Engineering Nanozymes Using DNA for Catalytic Regulation

Abstract

DNA treatment of metal nanoparticles provides a potent tool for tuning their native properties and constructing advanced materials. However, there have been limited studies on interactions between DNA and nanomaterial-based artificial enzymes (nanozymes) to influence their intrinsic peroxidase-like properties. Here, we present the utilization of DNA as a capping ligand to engineer various bio-nanointerfaces for high-precise and adjustable regulation of catalytic behaviors of nanozymes toward the oxidation of substrates. The treatment of stiff double-stranded DNA only induced a negligible enhancement of the catalytic activity of nanozymes, and both coil-like single-stranded DNA and hairpin DNA-capped nanoparticles produced a medium signal increase. Interestingly, hybridization chain reaction (HCR) product-treated nanoparticles showed the highest peroxidase-like activities among four DNA structures. Furthermore, significant parameters that influence HCR process and the modulation of catalysis, such as the concentration of the hairpin DNA, the ionic strength, and the amount of nanozyme, were also systematically investigated. On the basis of HCR amplification and iron oxide (Fe 3 O 4 ) nanoparticles, we develop a simple, fast, label-free, and sensitive colorimetric strategy for sensing of a Yersinia pestis-relevant DNA sequence with a detection limit as low as 100 pM as well as single nucleotide polymorphism discrimination. These results highlight DNA engineering as a facile strategy to regulate the catalytic activities of nanozymes and understand the interactions between metallic nanoparticles and nucleic acids for biosensing applications.

Tuning Atomically Dispersed Fe Sites in Metal–Organic Frameworks Boosts Peroxidase-Like Activity for Sensitive Biosensing

“…Recently, nanozymes, a series of nanomaterials with enzyme-mimicking characteristics, have been selected as the substitutes for natural enzymes and applied in various fields because of their high stability, low-cost and mass production [7][8][9][10][11]. However, the catalytic activities of nanozymes are still much lower than those of natural enzymes [12][13][14]. Given the electronic and geometrical structures of enzymes are two key factors toward catalytic activities, accurately designing and tuning the electronic and geometrical structure of active sites at the atomic scale are important for the development of advanced nanozymes [15][16][17][18].…”

Engineering Biofunctional Enzyme‐Mimics for Catalytic Therapeutics and Diagnostics

“…Synthetic polymers, such as polyethylene glycol (PEG), [ 220 ] polycaprolactones, [ 221 ] dextrans, [ 222 ] chitosan, [ 223 ] hyperbranched polyglycerol, [ 224,225 ] polyethyleneimine (PEI), [ 226 ] and amphiphilic lipid‐PEG, [ 227 ] are typically organic polymers used in inorganic nanoparticles surface‐modifications via “grafting to” method or “grafting from” method. [ 228–233 ] Besides, series of macromolecules (such as DNA, [ 234 ] proteins [ 235,236 ] ) can also be anchored onto the surface of Enz‐Ms via electrostatic adsorption, hydrophobic interaction, hydrogen bond formation, and molecular coordination. One could suppose that the regulation effects of macromolecular and the catalytic effects of Enz‐Ms are interdependent.…”

First-principles study of the surface structure and stability of BC5

“…The surface structure and properties is of great importance for various applications, such as catalysis and growth of nanoparticle [29][30][31][32]. For all considered low-index surfaces, we first identify the most stable termination of each surface.…”