氰基导向芳香氢亲核取代反应构建新型萘酰亚胺比色探针: 食品与水样中氰化物的高灵敏检测

doi:10.6023/cjoc202507013

摘要/Abstract

本研究基于缺电子芳烃芳香氢亲核取代(SNARH)反应机制, 提出氰基导向的SNARH反应策略, 成功设计并合成了一种新型萘酰亚胺探针Nap-CHCN. 紫外-可见吸收光谱研究表明, 探针与CN^－作用后, 630 nm处出现特征吸收带, 溶液颜色由无色变为蓝色, 检测限低至8.02 μmol/L, 且对CN^－表现出优异的选择性. 核磁滴定实验证实了CN^－诱导的脱质子化识别机制, 而可逆性实验显示探针可通过三氟乙酸(TFA)实现多次循环使用. 实际应用中, 探针在试纸条、食品样本及真实水样中均表现出可靠的CN^－检测能力. 该探针兼具合成简便、高灵敏度及环境适应性, 为复杂体系中CN^－的实时监测提供了有效工具.

关键词: 芳香氢亲核取代(SNARH), 氰根离子, 比色探针, 萘酰亚胺, 食品水样

A novel naphthalimide-based probe, Nap-CHCN was designed and synthesized based on cyano-directed electron- deficient aromatic nucleophilic substitution of hydrogen (SNARH) reaction mechanism. UV-Vis absorption spectroscopy studies revealed that after interaction with CN^－, a characteristic absorption band appeared at 630 nm, accompanied by a color change of the solution from colorless to blue. The probe demonstrated a low detection limit of 8.02 μmol/L and excellent selectivity for CN^－. Nuclear magnetic resonance (NMR) titration experiments confirmed a CN^－-induced deprotonation recognition mechanism, while reversibility tests showed that the probe could be recycled multiple times using trifluoroacetic acid (TFA). In practical applications, the probe exhibited reliable CN^－ detection capabilities in test strips, food samples, and real water samples. With its simple synthesis, high sensitivity, and environmental adaptability, this probe provides an effective tool for real-time monitoring of CN^－ in complex systems.

Key words: aromatic nucleophilic substitution of hydrogen (SNARH), cyanide anion, colorimetric sensor, naphthalimide, food and water sample

引用此文

杨洁, 佘湫楠, 周逸聪, 康丽琴, 赵佳丽, 刘传祥. 氰基导向芳香氢亲核取代反应构建新型萘酰亚胺比色探针: 食品与水样中氰化物的高灵敏检测[J]. 有机化学, 2026, 46(2): 531-538.

Jie Yang, Qiunan She, Yicong Zhou, Liqin Kang, Jiali Zhao, Chuanxiang Liu. Cyanide-Directed Aromatic Nucleophilic Substitution of Hydrogen Reaction for Constructing Novel Naphthalimide Colorimetric Probe: Highly Sensitive Detection of Cyanide in Food and Water Samples[J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 531-538.

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图/表 9

图式1. 1,8-萘酰亚胺碳-氢官能团化

Scheme 1. C—H functionalization of 1,8-naphthalimide

图式2. 探针Nap-CHCN的合成路线

Scheme 2. The synthetic route of probe Nap-CHCN

图1. (a)探针Nap-CHCN (20 μmol/L)与CN－ (0~42.0 equiv.)在CH3CN/PBS (V∶V=9∶1, pH=7.4)中的紫外滴定光谱图; (b)探针Nap-CHCN (20 μmol/L)与42.0 equiv.不同阴离子(5000 μmol/L)在CH3CN/PBS (V∶V=9∶1, pH=7.4)中的紫外吸收选择性图(插图为日光下探针Nap-CHCN与不同阴离子分析物作用后的溶液颜色变化图); (c)探针Nap-CHCN (20 μmol/L)与各种阴离子分析物在CH3CN/PBS (V∶V=9∶1, pH=7.4)溶液中的干扰性实验结果[采用双柱状图可视化呈现检测结果: 黄色条柱对应单一阴离子饱和浓度(42.0 equiv.)下探针在630 nm处的吸光度变化, 绿色条柱则表示非CN－阴离子共存时额外添加饱和量CN－的干扰效应. 图中标注的数字依次对应以下分析物: (1) CN－, (2) Br－, (3) ClO－, (4) DTT, (5) F－, (6) NaHS, (7) $\mathrm{HSO}_{4}^{-}$, (8) I－, (9) $\mathrm{NO}_{3}^{-}$, (10) $\mathrm{HPO}_{4}^{2-}$, (11) $\mathrm{HCO}_{3}^{-}$, (12) ATP, (13)甘氨酸, (14)亮氨酸]; (d)在不同pH值条件下探针Nap-CHCN (20 μmol/L, 42 equiv. CN－)在CH3CN/PBS (V∶V=9∶1, pH=7.4)体系中于630 nm波长处的紫外吸收光谱变化

