Long-term memory(LTM)allows animals to use remote past experiences to guide current and future decisions.One of the widely-used animal models for LTM research is the fruit-fly Drosophila melanogaster,which can form di...Long-term memory(LTM)allows animals to use remote past experiences to guide current and future decisions.One of the widely-used animal models for LTM research is the fruit-fly Drosophila melanogaster,which can form different types of LTM after different learning paradigms[1-6].Spaced training-induced LTM(spLTM),perhaps the most studied Drosophila LTM,requires multiple repeated learning trials with a 15-min resting interval between each trial.For decades,spLTM has been considered the only aversive olfactory LTM that can last for>7 days[1].Recently,two other types of LTM,context-dependent LTM(cLTM)[5]and merged LTM(mLTM)[6],have been discovered with the same long duration as spLTM,and can be formed with only one aversive learning trial.展开更多
Cation recognition by cationic receptors is typically challenging due to coulombic repulsion.In this study,we designed a hexacationic receptor,namely,3NDI^(6+).This tricycle naturally adopts a sandwichlike conformatio...Cation recognition by cationic receptors is typically challenging due to coulombic repulsion.In this study,we designed a hexacationic receptor,namely,3NDI^(6+).This tricycle naturally adopts a sandwichlike conformation as its hexafluorophosphate salt([3NDI^(6+)@2PF_(6)^(-)]·4PF_(6)^(-))but then recognizes two chloride anions upon treatment with a chloride anion source.The recognition of the first chloride anion(as an allosteric modulator)facilitates conformational regulation fromthe sandwich-like conformation with a collapsed cavity to a preorganized capsule-like conformation.After conformational switching,the second chloride anion is further recognized to form the inclusion complex[3NDI^(6+)■2Cl^(-)]^(4+).The chloridecontaining hexacationic capsule([3NDI^(6+)■2Cl^(-)]^(^(4+)))was found to recognize various cations(e.g.,K+from KCl),as supported by the crystal structure of the potassium complex,which revealed a single anionic[KCl_(2)]–entity within the capsule.Prior to conversion to the chloride anion-bound capsule-like form,no evidence of cation recognition is seen by[3NDI^(6+)@2PF_(6)^(-)]·4PF6^(-).The ability to accommodate a cation within the cationic framework of 3NDI^(^(6+))(as[3NDI^(^(6+))■2Cl^(-)]·4Cl^(-))is ascribed to specific anion(as Cl^(-))recognition and formation of a capsule-like species,rather than simple charge balance effects.This study presents a new strategy for cation recognition by a cationic capsule that underscores the promise of allosteric control over small-molecule receptor systems.展开更多
Modulating the photophysical of organic solid-state functional materials is crucial for advancing supramolecular chemistry and materials science.Here,we present aπ-conjugation enhanced charge-transfer strategy to tur...Modulating the photophysical of organic solid-state functional materials is crucial for advancing supramolecular chemistry and materials science.Here,we present aπ-conjugation enhanced charge-transfer strategy to turn on the photothermal conversion properties of crown ether cocrystals.Three crown ethers(H_(1),H_(2),and H_(3))bearing differentπ-conjugated moieties are synthesized,exhibiting enhanced solid-state luminescence upon increasing molecular conjugation.In addition,three sets of host–vip cocrystals are constructed via charge-transfer(CT)interactions between these electron-rich crown ethers and electron-deficient 1,2,4,5-tetracyanobenzene(TCNB).Based on the variations in CT interactions,the resulting cocrystals transform from primarily photoluminescent behavior to efficient photothermal conversion.Detailed structural and spectroscopic analyses reveal that the extent of π-donor/π-acceptor overlap within the cocrystals is the dominant factor governing their tunable photophysical properties.展开更多
基金supported by granes from the National Science Foundation of China(31970955)and the Tsinghua-Peking Center for Life Sciences.
