Atomically-precise clusterzymes have been widely studied for their special physicochemical properties,but it is still a challenge to enhance their peroxidase-like activity.Herein,we demonstrated that by substituting a...Atomically-precise clusterzymes have been widely studied for their special physicochemical properties,but it is still a challenge to enhance their peroxidase-like activity.Herein,we demonstrated that by substituting a single Ag atom into Au25 nanoclusters to form Au_(24)Ag_(1) nanoclusters,the peroxidase-like activity was enhanced greatly.In the presence of H_(2)O_(2),Au_(24)Ag_(1) could produce reactive oxygen species(ROS)to oxidize colorless 3,3'5,5'-tetramethylbenzidine(TMB)to the blue oxidized TMB(oxTMB).It is worth mentioning that pyrophosphate compounds inhibit the activity of Au_(24)Ag_(1).Since alkaline phosphatase(ALP)can dephosphorylate the substrate phosphate compound,that is,remove the phosphate group on the substrate by hydrolysis,the enzymatic activity of the clusterzyme is restored.Based on this,we have developed a sensitive and reliable colorimetric sensing system for the detection of pyrophosphate ion(PPi),adenosine triphosphate(ATP),adenosine diphosphate(ADP)and ALP,respectively.Importantly,the detection limit of the assay system is lower than those of most of the assays that have been reported.In addition,we also built a simple optical logic gate on this basis,further extending the application of metal nanoclusters as peroxidase mimics in bioanalysis.This work could help to shed light on the structure-activity relationship of nanozyme.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22172063 and 32202145)the Fund of Young Taishan Scholar Program,China(No.tsqn201812080)+1 种基金the Natural Science Foundation of Shandong Province,China(No.ZR2019YQ10)the Independent Cultivation Program of Innovation Team of Ji’nan City,China(No.2021GXRC052).
文摘Atomically-precise clusterzymes have been widely studied for their special physicochemical properties,but it is still a challenge to enhance their peroxidase-like activity.Herein,we demonstrated that by substituting a single Ag atom into Au25 nanoclusters to form Au_(24)Ag_(1) nanoclusters,the peroxidase-like activity was enhanced greatly.In the presence of H_(2)O_(2),Au_(24)Ag_(1) could produce reactive oxygen species(ROS)to oxidize colorless 3,3'5,5'-tetramethylbenzidine(TMB)to the blue oxidized TMB(oxTMB).It is worth mentioning that pyrophosphate compounds inhibit the activity of Au_(24)Ag_(1).Since alkaline phosphatase(ALP)can dephosphorylate the substrate phosphate compound,that is,remove the phosphate group on the substrate by hydrolysis,the enzymatic activity of the clusterzyme is restored.Based on this,we have developed a sensitive and reliable colorimetric sensing system for the detection of pyrophosphate ion(PPi),adenosine triphosphate(ATP),adenosine diphosphate(ADP)and ALP,respectively.Importantly,the detection limit of the assay system is lower than those of most of the assays that have been reported.In addition,we also built a simple optical logic gate on this basis,further extending the application of metal nanoclusters as peroxidase mimics in bioanalysis.This work could help to shed light on the structure-activity relationship of nanozyme.
