High-sensitivity Eu-MOF Fluorescent Probe for the Detection of 1-Hydroxypyrene in Urine★

doi:10.6023/A26010034

Abstract

1-Hydroxypyrene (1-HP) is the final metabolite of polycyclic aromatic hydrocarbons (PAHs) in the human body and is an important biomarker for assessing human exposure to genotoxic PAHs. However, the existing analytical methods are difficult to achieve high selectivity, ultra-high sensitivity, and rapid response simultaneously, which limits their application in on-site rapid screening. To address this issue, this study successfully constructed a new metal-organic framework (MOF) material NKM-456-Eu based on europium ions and the rigid octahedral acid ligand (H₈HPA-2Me). This material fully utilizes the large π conjugated system and restricted rotation ability of the ligand to achieve a unique fluorescence response to the target substance. As a fluorescence quenching sensor, NKM-456-Eu performs excellently in high sensitivity and high selectivity detection of 1-HP in N,N-diethylformamide (DEF) solution and complex human urine matrix. It shows the characteristics of ultra-fast response (5 s), ultra-high quenching constant (K_sv=83,280 L/mol), and ultra-low detection limit (0.0061 μmol/L). Moreover, this sensor exhibits excellent interference resistance to common urine components such as urea, creatinine, and glucose, and shows good recovery and reliability in artificial urine matrix detection, demonstrating its practical application potential. Mechanism studies show that NKM-456-Eu has a tunable "antenna effect", generating dual emissions at 432 nm (attributed to the π→π* transition of the ligand center) and 616 nm (caused by charge transfer from the ligand to the metal). The fluorescence quenching arises from a synergistic interplay of multiple mechanisms: 1-HP binds to the MOF via π-π interactions, and its absorption band overlaps with the excitation spectrum of the MOF, leading to an inner filter effect (IFE), concurrent with photoinduced electron transfer (PET). This competitive interplay disrupts the ligand-to-Eu³⁺ energy transfer, resulting in substantial fluorescence quenching. This study not only provides a promising strategy for the development of MOF-based luminescent sensors but also highlights the potential of Eu-MOFs in customizing antenna effects, promoting the development of high-performance fluorescent materials and sensor devices in the environmental and biomedical fields.

Key words: metal-organic frameworks, rare earth metals, 1-hydroxypyrene, fluorescent probe, high-efficiency

Cite this article

Yang Zhang, Jinli Zhang, Jiandong Pang, Xian-He Bu. High-sensitivity Eu-MOF Fluorescent Probe for the Detection of 1-Hydroxypyrene in Urine^★[J]. Acta Chimica Sinica, 2026, 84(5): 667-672.

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Fig. & Tab. 4

Figure 1. Schematic illustration of the structure of NKM-456-Eu. (a) Coordination environment of Eu3+; (b) 8-connected HPA-2Me8− fragment and (c) Crystal structure of NKM-456-Eu viewed along the c axis

Figure 2. (a) Luminescence spectra (λex=365 nm) and (b) relative luminescence intensities of NKM-456-Eu dispersed in suspensions with various urine components

Figure 3. Luminescence intensity of NKM-456-Eu in DEF solution with (a) stepwise addition of 1-HP or (b) different concentrations of 1-HP (0~1 mg/mL); (c) immediate response of NKM-456-Eu to 1-HP detection and (d) schematic diagram of the anti-interference ability of NKM-456-Eu for 1-HP detection

Figure 4. (a) Fluorescence lifetime spectra of NKM-456-Eu before and after immersion in 1-HP; (b) Emission spectra of NKM-456-Eu after immersion in 1-HP and that of 1-HP; (c) DFT calculations of HOMO and LUMO orbitals of 1-HP and NKM-456-Eu

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高灵敏Eu-MOF荧光探针用于尿液中1-羟基芘的检测^★