A [3]rotaxane I involving two naphtho-21-crown-7 （N21 C7） rings and a dumbbell-shaped component 4 was synthesized. The dumbbell-shape molecule 4 contains one viologen nucleus, two secondary alkyl ammonium sites and ...A [3]rotaxane I involving two naphtho-21-crown-7 （N21 C7） rings and a dumbbell-shaped component 4 was synthesized. The dumbbell-shape molecule 4 contains one viologen nucleus, two secondary alkyl ammonium sites and two phenyl stoppers. After threading the N21C7 ring with the thread-like ammonium guest 3, the copper（l）-catalyzed Huisgen alkyne-azide 1,3-dipolar cycloaddition （CuAAC ＂click＂ reaction）, was performed to connect the pseudorotaxanes with viologen unit 2 and generate 1. Through treating the [3]rotaxane by the base and acid circularly, the two N21 C7 rings can make shuttling motion along the axle. Meanwhile the distance between the electron-deficient viologen unit and the electron-rich naphthol group can be adjusted precisely along with a remarkable intramolecular charge- transfer （CT） behavior.展开更多
Controlling protein topology has been a long standing challenge to go beyond their linear configuration defined by the translation mechanism of cellular machinery. In this mini-review, we focus on the topological dive...Controlling protein topology has been a long standing challenge to go beyond their linear configuration defined by the translation mechanism of cellular machinery. In this mini-review, we focus on the topological diversity in proteins and review the major categories of protein topologies known to date, including branched/star proteins, circular proteins, lasso proteins, knotted proteins, and protein catenanes. The discovery of these topologically complex natural proteins and their synthetic pathways, the rational design and recombinant synthesis of artificial topological proteins and their biophysical studies, are summarized and discussed with regard to their general features and broad implications. The complexity of protein topology is recognized and the routes to diverse protein topologies are illustrated. We believe that topology engineering is an important way to modify protein properties without altemating their native sequences and shall bring in valuable dynamic features central to the creation of artificial protein machinery.展开更多
The composite polymer electrolyte has been obtained via incorporating LiCUST-701(a new metal–organic rotaxane framework modified by Li+)into poly(ethylene oxide)(PEO)matrix and give a high ionic conductivity of 4.02&...The composite polymer electrolyte has been obtained via incorporating LiCUST-701(a new metal–organic rotaxane framework modified by Li+)into poly(ethylene oxide)(PEO)matrix and give a high ionic conductivity of 4.02×10^(−4)S/cm at 60℃.DFT calculations were used to visualize the possible diffusion pathway of Li+.The all-solid-state cell assembled with LiFePO_(4),composite polymer electrolyte and lithium metal foil delivered with excellent cycling capability and stability even under high current densities.展开更多
As a promising imaging technology,the low sensitivity of fluorine-19 magnetic resonance imaging(^(19)F MRI)severely hinders its biomedical applications.Herein,we have developed an unprecedented rotaxanebased strategy ...As a promising imaging technology,the low sensitivity of fluorine-19 magnetic resonance imaging(^(19)F MRI)severely hinders its biomedical applications.Herein,we have developed an unprecedented rotaxanebased strategy to improve the sensitivity of^(19)F MRI agents.By threading the fluorinated macrocycle into2-blade pinwheel[2]rotaxanes,the^(19)F longitudinal relaxation rate R1was dramatically increased,resulting in a significant^(19)F MRI signal intensity enhancement of up to 79%.Through comparative molecular dynamics studies using a series of solution and solid-state^(1)H/^(19)F nuclear magnetic resonance(^(1)H/^(19)F NMR)and molecular dynamics simulations,it was found that the formation of mechanical bonds dramatically restricts the motion of the wheel fluorines and thus increasing the R1for higher^(19)F MRI sensitivity.Besides a novel strategy for improving^(19)F MRI sensitivity,this study has established^(19)F NMR/MRI as a valuable technology for monitoring the molecular dynamics of rotaxanes,which may shed new light on high-performance^(19)F MRI agents and molecular devices.展开更多
Molecular switches that can undergo reversible switching between two or more different states in response to external stimuli have been used in the fabrication of various optoelectronic devices and smart materials for...Molecular switches that can undergo reversible switching between two or more different states in response to external stimuli have been used in the fabrication of various optoelectronic devices and smart materials for many decades, and also found many applications in sensing, molecular self-assembly and photo-controlled biological systems. Recently, mechanically interlocked molecules, such as rotaxanes and catenanes, and molecular rotary motors based on overcrowded alkenes have emerged as two new kinds of molecular switches. Some novel applications of above-mentioned molecular switches have been discovered. In this mini review, we mainly highlight noticeable achievements over the past decade in this field, and summarize the applications of new types of molecular switches, for instance, controlling the chiral space to regulate catalytic reaction as organocatalysts, controlling molecular motions, synthesizing a peptide in a sequence-specific manner and modulating the wettability of the self-assembled monolayers.展开更多
