萘酰亚胺-菲并咪唑荧光探针用于Cu2+的比色比率检测

doi:10.16085/j.issn.1000-6613.2025-0184

摘要/Abstract

摘要：

开发高选择性、高灵敏度的Cu²⁺传感器在化学、生物和环境等领域具有重要意义。本研究利用ICT机制设计并合成了一种基于萘酰亚胺-菲并咪唑的新型Cu²⁺比色和荧光比率探针NP，并通过¹H NMR、¹³C NMR和HR-MS进行了表征。在Cu²⁺加入后，探针NP由“亮黄色”荧光变为“蓝色”荧光，肉眼可观察到颜色由“亮黄色”变为“无色”。UV-vis和荧光光谱研究表明，探针NP对Cu²⁺具有较高的选择性和灵敏度，并且响应时间短。根据荧光滴定实验，计算得到探针NP与Cu²⁺的结合常数为3.04×10⁴L/mol，NP对Cu²⁺的检出限为5.35×10^-8mol/L（53.5nmol/L）。Job曲线、¹H NMR和质谱数据分析显示，探针NP是通过菲并咪唑N原子、亚胺上的N原子与Cu²⁺结合的，二者结合的化学计量比为1∶1，DFT计算显示NP-Cu²⁺的HOMO-LUMO能带能隙差低于NP的能隙差，表明NP与Cu²⁺的配位是有利的。NP已成功应用于实际水样中Cu²⁺的定量识别；此外，制备了基于NP的试纸条，与智能手机结合，可实现Cu²⁺的快速视觉半定量检测。

关键词: 铜离子, 萘酰亚胺-菲并咪唑, 荧光比率探针, 分子内电荷转移, 比色识别

Abstract:

The development of highly selective and sensitive sensors for Cu²⁺ ions is of paramount significance in the realms of chemistry, biology and environmental science. In this paper, a colorimetric and ratiometric fluorescent sensor for Cu²⁺ based on intra molecular charge transfer (ICT) mechanism was developed using naphthalimide-phenanthroimidazole (NP), and well characterized by ¹H NMR, ¹³C NMR and HR-MS. NP showed the fluorescence color change from "bright yellow" to "blue" as well as naked-eye color alter from "bright yellow" to "colorless" after the Cu²⁺ adding. UV-vis and fluorescence spectroscopy results revealed that the sensor NP exhibited remarkable colorimetric and ratiometric fluorescence behavior towards Cu²⁺ with high selectivity and sensitivity, and the response time was short. Based on emission titration data, the binding constant between the NP and Cu²⁺ was 3.04×10⁴L/mol and the limit of detection (LOD) was 5.35×10^-8mol/L (53.5nmol/L). The response mechanism was revealed by Job plot analysis, ¹H NMR spectroscopy and mass spectrometry data. The results showed that the coordination of the sensor's N atoms of phenanthroimidazole and imide with Cu²⁺ ions, and the binding stoichiometry between NP and Cu²⁺ was 1∶1. DFT calculation results showed that the lower bandgap of the HOMO-LUMO after coordination indicated that the coordination between PZ and Cu²⁺ was stable. NP was successfully applied for the quantitative recognition of Cu²⁺ in real water samples. In addition, the sensor NP was loaded on filter paper to make test strips and combined with a smartphone to achieve rapid visual quantitative detection of Cu²⁺.

Key words: copper(Ⅱ) ion, naphthalimide-phenanthroimidazole, ratiometric fluorescent probe, intra molecular charge transfer (ICT), colorimetric

中图分类号:

O626.1

董智云, 石瑞丹, 周佳丽, 雷心星, 席福贵. 萘酰亚胺-菲并咪唑荧光探针用于Cu²⁺的比色比率检测[J]. 化工进展, 2025, 44(7): 4078-4088.

DONG Zhiyun, Ruidan SHI, ZHOU Jiali, LEI Xinxing, XI Fugui. A naphthalimide-phenanthroimidazole-based fluorescent sensor for the colorimetric and ratiometric detection of Cu²⁺[J]. Chemical Industry and Engineering Progress, 2025, 44(7): 4078-4088.

图/表 12

参考文献 33

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检测方式	溶剂	检出限/ mol·L^-1	参考文献
荧光猝灭(Turn off)	DMF/H₂O （9∶1，体积比）	9.37×10^-9	[14]
荧光猝灭(Turn off) 比色传感	Tris-HCl缓冲溶液, 0.01mol/L，pH 7.00	2.3×10^-6	[15]
荧光增强(Turn on)	H₂O/THF （7∶3，体积比）	0.48×10^-6	[16]
荧光比率(F₄₁₈/F₄₇₄)	CH₃CN/H₂O （1∶1，体积比）	0.27×10^-6	[17]
荧光比率(F₄₅₄/F₅₅₀) 比色传感	CH₃CN/H₂O （98∶2，体积比）	9.53×10^-9	[18]

检测方式	溶剂	检出限/ mol·L^-1	参考文献
荧光猝灭(Turn off)	DMF/H₂O （9∶1，体积比）	9.37×10^-9	[14]
荧光猝灭(Turn off) 比色传感	Tris-HCl缓冲溶液, 0.01mol/L，pH 7.00	2.3×10^-6	[15]
荧光增强(Turn on)	H₂O/THF （7∶3，体积比）	0.48×10^-6	[16]
荧光比率(F₄₁₈/F₄₇₄)	CH₃CN/H₂O （1∶1，体积比）	0.27×10^-6	[17]
荧光比率(F₄₅₄/F₅₅₀) 比色传感	CH₃CN/H₂O （98∶2，体积比）	9.53×10^-9	[18]

计算方法	线性回归方程	相关系数	检出限
单波长法（F₄₄₉）	y=1.733×10⁸x-235.282	0.9968	7.91×10^-8mol/L（79.1nmol/L）
比率法（F₄₄₉/F₅₅₇）	y=4.925×10⁵x-1.167	0.9954	5.35×10^-8mol/L（53.5nmol/L）

计算方法	线性回归方程	相关系数	检出限
单波长法（F₄₄₉）	y=1.733×10⁸x-235.282	0.9968	7.91×10^-8mol/L（79.1nmol/L）
比率法（F₄₄₉/F₅₅₇）	y=4.925×10⁵x-1.167	0.9954	5.35×10^-8mol/L（53.5nmol/L）

样品	pH	添加量/×10^-6mol·L^-1	检出量/×10^-6mol·L^-1	回收率/%	RSD(n=3)/%
自来水	7.11	0.1	0.106	106.0	1.27
		0.3	0.307	102.3	1.38
		0.6	0.581	96.8	1.36
河水	7.24	0.1	0.108	108.0	1.76
		0.3	0.304	101.3	1.85
		0.6	0.611	109.0	1.96
工业污水	8.16	0.1	0.109	106.0	1.88
		0.3	0.308	102.7	1.92
		0.6	0.614	102.3	2.17

萘酰亚胺-菲并咪唑荧光探针用于Cu²⁺的比色比率检测

A naphthalimide-phenanthroimidazole-based fluorescent sensor for the colorimetric and ratiometric detection of Cu²⁺

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