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
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.
