DNAzyme-Based Plasmonic Nanomachine for Ultrasensitive Selective Surface-Enhanced Raman Scattering Detection of Lead Ions via a Particle-on-a-Film Hot Spot Construction

We propose a highly sensitive and selective surface-enhanced Raman scattering (SERS) method for determining lead ions based on a DNAzyme-linked plasmonic nanomachine. A metallic nanoparticle-on-a-film structure was built through a rigid double-stranded bridge linker composed of a DNAzyme and its substrate. This DNAzyme could be activated by lead ions and catalyze a fracture action of the substrate. Thus, the double chain structure of DNA would turn into a flexible single strand, making the metal nanoparticles that connected to the terminal of DNAzyme fall to the surface of the metal film. Hereby, a narrow gap close to 2 nm generated between metal nanoparticles and the metal film, exhibiting a similar effect of a hot spot and remarkably enhancing the signal of randomly dispersed Raman-active molecules on the surface of metal film. By measuring the improvement of SERS intensity of the Raman-active molecules, we realized the lowest detection concentration of Pb2+ ions to 1.0 nM. This SERS analytical method is highly selective and can be extended universally to other targets via the accurate programming of corresponding DNA sequences.