Plasmonic Nanozymes: Engineered Gold Nanoparticles Exhibit Tunable Plasmon-Enhanced Peroxidase-Mimicking Activity

Abstract

Enzyme-mimicking inorganic nanoparticles, also known as nanozymes, have emerged as a rapidly expanding family of artificial enzymes that exhibit superior structural robustness and catalytic durability when serving as the surrogates of natural enzymes for widespread applications. However, the performance optimization of inorganic nanozymes has been pursued in a largely empirical fashion due to lack of generic design principles guiding the rational tuning of the nanozyme activities. Here we choose Au surface-roughened nanoparticles as a model plasmonic nanozyme that combines peroxidase-mimicking behaviors with tunable plasmonic characteristics to demonstrate the feasibility of fine-tuning nanozyme activities through plasmonic excitations using visible and near-infrared light sources. Taking full advantage of the unique plasmonic tunability offered by Au surface-roughened nanoparticles, we were able to unravel the detailed relationship between plasmonic excitations and nanozyme activities that underpins the hot electron-mediated working mechanism of peroxidase-mimicking plasmonic nanozymes.

Achieving enhanced peroxidase-like activity in multimetallic nanorattles

“…This can create an increase in the local concentration of OH radicals and therefore increase the reaction rate for the formation of oxTMB. 23,45,46 This hypothesis would support the significant enhancement of the NSs and NRs relative to the NPs and support the results in which the NSs are compared with the NRs. In the NSs, there was an increase in activity relative to the Au NPs due to nanoconfinement effects, a higher surface-to-volume ratio relative to the Au NPs enabled by the nanoshell/porous morphology, and the absence of citrate as the stabilizer.…”

“…The oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) was used to evaluate the catalytic performance ( peroxidase-like activity) of the Au NPs, AgAu NSs, or Au@AgAu NRs. 23 The oxidation reactions were carried out in 2 mL centrifuge tubes con-…”

“…Although these strategies have allowed for enhanced enzyme-mimicking performances relative to conventional Au NPs, it is clear that further improvements in activity are desperately still needed. [15][16][17][18][19] In this paper, we address this challenge by engineering NP morphologies to enable the combined optimization of several morphological features for the improved performances of Aubased nanozymes. We focus on multimetallic nanorattles (NRs) comprising an Au core inside a bimetallic AgAu shell, separated by a void (Au@AgAu NRs).…”

Micro‐Bio‐Chemo‐Mechanical‐Systems: Micromotors, Microfluidics, and Nanozymes for Biomedical Applications

“…[ 131 ] Optically active plasmonic nanozymes (AuNPs) exhibits enhanced peroxidase‐mimicking activity. [ 132 ] Nanozymes can also be endowed with multifunctional capability. Recently, experimentally derived multifunctional nanozyme based on MOFs, which contains catalytic Cu 2+ and luminescent Tb 3+ ions are also reported.…”

Modulating the catalytic activity of gold nanoparticles using amine-terminated ligands

“…[21][22][23] Few works have described phenomena such as self-catalysis and self-limiting activity of AuNPs, light-triggered plasmonic excitation of catalysis, electrostatic neutralization-controlled catalysis, molecular imprinting-induced selective catalysis, and metal ionassisted catalysis. [24][25][26][27][28][29][30] Our previous study demonstrated the self-catalyzed in situ deposition of AgNPs on surfaces of polydopamine-coated AuNPs. 31 The corona-like AgNPs@AuNP show spectral blue-shift and high activity.…”