{"title":"配体介导的不对称二铜位点用于稳健的儿茶酚酶模拟催化和选择性传感","authors":"Bojin Li, Meng Yuan, Nan Nan Xia, Xun Hu, Fei He","doi":"10.1039/d5sc05472a","DOIUrl":null,"url":null,"abstract":"Fabricating dicopper centers in nanozymes offered a promising route to mimic catecholase-like catalysis. However, some dicopper centers often suffered from symmetric configurations, which was prone to weaken the O-O bond polarization, thereby limiting O<small><sub>2</sub></small> activation. This resulted in the unsatisfied intrinsic activities of nanozymes, thus hindering their potential sensing applications. Here, we reported a CO-like nanozyme (DTD-Cu) engineered with proximal and asymmetrically coordinated dicopper centers via a N/S-rich ligand. The unique asymmetric N<small><sub>4</sub></small>Cu-CuN<small><sub>4</sub></small>S configuration facilitated the preferential O<small><sub>2</sub></small> adsorption/activation and the O-O bond polarization as well as subsequent 4-electron reduction to H<small><sub>2</sub></small>O via a H<small><sub>2</sub></small>O<small><sub>2</sub></small> intermediate, thus endowing DTD-Cu with dramatically enhanced intrinsic activity, as evidenced by orders-of-magnitude improvements in K<small><sub>m</sub></small> and K<small><sub>cat</sub></small>/K<small><sub>m</sub></small> over most reported CO-like nanozymes and artificial enzymes. Capitalizing on this superior activity, we achieved highly selective and sensitive detection of the cytotoxic tris(2-carboxyethyl)phosphine (TCEP) with a detection limit of 98.6 ppb via a synergistic dual-inhibition mechanism involving both TCEP-induced reduction of the oxidized substrate/ROS and direct TCEP-dominated chelation to the Cu sites.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"95 2 1","pages":""},"PeriodicalIF":7.4000,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Ligand-mediated asymmetric dicopper sites for robust catecholase-mimicking catalysis and selective sensing\",\"authors\":\"Bojin Li, Meng Yuan, Nan Nan Xia, Xun Hu, Fei He\",\"doi\":\"10.1039/d5sc05472a\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Fabricating dicopper centers in nanozymes offered a promising route to mimic catecholase-like catalysis. However, some dicopper centers often suffered from symmetric configurations, which was prone to weaken the O-O bond polarization, thereby limiting O<small><sub>2</sub></small> activation. This resulted in the unsatisfied intrinsic activities of nanozymes, thus hindering their potential sensing applications. Here, we reported a CO-like nanozyme (DTD-Cu) engineered with proximal and asymmetrically coordinated dicopper centers via a N/S-rich ligand. The unique asymmetric N<small><sub>4</sub></small>Cu-CuN<small><sub>4</sub></small>S configuration facilitated the preferential O<small><sub>2</sub></small> adsorption/activation and the O-O bond polarization as well as subsequent 4-electron reduction to H<small><sub>2</sub></small>O via a H<small><sub>2</sub></small>O<small><sub>2</sub></small> intermediate, thus endowing DTD-Cu with dramatically enhanced intrinsic activity, as evidenced by orders-of-magnitude improvements in K<small><sub>m</sub></small> and K<small><sub>cat</sub></small>/K<small><sub>m</sub></small> over most reported CO-like nanozymes and artificial enzymes. Capitalizing on this superior activity, we achieved highly selective and sensitive detection of the cytotoxic tris(2-carboxyethyl)phosphine (TCEP) with a detection limit of 98.6 ppb via a synergistic dual-inhibition mechanism involving both TCEP-induced reduction of the oxidized substrate/ROS and direct TCEP-dominated chelation to the Cu sites.\",\"PeriodicalId\":9909,\"journal\":{\"name\":\"Chemical Science\",\"volume\":\"95 2 1\",\"pages\":\"\"},\"PeriodicalIF\":7.4000,\"publicationDate\":\"2025-10-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemical Science\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d5sc05472a\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Science","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d5sc05472a","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Ligand-mediated asymmetric dicopper sites for robust catecholase-mimicking catalysis and selective sensing
Fabricating dicopper centers in nanozymes offered a promising route to mimic catecholase-like catalysis. However, some dicopper centers often suffered from symmetric configurations, which was prone to weaken the O-O bond polarization, thereby limiting O2 activation. This resulted in the unsatisfied intrinsic activities of nanozymes, thus hindering their potential sensing applications. Here, we reported a CO-like nanozyme (DTD-Cu) engineered with proximal and asymmetrically coordinated dicopper centers via a N/S-rich ligand. The unique asymmetric N4Cu-CuN4S configuration facilitated the preferential O2 adsorption/activation and the O-O bond polarization as well as subsequent 4-electron reduction to H2O via a H2O2 intermediate, thus endowing DTD-Cu with dramatically enhanced intrinsic activity, as evidenced by orders-of-magnitude improvements in Km and Kcat/Km over most reported CO-like nanozymes and artificial enzymes. Capitalizing on this superior activity, we achieved highly selective and sensitive detection of the cytotoxic tris(2-carboxyethyl)phosphine (TCEP) with a detection limit of 98.6 ppb via a synergistic dual-inhibition mechanism involving both TCEP-induced reduction of the oxidized substrate/ROS and direct TCEP-dominated chelation to the Cu sites.
期刊介绍:
Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.