University of Helsinki, Department of Chemistry, A.I. Virtasen aukio 1, Helsinki, Finland.
University of Georgia, Georgia Electron Microscopy, Athens, Georgia 30602, USA.
Dalton Trans. 2022 Oct 11;51(39):15133-15141. doi: 10.1039/d2dt02389j.
Gold nanoparticles (Au NPs) have been extensively used as artificial enzymes, but their performance is still limited. We address this challenge by focusing on multimetallic nanorattles comprising an Au core inside a bimetallic AgAu shell, separated by a void (Au@AgAu NRs). They were prepared by a galvanic replacement approach and contained an ultrathin and porous shell comprising an AgAu alloy. By investigating the peroxide-like activity using TMB oxidation as a model transformation, we have found an increase of 152 fold in activities for the NRs relative to conventional Au NPs. Based on the kinetics results, the NRs also showed the lowest , indicating better interaction with the substrate and faster product formation. We also observed a linear relationship between the concentration of the product and oxTMB as a function of HO concentration, which could be further applied for HO sensing applications (colorimetric detection). These data suggest that the NRs enable the combined effect of an increased surface area relative to solid counterparts, the possibility of exposing highly active surface sites, and the exploitation of nanoconfinement effects due to the void regions between the core and shell components. These results provide important insights into the optimization of peroxidase-like performances beyond what can be achieved in conventional NPs and may inspire the development of better-performing artificial enzymes.
金纳米颗粒(Au NPs)已被广泛用作人工酶,但它们的性能仍受到限制。我们通过专注于由 Au 核和双金属 AgAu 壳组成的多金属纳米笼(Au@AgAu NRs)来解决这一挑战,这些纳米笼通过电置换方法制备而成,内部有一个由 AgAu 合金组成的超薄多孔壳。通过使用 TMB 氧化作为模型转化来研究过氧化物样活性,我们发现 NRs 的活性相对于传统的 Au NPs 增加了 152 倍。基于动力学结果,NRs 还表现出最低的 ,这表明与底物的相互作用更好,产物形成更快。我们还观察到产物浓度与 oxTMB 之间存在线性关系,作为 HO 浓度的函数,这可进一步应用于 HO 传感应用(比色检测)。这些数据表明,NRs 能够实现相对于固体对应物的表面积增加、暴露高活性表面位点的可能性,以及由于核和壳组件之间的空隙区域而产生的纳米限域效应的综合效应。这些结果为超越传统 NPs 所能实现的过氧化物酶样性能的优化提供了重要的见解,并可能激发更好的人工酶的开发。