用于Fe3+检测的两种杂化HOFs荧光传感器：合成、表征及传感机理
Two Hybrid HOFs as Fluorescent Sensor for Fe3+ detection: Synthesis, Characterization and Sensing Mechanism
莫珊珊 1穆小静 1刘思怡1
作者信息
- 1. 重庆大学化学化工学院，重庆 401331
- 折叠
摘要
氢键有机框架（HOFs）是一类新型多孔结晶有机材料，在荧光传感、气体分离、催化和生物医学等众多领域展现出巨大的应用价值。本研究设计、合成并利用单晶X射线衍射（SXRD）、粉末X射线衍射（PXRD）、扫描电子显微镜（SEM）、能量色散X射线光谱（EDS）等技术表征了两种荧光吡啶-羧酸杂化HOFs（BTC-TPA和TCA-TPA）。SXRD分析表明，在BTC-TPA中，羧酸基团与吡啶基团之间仅存在一种氢键，比例为1:1；而在 TCA-TPA中，存在O-H…N和O-H…O两种类型的氢键，比例为1:2。BTC-TPA和TCA-TPA 均表现出强烈的荧光，且在与金属离子配位后发生猝灭。它们良好的稳定性和荧光特性使其能够作为传感器用于离子检测。进一步的研究表明，利用荧光猝灭效应，BTC-TPA是一种对Fe3?具有高选择性的传感器，其检测线性范围为5.0 ~ 600 μM，检测限低至0.84 μM。此外，利用密度泛函理论（DFT）计算、红外（IR）和紫外（UV）光谱等方法对其潜在的传感机理进行了深入探讨。与Fe3?结合后，BTC-TPA的HOMO-LUMO能隙（ΔE）从3.24 eV剧烈下降至1.69 eV，从而导致荧光猝灭。FT-IR研究显示，经Fe3?处理后，BTC-TPA中C-O和C-N的伸缩振动峰分别向低频方向移动了3 cm?1和5 cm?1。紫外光谱表明该荧光猝灭遵循动态猝灭机制。
Abstract
Hydrogen-bonded organic frameworks (HOFs) are a new class of porous crystalline organic materials showing great values in various fields such as luminescent sensing, gas separation, catalysis, and biomedicine. Two fluorescent pyridine-carboxylic acid hybrid HOFs (BTC-TPA and TCA-TPA) are designed, synthesized, and characterized using single-crystal X-ray diffraction (SXRD), PXRD, SEM, EDS, and other techniques. SXRD analysis revealed that only one type of hydrogen bonds exists between the carboxylic acid moiety and the pyridine moiety in 1:1 ratio in BTC-TPA. In TCA-TPA, two types of hydrogen bonds O-H…N and O-H…O are present in 1:2 ratio. Both BTC-TPA and TCA-TPA exhibited strong fluorescence, which was quenched upon coordination with metal ions. Their good stabilities and fluorescent properties allowed them to be sensors for detection. Further studies showed that BTC-TPA was a selective sensor toward Fe3? by using fluorescence quenching, with a detection linear range 5.0 ~ 600 μM and a detection limit as low as 0.84 μM. The underlying sensing mechanisms were investigated using Density Functional Theory (DFT) calculations, IR and UV methods. By binding with Fe3?, a dramatic decrease in the HOMO-LUMO energy gap (ΔE) from 3.24 eV to 1.69 eV for the BTC-TPA occurred, leading to fluorescence quenching. FT-IR studies revealed after treatment with Fe3? ions, the stretching vibration peak of C-O and the C-N in BTC-TPA shifted to a lower frequency by 3 cm?1 and 5 cm?1, respectively. UV spectra showed the fluorescence was quenched in a dynamic mechanism.关键词
氢键有机框架（HOFs）/杂化/荧光传感/Fe3?/机理探究Key words
HOFs/hybrid/fluorescent sensor/Fe3?/mechanism probing引用本文复制引用
莫珊珊,穆小静,刘思怡.用于Fe3+检测的两种杂化HOFs荧光传感器：合成、表征及传感机理[EB/OL].(2026-03-30)[2026-03-31].http://www.paper.edu.cn/releasepaper/content/202603-291.学科分类
化学/晶体学
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