The series of salen-bridged bis-pillar[1]arenes were conveniently prepared by condensation reaction of5,5'-methylenebis(2-hydroxybenzalde hyde)or 5,5'-(propane-2,2-diyl)bis(2-hydroxybenzaldehyde)with mono-amid...The series of salen-bridged bis-pillar[1]arenes were conveniently prepared by condensation reaction of5,5'-methylenebis(2-hydroxybenzalde hyde)or 5,5'-(propane-2,2-diyl)bis(2-hydroxybenzaldehyde)with mono-amido-functionalized pillar[5]arenes containing different terminal aminoalkyl groups in refluxing ethanol.The^1H NMR and 2D-NOESY spectra indicated that the salen-bridged bis-pillar[5]arenes with longer allcylene linker(n=3,4,6)formed the fascinating bis-[1]rotaxanes,while the salenbridged bis-pillar[5]arenes with short hydrazine and ethylenediamino linker(n=0,2)predominately existed in free form.The single crystal structure of the bis-pillar[5]are ne ambiguously indicated that two propylenediamino linker inserted in to two cavities of pillar[5]arene to form a novel bis-[1]rotaxanes.展开更多
Supramolecular polymer networks(SPNs)are celebrated for their dynamic nature,yet they often exhibit inadequate mechanical properties.Thus far,the quest to bolster the mechanical resilience of SPNs while preserving the...Supramolecular polymer networks(SPNs)are celebrated for their dynamic nature,yet they often exhibit inadequate mechanical properties.Thus far,the quest to bolster the mechanical resilience of SPNs while preserving their dynamic character presents a formidable challenge.Herein,we introduce[2]rotaxane into SPN to serve as another cross-link,which could effectively enhance the mechanical robustness of the polymer network without losing the dynamic properties.Compared with SPN,the dually cross-linked network(DPN)demonstrates superior breaking strength,Young’s modulus,puncture force and toughness,underscoring its superior robustness.Furthermore,the cyclic tensile tests reveal that the energy dissipation capacity of DPN rivals,and in some cases surpasses,that of SPN,owing to the efficient energy dissipation pathway facilitated by[2]rotaxane.In addition,benefiting from stable topological structure of[2]rotaxane,DPN exhibits accelerated recovery from deformation,indicating superior elasticity compared to SPN.This strategy elevates the performance of SPNs across multiple metrics,presenting a promising avenue for the development of high-performance dynamic materials.展开更多
基金the National Basic Research Program of China(973 Program,No.2011CB932500)the National Natural Science Foundation of China(Nos.20932004 and 20972077) for financial support
文摘A [3]rotaxane I involving two naphtho-21-crown-7 （N21 C7） rings and a dumbbell-shaped component 4 was synthesized. The dumbbell-shape molecule 4 contains one viologen nucleus, two secondary alkyl ammonium sites and two phenyl stoppers. After threading the N21C7 ring with the thread-like ammonium guest 3, the copper（l）-catalyzed Huisgen alkyne-azide 1,3-dipolar cycloaddition （CuAAC ＂click＂ reaction）, was performed to connect the pseudorotaxanes with viologen unit 2 and generate 1. Through treating the [3]rotaxane by the base and acid circularly, the two N21 C7 rings can make shuttling motion along the axle. Meanwhile the distance between the electron-deficient viologen unit and the electron-rich naphthol group can be adjusted precisely along with a remarkable intramolecular charge- transfer （CT） behavior.
基金supported by the National High Technology Research and Development Program of China (2015AA020941)the National Natural Science Foundation of China (21474003, 91427304)"1000 Plan (Youth)"
文摘Controlling protein topology has been a long standing challenge to go beyond their linear configuration defined by the translation mechanism of cellular machinery. In this mini-review, we focus on the topological diversity in proteins and review the major categories of protein topologies known to date, including branched/star proteins, circular proteins, lasso proteins, knotted proteins, and protein catenanes. The discovery of these topologically complex natural proteins and their synthetic pathways, the rational design and recombinant synthesis of artificial topological proteins and their biophysical studies, are summarized and discussed with regard to their general features and broad implications. The complexity of protein topology is recognized and the routes to diverse protein topologies are illustrated. We believe that topology engineering is an important way to modify protein properties without altemating their native sequences and shall bring in valuable dynamic features central to the creation of artificial protein machinery.
基金the National Natural Science Foundation of China(Nos.U1973201 and 22271023).
