Luminescence-Sensing Tb-MOF Nanozyme for the Detection and Degradation of Estrogen Endocrine Disruptors

Abstract

Using flexible structures and components of metal-organic framework (MOF) materials, we designed and developed an artificial nanozyme with dual functions of a catalyst and luminescent sensor specifically for the determination and degradation of hormone 17β-estradiol (E2) and its derivatives (E1, E3, and EE2), a class of disruptors with strong effect on the human endocrine system. This nanozyme composed of the luminescent Tb3+ ion, catalytic coenzyme factor hemin, and light-harvesting ligand can be used to both degrade E2 like natural horseradish peroxidase (HRP) and sense E2 as low as 50 pM by its luminescence. The nanozyme catalyzes the decomposition of E2 and its derivatives through a mechanism of active hydroxyl radicals and oxidative high-valent iron-oxo intermediates. The prepared nanozyme is pluripotent, stable, and cheap and can replace the widely used combination of natural enzyme and chromogenic substrate. The present strategy of constructing artificial enzymes directly from functional units provides a new way for the design and development of smart, multifunctional artificial enzymes.

Mechanistic Insight into Charge and Energy Transfers of Luminescent Metal–Organic Frameworks Based Sensors for Toxic Chemicals

“…The presence of 4,4′‐oxybisbenzoic acid and hemin in Tb‐MOF provided a good environment for electrostatic interactions between CO and the peroxide hydrogen atom in a complex system. [ 189 ] Furthermore, the introduction of nanoparticles into MOFs changed the sensing behavior for H 2 O 2 detection to the quenching effect. [ 190 ] Notably, MOFs bearing the same metal center but different linker functionalities showed different sensing behaviors.…”

Development of hybrid monoliths incorporating metal–organic frameworks for stir bar sorptive extraction coupled with liquid chromatography for determination of estrogen endocrine disruptors in water and human urine samples

“…Estrogens are known as endocrine-disruptor compounds (EDCs) widely spread in the aquatic system and other environments. Indeed, the attendance-and endocrine-disrupting potency of these molecules in waters, soil, and food are 10,000 times higher than common synthetic chemicals, for example pesticides [1][2][3]. Estrone (E1), 17β-estradiol (E2), 17β-ethinylestradiol (EE2), and estriol (E3) are the most extended estrogens in the environment and their origin can be various (human urine and feces, cattle activities, aquaculture, among others) [4].…”

A Long-Term Stable Sensor Based on Fe@PCN-224 for Rapid and Quantitative Detection of H2O2 in Fishery Products

“…Recently, metal-organic frameworks (MOFs) compounds composed of metal-oxygen clusters bridged by organic linking molecules are becoming a new class of enzyme mimics [32]. The porous 3D coordination polymers have larger specific surface areas and a higher density of accessible catalytic sites [33], which makes it possible to be a type of excellent peroxidase mimicking materials [34][35][36]. It has been reported that MOFs constructed by Zr6 and porphyrin possess framework hyperstability for the strong electrostatic interactions between high valence Zr IV and carboxylate linkers [37,38].…”