Selectively Controlled AuNP Superstructure Hierarchical Assembly by DNAzyme Catalysis

Gold nanoparticles (AuNPs) have become a promising assembly material for exploring and understanding physicochemical mechanisms in vitro and in vivo. Recent reports of AuNP superstructure assembly methods with conditional manipulation features usually require specific physicochemical triggering conditions and macroscopic control of the whole reaction system, thus lacking simple and selective regulation of the assemblies of the AuNP superstructure. In this study, a DNAzyme‐based method is developed to program selectively controlled hierarchical assembly of AuNP superstructures. In which the DNAzyme‐catalyzed network enabled the selective manipulation of the generation of different AuNP superstructures by programming the activation of local subsystems. First, the programming manipulation of AuNP superstructure assembly is demonstrated using four kinds of circuit programs (YES, AND, OR, and Cascade). Then, a selectively controlled superstructure cascade assembly platform is established by merging two independent cascade subsystems, utilized to achieve on‐demand manipulation of the three superstructure assembly states. This work provides a simple and selective tool to simultaneously manipulate the hierarchical assembly of multiple nanoparticle superstructures for applications such as dynamic nanomachines and medical sensing.