Metal-organic frameworks(MOFs)are a promising type of candidate for mimicking natural enzymes,where ligands play an important role,but are rarely considered.This work proves that the ligand 2-aminoterephthalic acid(AT...Metal-organic frameworks(MOFs)are a promising type of candidate for mimicking natural enzymes,where ligands play an important role,but are rarely considered.This work proves that the ligand 2-aminoterephthalic acid(ATA)with photoresponsive oxidase-like activity could catalyze the substrate 3,3’,5,5’-tetramethylbenzidine(TMB)to form blue oxTMB under ultraviolet light illumination,and the oxidation reaction could be initiated,suspended,or terminated by light control,ensuring the precision of the spatial and temporal resolution.The presumable mechanism of enzyme-like activity is demonstrated to be relevant to the formation of superoxide radicals(O_(2)^(•−))by photogenerated electron transfer.However,once Cu^(2+)ions are added to the ATA catalytic chromogenic system,the photooxidase-like activity of ATA could be inhibited due to the electron transfer and the formation of Cu-MOF,establishing a photoresponsive colorimetric sensor of Cu^(2+).In light of the role of ATA as a ligand in the MOF synthesis and the unique characteristics of MOFs,this paper reports an aluminum-based MOF made of ATA(Al-ATA),which has no oxidase-mimicking activity under dark conditions but shows photooxidase-like activity,confirming the importance of light for enzyme mimicking activity and throwing light on the exploration of the construction of ATA-based MOFs(ATA-MOFs)with photocontrollable oxidase mimicking activity as well as the possible photocatalytic mechanism of the MOFs.展开更多
基金the National Science Foundation of China(21675127,31901794)the National Postdoctoral Program for Innovative Talents(BX20180263)+4 种基金the China Postdoctoral Science Foundation(2018M641026)the Shaanxi Provincial Science Fund for Distinguished Young Scholars(2018JC-011)the Young Talent Fund of University Association for Science and Technology in Shaanxi,China(2019-02-03)the Key Research and Development Program of Shaanxi Province(2019NY-111)the Tang Scholar by Cyrus Tang Foundation.
文摘Metal-organic frameworks(MOFs)are a promising type of candidate for mimicking natural enzymes,where ligands play an important role,but are rarely considered.This work proves that the ligand 2-aminoterephthalic acid(ATA)with photoresponsive oxidase-like activity could catalyze the substrate 3,3’,5,5’-tetramethylbenzidine(TMB)to form blue oxTMB under ultraviolet light illumination,and the oxidation reaction could be initiated,suspended,or terminated by light control,ensuring the precision of the spatial and temporal resolution.The presumable mechanism of enzyme-like activity is demonstrated to be relevant to the formation of superoxide radicals(O_(2)^(•−))by photogenerated electron transfer.However,once Cu^(2+)ions are added to the ATA catalytic chromogenic system,the photooxidase-like activity of ATA could be inhibited due to the electron transfer and the formation of Cu-MOF,establishing a photoresponsive colorimetric sensor of Cu^(2+).In light of the role of ATA as a ligand in the MOF synthesis and the unique characteristics of MOFs,this paper reports an aluminum-based MOF made of ATA(Al-ATA),which has no oxidase-mimicking activity under dark conditions but shows photooxidase-like activity,confirming the importance of light for enzyme mimicking activity and throwing light on the exploration of the construction of ATA-based MOFs(ATA-MOFs)with photocontrollable oxidase mimicking activity as well as the possible photocatalytic mechanism of the MOFs.
