Three-in-One: Sensing, Self-Assembly, and Cascade Catalysis of Cyclodextrin Modified Gold Nanoparticles

We herein present a three-in-one nanoplatform for sensing, self-assembly, and cascade catalysis, enabled by cyclodextrin modified gold nanoparticles (CD@AuNPs). Monodisperse AuNPs 15-20 nm in diameter are fabricated in an eco-friendly way by the proposed one-step colloidal synthesis method using CD as both reducing agents and stabilizers. First, the as-prepared AuNPs are employed as not only scaffolds but energy acceptors for turn-on fluorescent sensing based on guest replacement reaction. Then, the macrocyclic supramolecule functionalized AuNPs can be controllably assembled and form well-defined one- and two-dimensional architectures using tetrakis(4-carboxyphenyl)porphyrin as mediator. Finally, in addition to conventional host-guest interaction based properties, the CD@AuNPs possess unpredictable catalytic activity and exhibit mimicking properties of both glucose oxidase and horseradish peroxidase simultaneously. Especially, the cascade reaction (glucose is first catalytically oxidized and generates gluconic acid and H₂O₂; then the enzymatic H₂O₂ and preadded TMB (3,3',5,5'-tetramethylbenzidine) are further catalyzed into H₂O and oxTMB, respectively) is well-achieved using the AuNPs as the sole catalyst. By employing a joint experimental-theoretical study, we reveal that the unique catalytic properties of the CD@AuNPs probably derive from the special topological structures of CD molecules and the resulting electron transfer effect from the AuNP surface to the appended CD molecules.