Modulating the Biomimetic and Fluorescence Quenching Activities of Metal-Organic Framework/Platinum Nanoparticle Composites and Their Applications in Molecular Biosensing.

Abstract

Nanoscale metal-organic frameworks (nMOFs) have gained considerable attention with significant potential applications. Although great efforts have been devoted to designing and fabricating nanoscaffold structures, approaches of deliberately regulating the intrinsic functionality of nMOFs have been poorly explored. Herein, we report a simple and novel strategy to regulate the catalytic and fluorescence quenching behaviors of nMOFs through coordination-driven self-assembly. As a proof-of-concept, we synthesized a synergistic and stable MOF-metal nanocomposite by loading platinum nanoparticles (PtNPs) on a commonly used Fe-MOF, i.e., MIL-88B-NH2/Pt, as a MOF composite model for exploration. On one hand, the complexation with ATP effectively broke the pH limitation of the peroxidase-mimicking MIL-88B-NH2/Pt nanozyme, bringing a 10-fold increased catalytic activity under alkaline condition. Based on the distinct catalytic enhancement between ATP and other nucleotides, real-time monitoring of apyrase activity as well as colorimetric detection of alkaline phosphatase (ALP) was performed. On the other hand, interactions of MIL-88B-NH2/Pt with fluorescent DNA were tolerant of different nucleic acids and, more importantly, were further manipulated by inorganic molecules. As a result, H2O2 could only trigger the release of a G-rich sequence, while phosphates could readily induce desorption of various DNA molecules with varying lengths, sequences, and fluorescent dyes. Accordingly, fluorescent DNA and MIL-88B-NH2/Pt as functional probe-quencher pairs were proposed, allowing the establishment of a fluorescence bioassay for ALP and PPase detection and Boolean logic calculations. This work offers a means to tune the intrinsic activities of nMOFs by surface engineering, benefiting design of functional nanomaterials and development of advanced biosensing systems.