一种用于次氯酸根实时高灵敏度检测的络合物基荧光探针

doi:10.6023/cjoc202310014

摘要/Abstract

报道了一个实时检测次氯酸根阴离子的荧光探针TS1. 首先, 铜离子的引入可与化合物TS1形成稳定的络合物TS1-Cu, 导致溶液荧光被极大地猝灭. 然后, 继续加入次氯酸根, 由于次氯酸根的强氧化性, 可诱导TS1中席夫碱发生水解反应, 并转化为醛类化合物, 导致溶液荧光明显增强. 因此, 络合物TS1-Cu可实现对次氯酸根的快速实时检测, 且检测限低至120 nmol/L. 重要的是, 该络合物体系可成功地应用于商业消毒剂样品中次氯酸根的实际检测.

关键词: 荧光探针, 实时响应, 络合物基, 次氯酸根, 实际应用

A novel fluorescent probe TS1 for real-time monitoring of hypochlorite was reported. The introduction of Cu²⁺could lead to the formation of stable complex TS1-Cu and simultaneous remarkable fluorescence quenching. Next, “off-on” fluorescence changes of TS1-Cu were proceeded by the subsequent addition of hypochlorite, which induced the hydrolytic cleavage of the Schiff base in TS1 and the transformation to strongly fluorescent aldehyde. TS1-Cu could recognize hypochlorite through an instantaneous marked fluorescence enhancement with the detection limit as low as 120 nmol/L. Furthermore, the sensitive and rapid detection of hypochlorite with TS1-Cu for the practical application was also performed in commercial disinfectant samples.

Key words: fluorescent probe, real-time response, ensemble-based, hypochlorite, practical application

引用此文

程晓红, 刘发龙, 孙进博, 张锐. 一种用于次氯酸根实时高灵敏度检测的络合物基荧光探针[J]. 有机化学, 2024, 44(4): 1284-1292.

Xiaohong Cheng, Falong Liu, Jinbo Sun, Rui Zhang. An Ensemble-Based Fluorescent Probe for Real-Time and High Sensitive Detection of Hypochlorite[J]. Chinese Journal of Organic Chemistry, 2024, 44(4): 1284-1292.

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图/表 7

Scheme 1. Schematic representations of the detection for hypochlorite based on the TS1-Cu

Figure 1. Fluorescent emission spectra of TS1 in the presence of different concentrations of Cu2+ The inset plot showed the intensity changes at 490 nm of compound TS1 with different concentrations of Cu2+ (excitation wavelength: 390 nm)

Figure 2. Fluorescent emission spectra of TS1-Cu2+ in the presence of different concentrations of ClO– The inset plot showed the fluorescence intensities at 595 nm of compound TS1 with different concentrations of ClO– (Excitation wavelength: 390 nm)

Limit of detection	Switching type	Response time	Reference
59 nmol/L	Ratiometric response	<30 s	[15]
0.17 μmol/L	Off-on	2 min	[16]
0.2 μmol/L	Ratiometric response	10 min	[17]
96 nmol/L	Ratiometric response	With 60 s	[18]
0.356 μmol/L	Off-on	5 min	[19]
8.2 nmol/L	Off-on	20 min	[20]
9.6 nmol/L	Off-on	1 min	[21]
787 nmol/L	Ratiometric response	Within 100 s	[22]
28.8 nmol/L	Off-on	Within 30 s	[23]
120 nmol/L	Off-on	Within seconds	This work

Table 1. Brief detail about the reported fluorescence sensors based on the oxidation reaction of hypochlorite

Figure 3. Emission intensity changes of TS1-Cu to ClO– (25 μmol/L) in the presence of other competitive species (100 μmol/L) The error bars represent the standard deviation of three measurements

Figure 4. Calculated HOMOs and LUMOs of compounds TS1 (left) and TS1+Cu2+ (right)

Figure 5. Proposed plausible mechanisms for detection of ClO– by TS1-Cu and the 1H NMR spectra of the reaction product between TS1 and ClO–

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