Organometallic nanozymes, organometallics of which mimic the cofactor of natural enzymes, have the advantages of tunable catalytic activity, high stability, and material variety. By assembling organometallics (catalytic site) on inorganic nanoparticles (support), organometallic nanozymes have been rationally designed, but modulating their assembly and activity remains a tough challenge. Here, we construct a photo-modulated organometallic nanozyme by anchoring azobenzene-modified triethylenetetramine (Azo-N4) to the surface of β-cyclodextrin-capped gold nanoparticles (AuNP@CDs) through host–guest interaction, followed by Zn(II) coordination to form organometallics. The catalytic site derives from the outer organometallic layer. The nanozyme catalyzes the hydrolysis of 4-nitrophenyl acetate to 4-nitrophenol and the catalytic signal is used to detect Zn(II). Due to the photoisomerization of azobenzene, the supramolecular assembly of host–guest interaction is modulated by light. The disassembly leads to cascade catalysis of AuNP@CDs-Azo-N4-Zn and the recovery of AuNP@CDs. Our study provides a new idea and reference for the rational design and activity modulation of organometallic nanozymes.

中文翻译：

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基于β-环糊精封端金纳米颗粒的光调制有机金属纳米酶，用于检测 Zn(II) 和级联催化


有机金属纳米酶是模仿天然酶辅因子的有机金属化合物，具有催化活性可调、稳定性高、材料多样等优点。通过在无机纳米粒子（载体）上组装有机金属（催化位点），有机金属纳米酶已被合理设计，但调节其组装和活性仍然是一个艰巨的挑战。在这里，我们通过主客体相互作用将偶氮苯修饰的三乙烯四胺（Azo-N4）锚定到β-环糊精封端的金纳米颗粒（AuNP@CDs）表面，然后进行Zn（II）配位，构建了光调制的有机金属纳米酶形成有机金属化合物。催化位点来自外部有机金属层。该纳米酶催化4-硝基苯乙酸酯水解为4-硝基苯酚，并利用催化信号检测Zn(II)。由于偶氮苯的光致异构化，主客体相互作用的超分子组装受到光的调节。分解导致 AuNP@CDs-Azo-N4-Zn 的级联催化和 AuNP@CDs 的回收。我们的研究为有机金属纳米酶的合理设计和活性调控提供了新的思路和参考。