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

IF 7.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Bojin Li, Meng Yuan, Nan Nan Xia, Xun Hu, Fei He
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引用次数: 0

摘要

在纳米酶中制造二铜中心为模拟儿茶酚酶样催化提供了一条有前途的途径。然而,一些迪铜中心往往存在对称构型,这容易削弱O-O键的极化,从而限制了O2的活化。这导致纳米酶的内在活性不理想,从而阻碍了其潜在的传感应用。在这里,我们报道了一种co样纳米酶(DTD-Cu),它通过富氮/硫配体具有近端和不对称协调的铜中心。独特的不对称N4Cu-CuN4S结构有利于O2的优先吸附/活化和O-O键极化,以及随后通过H2O2中间体将4电子还原为H2O,从而使td - cu具有显著增强的内在活性,Km和Kcat/Km比大多数报道的CO-like纳米酶和人工酶提高了数量级。利用这一优越的活性,我们实现了对细胞毒性三(2-羧基乙基)膦(TCEP)的高选择性和高灵敏度检测,检测限为98.6 ppb,通过协同双重抑制机制,包括TCEP诱导氧化底物/ROS的还原和TCEP主导的直接螯合到Cu位点。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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.
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来源期刊
Chemical Science
Chemical Science CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
14.40
自引率
4.80%
发文量
1352
审稿时长
2.1 months
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.
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