The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycl...The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.展开更多
Biological ion channels are essential for ion and molecule transport,playing a critical role in maintaining cellular equilibrium and regulating vital physiological functions such as cell growth,hormone secretion,and n...Biological ion channels are essential for ion and molecule transport,playing a critical role in maintaining cellular equilibrium and regulating vital physiological functions such as cell growth,hormone secretion,and nerve-muscle interactions.Drawing inspiration from nature,researchers have crafted an array of supramolecular artificial ion channels(AICs)using both unimolecular and self-assembly approaches.Notably,AICs based on macrocyclic molecules,such as cyclodextrins,crown ethers,and pillararenes,offer distinct advantages,including biocompatibility,precise structural design,ease of customization,and simple preparation.This review spotlights recent progress in bioinspired AICs rooted in macrocycles and their applications in the realm of biomedicine.We commence with an overview of the significance of biological channels and the strategies employed for fashioning supramolecular artificial channels.Subsequently,we navigate through the intricate landscape of molecular design,structural modulation,and the ion transport prowess exhibited by macrocycle-based AICs.Furthermore,we explore the promising biomedical applications of these AICs,encompassing roles in antibacterial measures,anticancer interventions,biosensing technologies,and treatments for channelopathies.Finally,we address the persisting challenges and illuminate prospects within this field,with the ultimate aim of steering future innovations in the development of supramolecular AICs.展开更多
Electrochemical conversion of carbon dioxide(CO_(2))to higher-value products provides a forward-looking way to solve the problems of environmental pollution and energy shortage.However,the low solubility of CO_(2)in a...Electrochemical conversion of carbon dioxide(CO_(2))to higher-value products provides a forward-looking way to solve the problems of environmental pollution and energy shortage.However,the low solubility of CO_(2)in aqueous electrolytes,sluggish kinetics,and low selectivity hamper the efficient conversion of CO_(2).Here,we report a Au-based hybrid nanomaterial by modifying Au nanoparticles(NPs)with the macrocyclic molecule cucurbit[6]uril(Au@CB[6]).Au@CB[6]displays the optimal selectivity of CO,with the highest CO Faraday efficiency(FECO)reaching 99.50%at−0.6 V vs.reversible hydrogen electrode(RHE).The partial current density of CO formed by Au@CB[6]increases dramatically,as 3.18 mA/cm2 at−0.6 V,which is more than ten times as that of oleylamine-coated Au NPs(Au@OAm,0.31 mA/cm2).Operando electrochemical measurement combined with density functional theory(DFT)calculations reveals that CB[6]can gather CO_(2)and lead the increased local CO_(2)concentration near metal interface,which realizes significantly enhanced electrochemical CO_(2)reduction reaction(CO_(2)RR)performance.展开更多
文摘The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.
基金supported by the National Key Research and De-velopment Program of China(2022YFB3203801,2022YFB3203804,2022YFB3203800)the Shanghai Sailing Program(23YF1420100),the National Natural Science Foundation of China(32071374)+5 种基金the Program of Shanghai Academic Research Leader under the Science and Technology Innovation Action Plan(21XD1422100)Program of Shanghai Science and Technology Development(22TS1400700)CAS Interdisciplinary Innovation Team(JCTD-2020-08),start-up funds from Shanghai Jiao Tong University(22X010201631)the Zhejiang Provin-cial Natural Science Foundation of China(LR22C100001)the Inno-vative Research Team of High-level Local Universities in Shanghai(SHSMU-ZDCX20210900)Shanghai Municipal Science and Tech-nology Commission(21dz2210100).
文摘Biological ion channels are essential for ion and molecule transport,playing a critical role in maintaining cellular equilibrium and regulating vital physiological functions such as cell growth,hormone secretion,and nerve-muscle interactions.Drawing inspiration from nature,researchers have crafted an array of supramolecular artificial ion channels(AICs)using both unimolecular and self-assembly approaches.Notably,AICs based on macrocyclic molecules,such as cyclodextrins,crown ethers,and pillararenes,offer distinct advantages,including biocompatibility,precise structural design,ease of customization,and simple preparation.This review spotlights recent progress in bioinspired AICs rooted in macrocycles and their applications in the realm of biomedicine.We commence with an overview of the significance of biological channels and the strategies employed for fashioning supramolecular artificial channels.Subsequently,we navigate through the intricate landscape of molecular design,structural modulation,and the ion transport prowess exhibited by macrocycle-based AICs.Furthermore,we explore the promising biomedical applications of these AICs,encompassing roles in antibacterial measures,anticancer interventions,biosensing technologies,and treatments for channelopathies.Finally,we address the persisting challenges and illuminate prospects within this field,with the ultimate aim of steering future innovations in the development of supramolecular AICs.
基金the financial support from the National Key R&D Program of China(Nos.2017YFA0700103 and 2018YFA0704502)the National Natural Science Foundation of China(No.22033008),and Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(No.2021ZZ103).
文摘Electrochemical conversion of carbon dioxide(CO_(2))to higher-value products provides a forward-looking way to solve the problems of environmental pollution and energy shortage.However,the low solubility of CO_(2)in aqueous electrolytes,sluggish kinetics,and low selectivity hamper the efficient conversion of CO_(2).Here,we report a Au-based hybrid nanomaterial by modifying Au nanoparticles(NPs)with the macrocyclic molecule cucurbit[6]uril(Au@CB[6]).Au@CB[6]displays the optimal selectivity of CO,with the highest CO Faraday efficiency(FECO)reaching 99.50%at−0.6 V vs.reversible hydrogen electrode(RHE).The partial current density of CO formed by Au@CB[6]increases dramatically,as 3.18 mA/cm2 at−0.6 V,which is more than ten times as that of oleylamine-coated Au NPs(Au@OAm,0.31 mA/cm2).Operando electrochemical measurement combined with density functional theory(DFT)calculations reveals that CB[6]can gather CO_(2)and lead the increased local CO_(2)concentration near metal interface,which realizes significantly enhanced electrochemical CO_(2)reduction reaction(CO_(2)RR)performance.
