Porous Oxyhydroxide Derived from Metal-Organic Frameworks as Efficient Triphosphatase-like Nanozyme for Chromium(III) Ion Colorimetric Sensing.

Abstract

The dephosphorylation that involves the removal of a phosphate group from a substrate molecule plays a significant role in living organisms. An enzyme mimic (nanozyme) with phosphatase-like catalytic activity has recently received attention in terms of its capacity for dephosphorylation. In this study, three types of highly porous oxyhydroxide with remarkable triphosphatase-like catalytic activities, ZrOOH, GdOOH, and HfOOH, have been prepared through the transformation of metal-organic frameworks (MOFs) using a simple alkaline hydrolysis method. The triphosphatase mimetic activities of ZrOOH, GdOOH, and HfOOH were then thoroughly investigated and verified. In particular, an isotopic tracing experiment revealed that abundant surface hydroxyls could serve as nucleophilic agents to directly attack the electropositive phosphorus atom, causing the cleavage of the terminal phosphoester bonds of phosphoester substrate molecules. The kinetic analysis provided calculated values of Km of 105.7, 90.5, and 46.1 μM, while the Vmax values were 3.57, 4.76, and 2.74 × 10-8 M s-1 and Ea values were estimated to be 47.52, 41.15, and 52.79 kJ/mol for ZrOOH, GdOOH, and HfOOH, respectively. The chromium(III) ions acting as "poisoning" inhibitors efficiently downregulated the triphosphatase mimetic activity of GdOOH. On the basis of this effect, a colorimetric chromium(III) ion-sensing system was explored, which provided a relevant linear response range for the detection of chromium(III) ions of 5.0-200 μM and a low detection limit of 0.84 μM. This work not only shows the great potential of ZrOOH, GdOOH, and HfOOH as triphosphatase nanozymes but also deepens our understanding of the role of surface hydroxyls on phosphatase-mimicking nanozyme catalytic dephosphorization, which could be used in the rational design of phosphatase-mimicking nanozymes. Furthermore, the developed colorimetric sensing system could be applied to chromium(III) ion detection in biological systems.