文摘Long-term memory(LTM)allows animals to use remote past experiences to guide current and future decisions.One of the widely-used animal models for LTM research is the fruit-fly Drosophila melanogaster,which can form different types of LTM after different learning paradigms[1-6].Spaced training-induced LTM(spLTM),perhaps the most studied Drosophila LTM,requires multiple repeated learning trials with a 15-min resting interval between each trial.For decades,spLTM has been considered the only aversive olfactory LTM that can last for>7 days[1].Recently,two other types of LTM,context-dependent LTM(cLTM)[5]and merged LTM(mLTM)[6],have been discovered with the same long duration as spLTM,and can be formed with only one aversive learning trial.
基金the National Key Research and Development Program of China(grant no.2021YFA0910100)the National Natural Science Foundation of China(grant nos.22035006,22320102001,and 22350007)+3 种基金the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study(grant no.SN-ZJU-SIAS-006)the“pioneer”and“Leading Goose”R&D Program of Zhejiang(grant no.2025C04010)the Leading Innovation Team grant from the Department of Science and Technology of Zhejiang Province(grant no.2022R01005)for financial support.F.Hthanks the Chemistry Instrumentation Center of Zhejiang University for technical support.We are grateful for the access to the research facilities in Chemistry Department of the University of Hong Kong(HKU).Thework in Austinwas supported by the Robert A.Welch Foundation(F-0018 to J.L.S.).We thank HKU for their continued support of this research.
文摘Cation recognition by cationic receptors is typically challenging due to coulombic repulsion.In this study,we designed a hexacationic receptor,namely,3NDI^(6+).This tricycle naturally adopts a sandwichlike conformation as its hexafluorophosphate salt([3NDI^(6+)@2PF_(6)^(-)]·4PF_(6)^(-))but then recognizes two chloride anions upon treatment with a chloride anion source.The recognition of the first chloride anion(as an allosteric modulator)facilitates conformational regulation fromthe sandwich-like conformation with a collapsed cavity to a preorganized capsule-like conformation.After conformational switching,the second chloride anion is further recognized to form the inclusion complex[3NDI^(6+)■2Cl^(-)]^(4+).The chloridecontaining hexacationic capsule([3NDI^(6+)■2Cl^(-)]^(^(4+)))was found to recognize various cations(e.g.,K+from KCl),as supported by the crystal structure of the potassium complex,which revealed a single anionic[KCl_(2)]–entity within the capsule.Prior to conversion to the chloride anion-bound capsule-like form,no evidence of cation recognition is seen by[3NDI^(6+)@2PF_(6)^(-)]·4PF6^(-).The ability to accommodate a cation within the cationic framework of 3NDI^(^(6+))(as[3NDI^(^(6+))■2Cl^(-)]·4Cl^(-))is ascribed to specific anion(as Cl^(-))recognition and formation of a capsule-like species,rather than simple charge balance effects.This study presents a new strategy for cation recognition by a cationic capsule that underscores the promise of allosteric control over small-molecule receptor systems.
基金supported by the Scientific Research Startup Foundation of Hunan Institute of Technology(HQ23047)Natural Science Foundation of Hunan Province(2025JJ70140)Key Scientific Research Projects of the Department of Education of Hunan Province(22A0628).
文摘Modulating the photophysical of organic solid-state functional materials is crucial for advancing supramolecular chemistry and materials science.Here,we present aπ-conjugation enhanced charge-transfer strategy to turn on the photothermal conversion properties of crown ether cocrystals.Three crown ethers(H_(1),H_(2),and H_(3))bearing differentπ-conjugated moieties are synthesized,exhibiting enhanced solid-state luminescence upon increasing molecular conjugation.In addition,three sets of host–vip cocrystals are constructed via charge-transfer(CT)interactions between these electron-rich crown ethers and electron-deficient 1,2,4,5-tetracyanobenzene(TCNB).Based on the variations in CT interactions,the resulting cocrystals transform from primarily photoluminescent behavior to efficient photothermal conversion.Detailed structural and spectroscopic analyses reveal that the extent of π-donor/π-acceptor overlap within the cocrystals is the dominant factor governing their tunable photophysical properties.
