent afterglow luminophore design.
基金the National Natural Science Foundation of China(Nos.U21A20277,21975065,22101264,21825106)the China Postdoctoral Science Foundation(No.2021TQ0292)the Excellent Youth Foundation of Henan Scientific Committee(No.232300421022).
文摘Comprehensive Summary In this work,we have successfully obtained a series of novel copper(I)–iodide clusters(CuI NCs)based assembly materials by combining supramolecular pseudorotaxane ligands{[Mebpe^(+)]PF_(6)^(–)@CB[6](CB[6]=cucurbit[6]uril),L’·PF_(6)}and linkers{BPHF@CB[6],[BPHF=C_(14)H_(20)N_(4)(PF_(6))_(2)],L·PF_(6)},including discrete cluster CuI 1 and extended cluster organic frameworks MORF 1 and MORF 2.CuI 1 can be described as a dumbbell-shaped molecule with its body-centered site and two vertexes respectively occupied by one[Cu_(5)I_(6)]^(–)cluster and two CB[6]held together by two L’·PF_(6) ligands.The crystal structures of MORF 1 and MORF 2 are 1D anionic chain and four-fold interpenetrated 3D cationic diamondoid structure,respectively,which all featured intriguing alternating CB[6]and CuI NCs.
基金supported by the National Natural Science Foundation of China(21673239,92061202,U22A20387)the Fujian Science and Technology Project(2020L3022)+2 种基金the Science and Technology Service Network Initiative(STS)Foundation of Fujian Provincial Department of Science and Technology(2021T3004)the financial support provided by the National Science Foundation(CHE-1800354)the South Dakota Governor’s Office of Economic Development through the Center for Fluorinated Functional Materials(CFFM)。
文摘Coordination cages with intrinsic enzyme-like activity are a class of promising catalysts for improving the efficiency of organic reactions.We present herein a viable strategy to conveniently construct multimetallic active sites into a coordination cage via self-assembly of a pre-formed sulfonylcalix[4]arene-based tetranuclear copper(II)precursor and an amino-functionalized dicarboxylate linker.The cage exhibits a“defective”,partially open cylindrical structure and features coordinatively labile dimetallic Cu(II)sites.Modulated by this unique inner cavity environment,promising catalytic activity toward selective oxidation of primary alcohols to carboxylic acids at room temperature is achieved.Mechanistic studies reveal that the coordinatively labile dimetallic Cu(II)sites can efficiently capture and activate the substrate and oxidant to catalyze the reaction,while the confined nano-cavity environment modulates substrate binding and enhances the catalytic turnover.This study provides a new approach to designing biomimetic multifunctional coordination cages and environmentally friendly supramolecular catalysts.
基金This work was supported by the National Natural Science Foundation of China （（Nos. 21420102007, 21234004, 21574056, 91527302）, the Chang Jiang Scholars Program of China, and Project 2016014 Sup- ported by Graduate Innovation Fund of Jilin University.
文摘Redox responsive vesicles were constructed based on guest interaction between fl-cyclodextrin and a ferrocene self-assembly of a supra-amphiphile built by the host- derivative. The structure and destruction-reconstruction reversibility of the ＂smart＂ vesicles were clearly characterized by electron microscopy and dynamic light scattering. Notably, these vesicles were proved to be capable of controlled release function and bringing protease resistance to the enzyme, showing great biocompatibility and promising applications.
文摘Excellent electro-optical （E-O） performances are essential for high-quality reflective cholesteric liquid crystal （LC） displays, but are often limited by the high driving voltages required by these displays. Dispersing functional nanomaterials into the LCs has emerged as a promising approach to achieve outstanding E-O properties. In this work, we report the facet-controlled E-O properties of a chiral nematic LC （N＊LC） doped with cubic, octahedral, and rhornbic dodecahedral Cu20. The outstanding E-O properties of the doped systems are related to the interaction between the liquid crystals and Cu20 dopants with different exposed crystal planes. Doping with octahedral and rhombic dodecahedral Cu20 reduces the stability of the planar state, as a result of both the surface abundance of active Cu atoms that interact with the polarized LC molecules, and the large amounts of vertexes and edges on the crystal surfaces, which accelerate the transition from the planar to the focal conic state under an applied electric field. Rhombic Cu20 is the most effective dopant for improving the E-O properties of the present LCs, resulting in a 65.31% reduction of the threshold voltage. The facet and morphology effects highlighted in this work provide a new pathway to develop excellent energy-saving meso-materials with exposed high-reactivity facets, improving their potential applications in electro-optical technologies and information displays.
