高灵敏Eu-MOF荧光探针用于尿液中1-羟基芘的检测★

doi:10.6023/A26010034

摘要/Abstract

1-羟基芘(1-HP)是人体内多环芳烃(PAHs)代谢的终产物, 可作为一项生物学指标用于监测人类暴露于具有遗传毒性的PAHs的情况. 然而开发兼具高选择性、超高灵敏度与快速响应特性的1-HP检测方法仍面临重大挑战. 本研究成功构建了一种基于稀土金属铕(Eu³⁺)和刚性八羧酸配体H₈HPA-2Me的金属-有机框架(MOF)材料NKM-456-Eu. 值得注意的是, NKM-456-Eu被证明是一种卓越的发光传感器, 可以识别N,N-二乙基甲酰胺(DEF)溶液和人尿液中的1-HP, 具有快速响应性(5 s)、高猝灭效率K_sv(83280 L/mol)、低检测限(0.0061 μmol/L)和基于肉眼可观察的发光猝灭性能, 并且对尿液中的其他成分具有良好的抗干扰能力. 该Eu-MOF具有可调的天线效应, 在432 nm(配体π→π*跃迁)和616 nm(配体到金属电荷转移, LMCT)处表现出双发射, 在1-HP存在时实现了高效的荧光猝灭. 本研究为探索基于MOFs的潜在发光传感器提供了一种新策略, 这一具有可调天线效应的Eu-MOF开创性设计将积极推动高性能MOF荧光材料和器件的发展.

关键词: 金属-有机框架, 稀土金属, 1-羟基芘, 荧光探针, 高效率

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

引用此文

张杨, 张金莉, 庞建东, 卜显和. 高灵敏Eu-MOF荧光探针用于尿液中1-羟基芘的检测^★[J]. 化学学报, 2026, 84(5): 667-672.

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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图/表 4

图1. NKM-456-Eu的晶体结构图. (a) Eu3+配位方式; (b) 8-连接HPA-2Me8−配体片段和(c)沿c轴观察的NKM-456-Eu三维框架结构

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

图2. NKM-456-Eu在不同尿液成分的悬浮液中分散时的(a)发光光谱(λex=365 nm)和(b)相对发光强度

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

图3. NKM-456-Eu在DEF溶液中的发光强度在(a)逐步加入1-HP及(b)不同浓度1-HP含量(0~1 mg/mL)时的变化情况; (c) NKM-456-Eu检测1-HP的即时响应性; (d) NKM-456-Eu对1-HP的检测抗干扰能力示意图

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

图4. (a) NKM-456-Eu浸泡1-HP前后的荧光寿命图谱; (b) NKM-456-Eu浸泡1-HP后和1-HP的发射光谱; (c) DFT计算给出的1-HP和NKM-456-Eu配体HOMO和LUMO轨道

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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