Constructing high-performance nanozymes for specific biomolecules is crucial but challenging for practical applications and fundamental research.Herein,through the examination of the catalytic reaction paths of natura...Constructing high-performance nanozymes for specific biomolecules is crucial but challenging for practical applications and fundamental research.Herein,through the examination of the catalytic reaction paths of natural nicotinamide adenine dinucleotide(NADH)oxidase(NOX),a novel and efficient single-atom rhodium catalyst(Rh1/NC)was developed to mimic NOX.The Rh_(1)/NC demonstrated the ability to catalyze the dehydrogenation of NADH and transfer electrons to O_(2)to generate H_(2)O_(2)through the typical two-electron pathway.Furthermore,our findings revealed that Rh_(1)/NC exhibits the ability to catalyze the conversion of produced H_(2)O_(2)into OH under mildly acidic conditions.This process amplifies the oxidation of NADH,showcasing NADH peroxidase-like activity(NPx-like).As a paradigm,this unique dual enzyme-like property of Rh_(1)/NC with a positive feedback effect holds significance in disrupting cancer cellular homeostasis.Rh_(1)/NC can effectively consume NADH via cascade biocatalytic reactions within cancer cells,further triggering the elevation of reactive oxygen species(ROS),leading to impaired oxidative phosphorylation and decreased mitochondrial membrane potential,thus damaging the adenosine triphosphate(ATP)synthesis.The resulting'domino effect'interferes with the energy metabolism homeostasis of cancer cells,ultimately promoting cell apoptosis.This study provides potential guidance for the rational design of materials with greater capabilities.展开更多
Photodynamic therapy(PDT)has received much attention in recent years.However,traditional photosensitizers(PSs)applied in PDT usually suffer from aggregation-caused quenching(ACQ)effect in H_(2)O,single and inefficient...Photodynamic therapy(PDT)has received much attention in recent years.However,traditional photosensitizers(PSs)applied in PDT usually suffer from aggregation-caused quenching(ACQ)effect in H_(2)O,single and inefficient photochemical mechanism of action(MoA),poor cancer targeting ability,etc.In this work,two novel Ru(II)-based aggregation-induced emission(AIE)agents(Ru1 and Ru2)were developed.Both complexes exhibited long triplet excited lifetimes and nearly 100%singlet oxygen quantum yields in H_(2)O.In addition,Ru1 and Ru2 displayed potent photo-catalytic reduced nicotinamide adenine dinucleotide(NADH)oxidation activity with turnover frequency(TOF)values of about 1779 and 2000 h^(−1),respectively.Therefore,both Ru1 and Ru2 showed efficient PDT activity towards a series of cancer cells.Moreover,Ru2 was further loaded in bovine serum albumin(BSA)to enhance the tumor targeting ability in vivo,and the obtained Ru2@BSA could selectively accumulate in tumor tissues and effectively inhibit tumor growth on a 4T1 tumor-bearing mouse model.So far as we know,this work represents the first report about Ru(Ⅱ)-)AIE agents that possess high singlet oxygen quantum yields and also potent photocatalytic NADH oxidation activity,and may provide new ideas for rational design of novel PSs with efficient PDT activity.展开更多
基金financially supported by the National Natural Science Foundation of China(No.22207066)Taishan Scholars Program of Shandong Province(No.TS201712065)+2 种基金the Academic Promotion Program of Shandong First Medical University(No.2019QL009)the Science and Technology Funding from Jinan(No.2020GXRC018)the Traditional Chinese Medicine Science and Technology Project of Shandong Province(No.Q-2022142)。
文摘Constructing high-performance nanozymes for specific biomolecules is crucial but challenging for practical applications and fundamental research.Herein,through the examination of the catalytic reaction paths of natural nicotinamide adenine dinucleotide(NADH)oxidase(NOX),a novel and efficient single-atom rhodium catalyst(Rh1/NC)was developed to mimic NOX.The Rh_(1)/NC demonstrated the ability to catalyze the dehydrogenation of NADH and transfer electrons to O_(2)to generate H_(2)O_(2)through the typical two-electron pathway.Furthermore,our findings revealed that Rh_(1)/NC exhibits the ability to catalyze the conversion of produced H_(2)O_(2)into OH under mildly acidic conditions.This process amplifies the oxidation of NADH,showcasing NADH peroxidase-like activity(NPx-like).As a paradigm,this unique dual enzyme-like property of Rh_(1)/NC with a positive feedback effect holds significance in disrupting cancer cellular homeostasis.Rh_(1)/NC can effectively consume NADH via cascade biocatalytic reactions within cancer cells,further triggering the elevation of reactive oxygen species(ROS),leading to impaired oxidative phosphorylation and decreased mitochondrial membrane potential,thus damaging the adenosine triphosphate(ATP)synthesis.The resulting'domino effect'interferes with the energy metabolism homeostasis of cancer cells,ultimately promoting cell apoptosis.This study provides potential guidance for the rational design of materials with greater capabilities.
基金supported by National Natural Science Foundation of China(NSFC,No.22371289).
文摘Photodynamic therapy(PDT)has received much attention in recent years.However,traditional photosensitizers(PSs)applied in PDT usually suffer from aggregation-caused quenching(ACQ)effect in H_(2)O,single and inefficient photochemical mechanism of action(MoA),poor cancer targeting ability,etc.In this work,two novel Ru(II)-based aggregation-induced emission(AIE)agents(Ru1 and Ru2)were developed.Both complexes exhibited long triplet excited lifetimes and nearly 100%singlet oxygen quantum yields in H_(2)O.In addition,Ru1 and Ru2 displayed potent photo-catalytic reduced nicotinamide adenine dinucleotide(NADH)oxidation activity with turnover frequency(TOF)values of about 1779 and 2000 h^(−1),respectively.Therefore,both Ru1 and Ru2 showed efficient PDT activity towards a series of cancer cells.Moreover,Ru2 was further loaded in bovine serum albumin(BSA)to enhance the tumor targeting ability in vivo,and the obtained Ru2@BSA could selectively accumulate in tumor tissues and effectively inhibit tumor growth on a 4T1 tumor-bearing mouse model.So far as we know,this work represents the first report about Ru(Ⅱ)-)AIE agents that possess high singlet oxygen quantum yields and also potent photocatalytic NADH oxidation activity,and may provide new ideas for rational design of novel PSs with efficient PDT activity.
