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.