基金supported by the National Natural Science Foundation of China(Grant Nos.51922074,22075194,51820105003,and 52203233)the National Key Research and Development Program of China(Grant No.2020YFB1506400)+4 种基金the Natural Science Foundation of the Jiangsu Higher Education Insti-tutions of China(Grant No.20KJA430010)the Tang Scholar,the Priority Academic Program Development of Jiangsu Higher Educa-tion Institutions(PAPD)the National Postdoctoral Program for Innovative Talents(Grant Nos.BX2021205 and BX20220221)project funded by China Postdoctoral Science Foundation(Grant No.2022M710102)Collaborative Innovation Center of Suzhou Nano Science and Technology.
文摘Recent advances in non-fullerene acceptors(NFAs)like Y6 have pushed the power conversion efficiencies(PCEs)of organic solar cells(OSCs)above 19%.However,the harsh fabrication conditions,such as the use of the highly volatile chloroform(CF)solvent and the thermal annealing process,are not suitable for large-area printing technologies and environmental standards.Here,a series of guest molecules,BT2O,BTO,and BT4O,are designed and synthesized with different numbers of oligo ethylene glycol(OEG)repeating units in side chains.All these guest molecules could tune the crystallization kinetics of the annealing-free host-guest active layers by inducing the self-assembly of Y6 in non-halogenated paraxylene(PX)solution.The increasing number of OEG repeating units in guest molecules could enhance the molecular assembly ability but molecular stacking steric hindrance simultaneously.Therefore,BTO with three OEG repeating units blended with PM6:PM7:Y6 delivers the highest PCE of 17.78%.Our results demonstrate controlling the crystallization kinetics via delicate side-chain engineering of guest molecules is an effective way to achieve efficient OSCs in non-halogenated solution.
基金supported by the Vanke Special Fund for Public Health and Health Discipline Development,Tsinghua University(2022Z82WKJ005,2022Z82WKJ013)the Tsinghua University Spring Breeze Fund(2021Z99CFZ007)+2 种基金the National Natural Science Foundation of China(22175107)Funding by Tsinghua Universitythe Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study(SN-ZJU-SIAS-006)。
文摘The clinical translation of nanomedicines has been strongly hampered by the limitations of delivery vehicles,promoting scientists to search for novel nanocarriers.Although cell membrane-based delivery systems have attracted extensive attention,further functionalizations are urgently desired to augment their theranostic functions.We propose a cell-friendly supramolecular strategy to engineer cell membranes utilizing cyclodextrin-based host–guest molecular recognitions to fix the defects arising from chemical and genetic modifcations.In this study,the supramolecular cell membrane vesicles(SCMVs)specifcally accumulate in tumors,benefting from tumor-homing capability and the enhanced permeability and retention effect.SCMVs co-delivering indocyanine green and an indoleamine 2,3-dioxygenase inhibitor effectively ablate tumors combining photodynamic therapy and immunotherapy.Driven by host–guest inclusion complexation,SCMVs successfully encapsulate resiquimod to repolarize tumor-associated macrophages into M1 phenotype,synergizing with immune checkpoint blockade therapy.This supramolecular engineering methodology based on noncovalent interactions presents a generalizable and cell-friendly tactic to develop living cell–originated nanomaterials for precise cancer therapy.
文摘In the presence of cucurbit[7]uril （CB[7]）, the CB[7] could react with palmatine, which served as a sensitive fluorescence probe, to form host-guest stable complexes and the fluorescence intensity of the complexes was greatly enhanced. The fluorescence intensity decreased linearly with an increasing number of L-cystine in the inclusion system. The experimental results show that there exists a competition between L-cystine and palmatine for the CB[7] hydrophobic cavity and L-cystine occupies the space of CB[7] cavity, leading palmatine molecules to be forced to reside in the aqueous environment. Based on the fluorescence quenching of the CB[7]/palmatine complexes resulting from complex formation between CB[7] and L-cystine, a spectrofluorimetric method for the determination of L-cystine in aqueous solution in the presence of CB[7] was developed. The linear relationship between the corresponding values of the fluorescence quenching AF and L-cystine concentration was obtained in the range of 6.0 to 1.5 × 10^3 ngomL l, with a correlation coefficient （r） of 0.9996. The detection limit was 2.0 ng·mL -1. The application of the present method to the determination of L-cystine in tablets gave satisfactory results. This paper also discussed the mechanism of the fluorescence indicator probe.