文摘The composite polymer electrolyte has been obtained via incorporating LiCUST-701(a new metal–organic rotaxane framework modified by Li+)into poly(ethylene oxide)(PEO)matrix and give a high ionic conductivity of 4.02×10^(−4)S/cm at 60℃.DFT calculations were used to visualize the possible diffusion pathway of Li+.The all-solid-state cell assembled with LiFePO_(4),composite polymer electrolyte and lithium metal foil delivered with excellent cycling capability and stability even under high current densities.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0540000)the National Key R&D Program of China(No.2018YFA0704000)+2 种基金the National Natural Science Foundation of China(Nos.22327901,22077098,U21A20392,21921004,and 82127802)the Knowledge Innovation Program of WuhanBasic Research(No.2022020801010137)support from the Youth Innovation Promotion Association and the Young Top-notch Talent Cultivation Program。
文摘As a promising imaging technology,the low sensitivity of fluorine-19 magnetic resonance imaging(^(19)F MRI)severely hinders its biomedical applications.Herein,we have developed an unprecedented rotaxanebased strategy to improve the sensitivity of^(19)F MRI agents.By threading the fluorinated macrocycle into2-blade pinwheel[2]rotaxanes,the^(19)F longitudinal relaxation rate R1was dramatically increased,resulting in a significant^(19)F MRI signal intensity enhancement of up to 79%.Through comparative molecular dynamics studies using a series of solution and solid-state^(1)H/^(19)F nuclear magnetic resonance(^(1)H/^(19)F NMR)and molecular dynamics simulations,it was found that the formation of mechanical bonds dramatically restricts the motion of the wheel fluorines and thus increasing the R1for higher^(19)F MRI sensitivity.Besides a novel strategy for improving^(19)F MRI sensitivity,this study has established^(19)F NMR/MRI as a valuable technology for monitoring the molecular dynamics of rotaxanes,which may shed new light on high-performance^(19)F MRI agents and molecular devices.
基金supported by the National Natural Science Foundation of China(21272073,21421004,21190033)the National Basic Research Program of China(2011CB808400)+1 种基金the Fok Ying Tong Education Foundation(121069)the Fundamental Research Funds for the Central Universities,and the Innovation Program of Shanghai Municipal Education Commission
文摘Molecular switches that can undergo reversible switching between two or more different states in response to external stimuli have been used in the fabrication of various optoelectronic devices and smart materials for many decades, and also found many applications in sensing, molecular self-assembly and photo-controlled biological systems. Recently, mechanically interlocked molecules, such as rotaxanes and catenanes, and molecular rotary motors based on overcrowded alkenes have emerged as two new kinds of molecular switches. Some novel applications of above-mentioned molecular switches have been discovered. In this mini review, we mainly highlight noticeable achievements over the past decade in this field, and summarize the applications of new types of molecular switches, for instance, controlling the chiral space to regulate catalytic reaction as organocatalysts, controlling molecular motions, synthesizing a peptide in a sequence-specific manner and modulating the wettability of the self-assembled monolayers.
基金financial support by the National Natural Science Foundation of China(Nos.21372192,21871227)the Priority Academic Program Development of Jiangsu Higher Education Institutions。
文摘The series of salen-bridged bis-pillar[1]arenes were conveniently prepared by condensation reaction of5,5'-methylenebis(2-hydroxybenzalde hyde)or 5,5'-(propane-2,2-diyl)bis(2-hydroxybenzaldehyde)with mono-amido-functionalized pillar[5]arenes containing different terminal aminoalkyl groups in refluxing ethanol.The^1H NMR and 2D-NOESY spectra indicated that the salen-bridged bis-pillar[5]arenes with longer allcylene linker(n=3,4,6)formed the fascinating bis-[1]rotaxanes,while the salenbridged bis-pillar[5]arenes with short hydrazine and ethylenediamino linker(n=0,2)predominately existed in free form.The single crystal structure of the bis-pillar[5]are ne ambiguously indicated that two propylenediamino linker inserted in to two cavities of pillar[5]arene to form a novel bis-[1]rotaxanes.
基金support from the National Natural Science Foundation of China(Nos.22122105 and22071152)Natural Science Foundation of Shanghai(No.22dz1207603)+4 种基金the Shuguang Program of Shanghai Education Development Foundation and the Shanghai Municipal Education Commission(No.22SG11)the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study(No.SN-ZJU-SIAS-006)L.Y.acknowledges the financial support from the National Natural Science Foundation of China(No.22305150)Z.Z.acknowledges the financial support from the National Natural Science Foundation of China(Nos.22101175 and 52333001)supported by State Key Laboratory of Polyolefins and Catalysis and Shanghai Key Laboratory of Catalysis Technology for Polyolefins(No.SKL-LCTP-202301)。
文摘Supramolecular polymer networks(SPNs)are celebrated for their dynamic nature,yet they often exhibit inadequate mechanical properties.Thus far,the quest to bolster the mechanical resilience of SPNs while preserving their dynamic character presents a formidable challenge.Herein,we introduce[2]rotaxane into SPN to serve as another cross-link,which could effectively enhance the mechanical robustness of the polymer network without losing the dynamic properties.Compared with SPN,the dually cross-linked network(DPN)demonstrates superior breaking strength,Young’s modulus,puncture force and toughness,underscoring its superior robustness.Furthermore,the cyclic tensile tests reveal that the energy dissipation capacity of DPN rivals,and in some cases surpasses,that of SPN,owing to the efficient energy dissipation pathway facilitated by[2]rotaxane.In addition,benefiting from stable topological structure of[2]rotaxane,DPN exhibits accelerated recovery from deformation,indicating superior elasticity compared to SPN.This strategy elevates the performance of SPNs across multiple metrics,presenting a promising avenue for the development of high-performance dynamic materials.
