Block-Polymer-Restricted Sub-nanometer Pt Nanoclusters Nanozyme-Enhanced Immunoassay for Monitoring of Cardiac Troponin I

Noble-metal nanozymes have demonstrated great potential in various fields. However, aggregation of single-particle nanoparticles severely affects their exposed catalytically active sites to the extent of exhibiting weak enzyme-like activity. Here, we present an organic block surfactant (polyvinylpyrrolidone, PVP) to construct monodisperse water-stable Pt nanoclusters (Pt NCs) for an enhanced immunoassay of cardiac troponin I (cTnI). The PVP-modified Pt NC nanozyme exhibited up to 16.3 U mg –1 peroxidase-mimicking activity, which was mainly attributed to the ligand modification on the surface and the electron-absorbing effect of the ligand on the Pt NCs. The PVP-modified Pt NCs have a lower OH-transition potential, as determined by density functional theory. Under optimized experimental conditions, the enhanced nanozyme immunoassay strategy exhibited an ultrawide dynamic response range of 0.005–50 ng mL –1 for cTnI targets with a detection limit of 1.3 pg mL –1, far superior to some reported test protocols. This work provides a designable pathway for the design of artificial enzymes with high enzyme-like activity to further expand the practical range of enzyme alternatives.