基金supported by the National Basic Research Program of China (No. 2016YFA0200700)the National Natural Science Foundation of China (Nos. 21773041 and 21472029)
文摘Aromatic carboxylic acid self-assembly has been a hot research field for many scientists due to its strong coordination ability and flexible coordination mode.The hydrogen bond formed between aromatic carboxylic acids is a strong intermolecular force and has directionality and saturation,which plays a very important role in the self-assembly and regulation of aromatic carboxylic acids.In this review,we introduce surface organization formed by aromatic carboxylic acids with the aid of scanning tunneling microscopy(STM).These two-dimensional structures include molecular templates,host-guest systems,and photo-isomerization structures.We also emphasize the thermodynamics and dynamics,which are important research topics of current and future study.
基金the National Natural Science Foundation of China(21871108)Jilin Province-University Cooperative Construction Project-Special Funds for New Materials(SXGJSF2017-3)Jilin University Talents Cultivation Program for financial support.
文摘The production of high-purity n-hexane under mild conditions is of great significance in both the petrochemical industry and synthetic chemistry.Here,we report an easy-to-operate and energy-efficient n-hexane purification strategy using nonporous adaptive crystals of perethylated leaning pillar[6]arene(EtLP6).Adaptive EtLP6 crystals preferentially absorb n-hexane over other branched or cyclic C6 alkanes with similar boiling points.This selectivity arises from the different thermodynamic stabilities and variabilities of EtLP6 crystalloids loaded with n-hexane and other C6 alkanes.Moreover,the reversible transformations between the nonporous guest-free and n-hexane-containing structures make the EtLP6 crystals highly recyclable.
基金supported by the American Chemical Society Petroleum Research Fund Doctoral New Investigator grant(No.59067-DNI7)Further support was provided by the College of Engineering and Applied Science at the University of Colorado Boulder.This work utilized resources from the University of Colorado Boulder Research Computing Group,which is supported by the National Science Foundation(awards ACI-1532235 and ACI-1532236)the University of Colorado Boulder,and Colorado State University.
文摘Polycyclic aromatic hydrocarbons(PAHs)are promising nanocarbon materials with diverse optoelectronic properties,yet they also pose concerning environmental and health risks.Despite the ubiquity of PAHs in the environment(crude oil,emissions,and biomass),most supermolecules rely on heteroatoms for stability.We discovered and characterized a family of all-hydrocarbon,all-π-conjugated[n]cycloparaphenylene-PAH host–guest complexes.We built a theoretical framework to rapidly select these complexes and predict their stabilities,driven exclusively by CH–πinteractions.More than a dozen complexes were confirmed experimentally and assembled directly from commercially available compounds.This motif offers a versatile way to combine the advantageous properties of organic semiconductors with the rich dynamic,stereochemical,stimulus-responsive,and stressdissipative behavior of host–guest complexes,while creating new opportunities for bespoke PAH separation or remediation materials.
基金This work was supported by the National Natural Science Foundation of China(Nos.21971032,51725204,21771132,51972216).
文摘Via the bottom-up synthetic strategy,we synthesized a pair of dodecanuclear metal clusters of Eu_(12)(C_(2)O_(4))_(9)(R/S-BNP)_(18)(EtOH)_(6)-(H_(2)0)_(6)·8EtOH-7H_(2)0(complex 2),which represent the largest axial chiral lanthanide metal clusters.In the structure,rare four-pointed star coordination mode of oxalic acid is reported by this work.In addition,as a fluorescence sensor,the complex 2 exhibits high enantioselectivity for R-/S-BINOL-TF_(2)(EF=2.87)and other chiral binaphthyl derivatives.
