Enzymatic Behavior Regulation-Based Colorimetric and Electrochemiluminescence Sensing of Phosphate Using the Cobalt Oxyhydroxide Nanosheet.

In this work, a convenient and flexible assay for colorimetric and electrochemiluminescence (ECL) sensing of phosphate was proposed based on the enzymatic behavior regulation of the cobalt oxyhydroxide (CoOOH) nanosheet. CoOOH as a novel nanoenzyme exhibited a peroxidase-like activity, which could catalyze different substrates such as 2, 2'-azinobis-3-ethylbenzthiazoline-6-sulfonate (ABTS) and 4-chloro-1-naphthol (4-CN) with hydrogen peroxide (H2O2) as the electron acceptor. Phosphate could specifically regulate the enzymatic behavior of the CoOOH nanosheet via the deactivating effect. A high level of phosphate enabled a weak color change of ABTS, which offered a "turn-off" model of the colorimetric assay with a limit of detection of 0.673 μM. Based on the similar enzymatic behavior, this strategy could then be applied in the ECL assay utilizing l-arginine-6-aza-2-thiothymine-protected gold nanoclusters (Arg-ATT-AuNCs) as ECL signal indicators. Specifically, 4-CN was catalyzed to generate the precipitate and lead to the quenching on ECL emission. Different from colorimetric behavior, phosphate with a high concentration could induce strong ECL performance, which enabled the "turn-on" model of the ECL assay with a more sensitive determination down to 0.434 nM. This flexible enzymatic behavior regulation could then allow the phosphate measurement in environmental samples including tap water and river water with satisfactory accuracy, which holds the potential in the field of environmental protection.