Hydrazine Hydrate and Dissolved Oxygen-Triggered Near-Infrared Chemiluminescence from CuInS₂@ZnS Nanocrystals for Bioassays

Abstract

The overwhelming majority of commercially available chemiluminescence (CL) assays are conducted in the eye-visible region. Herein, a near-infrared (NIR) aqueous CL strategy was proposed with CuInS₂@ZnS nanocrystals (CIS@ZnS NCs) as emitters. Hydrazine hydrate (N₂H₄·H₂O) could inject electrons into the conduction band of the CIS@ZnS NCs and simultaneously transformed to the intermediate radical N₂H₃^•. N₂H₃^• reduced dissolved oxygen (O₂) to O₂^-•, while the O₂^-• could inject holes into the valence band of the CIS@ZnS NCs. The recombination of electrons and holes at Cu⁺ defects in CIS@ZnS NCs eventually yielded efficient NIR CL at around 824.1 nm, which is the longest waveband for NCs CL to the best of our knowledge. The NIR CL could be conveniently performed in the neutral aqueous medium (pH 7.0) with a quantum yield of 0.0155 Einstein/mol and was successfully employed for constructing a signal-off CL biosensor with ascorbic acid as the analyte as well as a signal-on CL biosensor for determining ascorbate oxidase, which indicates that this NIR CL system has a promising potential for bioassays in diverse ways.