Oligonucleotide-Functionalized Enzymes Chemisorbing on Magnetic Layered Double Hydroxides: A Multimodal Catalytic Platform with Boosted Activity for Ultrasensitive Glucose Detection

Abstract

A reasonable design of multifarious chemo- and biocatalytic functions within individual nano/microunits is urgently desired for high-performance cascade reactions but has heretofore remained elusive. Herein, glucose oxidase was functionalized with oligonucleotides and steadily chemisorbed on magnetic layered double hydroxides (mLDHs) to construct a multimodal catalytic platform for realizing divergent reactions with heterogeneous and biocatalytic steps. The flowerlike mLDHs served both as an enzyme support and a peroxidase mimic cooperating with enzymes for tandem catalysis. Oligo-DNA connected the enzymes to mLDHs like a bridge, and a stepwise ligand-exchange-assisted coordination mechanism was proposed to explain the robust interaction between DNA and mLDHs. More importantly, DNA significantly improved the bioactivity of the whole system. The acceleration mechanism was attributed to the diffusion tunnels for the substrate/product and enhanced substrates binding on mLDHs. The multimodal catalytic platform was applied for colorimetric and electrochemical sensing of glucose with a low limit of detection and high selectivity. The practical analysis capability of the ultrasensitive sensor was evaluated by detecting glucose in human serum and sweat, showing reliable results, satisfactory recovery, and excellent stability. The strategy of combining mLDHs and enzymes for cascade catalysis provides a universal approach to prepare chemo-enzyme hybrids with high performance, which holds great promise for applications in biosensors and industrial catalysis.