Recently,reactive oxygen species(ROS)-independent mimetics of oxidase with Au nanoclusters(NCs)as the catalysts and MnO_(2)as electron acceptor have gained attention.In this study,we aim to explore the oxidase-mimicki...Recently,reactive oxygen species(ROS)-independent mimetics of oxidase with Au nanoclusters(NCs)as the catalysts and MnO_(2)as electron acceptor have gained attention.In this study,we aim to explore the oxidase-mimicking potential of bovine serum albumin(BSA)-templated metal nanoclusters(BSA-M NCs,where M=Ag,Pt,Cu,or Cd)beyond Au NCs in boosting the oxidation of 3,3',5,5'-tetramethylbenzidine(TMB)by MnO_(2),denoted as BM@Metal.The oxidase-mimetic activity of BM@Metal is independent of ROS and generally enhanced by the incorporation of metal nanoclusters.Notably,this enhancement varies with the metal species,with BSA-Cd exhibiting the highest activity.The X-ray photoelectron spectroscopy(XPS)analysis confirms mixed valence states(Mn(Ⅳ)/Mn(Ⅱ))in BM@Cd.Given that the catalytic activity is closely linked to the substrate adsorption,the label-free isothermal titration calorimetry was employed to probe the affinity between TMB and BSA-M NCs,which provides a robust approach for probing the interface adsorption.The results reveal that the superior catalytic performance of BSA-Cd correlates with enhanced TMB adsorption,likely facilitated by coordination and hydrophobic interactions.Finally,the superior catalytic performance of BSA-M NCs on the oxidation of TMB by MnO_(2)has inspired us to fabricate the assay for analyzing α-glucosidase’s activity.This work not only demonstrates the versatility of metal NCs in constructing ROS-independent oxidase mimetics but also provides interfacial adsorption engineered strategy for the rational design of superior ROS independent mimetics of natural oxidase.展开更多
基金the financial support from the National Natural Science Foundation of China(Nos.22073025,21603067,and U23A2089)the Program of Science and Technology Plan of the City of Tianjin(No.24JRRCRC00040)+1 种基金Opening Fund of Hubei Key Laboratory of Bioinorganic Chemistry&Materia Medica(No.BCMM202507)the Open Fund of Hubei Key Laboratory of Resources and Chemistry of Chinese Medicine(No.KLRCCM2404).
文摘Recently,reactive oxygen species(ROS)-independent mimetics of oxidase with Au nanoclusters(NCs)as the catalysts and MnO_(2)as electron acceptor have gained attention.In this study,we aim to explore the oxidase-mimicking potential of bovine serum albumin(BSA)-templated metal nanoclusters(BSA-M NCs,where M=Ag,Pt,Cu,or Cd)beyond Au NCs in boosting the oxidation of 3,3',5,5'-tetramethylbenzidine(TMB)by MnO_(2),denoted as BM@Metal.The oxidase-mimetic activity of BM@Metal is independent of ROS and generally enhanced by the incorporation of metal nanoclusters.Notably,this enhancement varies with the metal species,with BSA-Cd exhibiting the highest activity.The X-ray photoelectron spectroscopy(XPS)analysis confirms mixed valence states(Mn(Ⅳ)/Mn(Ⅱ))in BM@Cd.Given that the catalytic activity is closely linked to the substrate adsorption,the label-free isothermal titration calorimetry was employed to probe the affinity between TMB and BSA-M NCs,which provides a robust approach for probing the interface adsorption.The results reveal that the superior catalytic performance of BSA-Cd correlates with enhanced TMB adsorption,likely facilitated by coordination and hydrophobic interactions.Finally,the superior catalytic performance of BSA-M NCs on the oxidation of TMB by MnO_(2)has inspired us to fabricate the assay for analyzing α-glucosidase’s activity.This work not only demonstrates the versatility of metal NCs in constructing ROS-independent oxidase mimetics but also provides interfacial adsorption engineered strategy for the rational design of superior ROS independent mimetics of natural oxidase.