Figure 1. (a) UV titration spectrum of the probe Nap-CHCN (20 μmol/L) with CN－ (0~42.0 equiv.) in CH3CN/PBS solution (V∶V=9∶1, pH=7.4); (b) UV absorption selectivity profile of probe Nap-CHCN (20 μmol/L) in the presence of 42.0 equiv. of various anions (5000 μmol/L each) within a CH3CN/PBS solution (V∶V=9∶1, pH=7.4) [The inset illustrates the color change of the probe Nap-CHCN solution upon interaction with various anionic analytes under natural daylight]; (c) Interference study of the probe Nap-CHCN (20 μmol/L) with various anionic analytes in CH3CN/PBS solution (V∶V=9∶1, pH=7.4) using dual bar graphs [Yellow bars represent the UV absorption intensity (630 nm) of the probe under saturated concentrations (42.0 equiv.) of individual anions, while green bars indicate the combined effect of non-CN－ analytes (5000 μmol/L) with additional saturated CN－. The numbered entries in the figure correspond to specific analytes as follows: (1) CN－, (2) Br－, (3) ClO－, (4) DTT, (5) F－, (6) NaHS, (7) $\mathrm{HSO}_{4}^{-}$, (8) I－, (9) $\mathrm{NO}_{3}^{-}$, (10) $\mathrm{HPO}_{4}^{2-}$, (11) $\mathrm{HCO}_{3}^{-}$, (12) ATP, (13) Glycine, and (14) Leucine]; (d) UV absorption spectrum (630 nm) of the probe Nap-CHCN (20 μmol/L, 42 equiv. of CN－) in CH3CN/PBS solution (V∶V=9∶1, pH=7.4) at different pH values

图2. (a)在CH3CN/PBS缓冲液(V∶V=9∶1, pH=7.4)中通过TFA (0~44.0 equiv.)对[Nap-CHCN＋CN－]络合物进行紫外-可见滴定(插图显示了在630 nm波长处的吸光度与TFA浓度的关系); (b)在CH3CN中用CN－和H＋ (TFA)滴定探针Nap-CHCN的相对紫外-可见吸光度循环性实验; (c)在CH3CN/PBS缓冲液(V∶V=9∶1, pH=7.4)中连续添加CN－和H＋ (TFA)后探针Nap-CHCN的颜色变化

Figure 2. (a) UV-Vis titration of [Nap-CHCN＋CN－] complexes with TFA (0~44.0 equiv.) performed in CH3CN/PBS solution (V∶ V=9∶1, pH=7.4) (The inset demonstrates the linear relationship between the absorbance at 630 nm and the concentration of TFA); (b) Cycling behavior of relative UV-Vis absorbance investigated by titrating the probe Nap-CHCN with CN－ and H＋ (provided by TFA) in CH3CN solution; (c) Color change of probe Nap-CHCN upon sequential addition of CN－ and H＋ (TFA) in a CH3CN/PBS solution (V∶V=9∶1, pH=7.4) system

图3. (a)探针Nap-CHCN与CN－在CDCl3中的1H NMR核磁滴定谱图(自下而上: 0, 0.2, 0.4, 0.8, 1.0, 1.5, 1.8 equiv.); (b) Nap-CHCN与CN－在CDCl3中的13C NMR核磁滴定谱图(自下而上: 0, 1.5 equiv.四丁基氰化铵); (c)识别机理

Figure 3. (a) 1H NMR titration spectra of probe Nap-CHCN upon addition of CN－ in CDCl3 (from the bottom to top: 0, 0.2, 0.4, 0.8, 1.0, 1.5, 1.8 equiv.); (b) 13C NMR titration spectra of probe Nap-CHCN in CDCl3 upon addition of CN－ ions (from the bottom to top: 0, 1.5. equiv. TBACN); (c) Sensing mechanism

图4. (a)探针Nap-CHCN的检测试纸条随不同CN－浓度梯度作用后的颜色变化; (b)探针Nap-CHCN的检测试纸条随不同OH－浓度(TBAOH)梯度作用后的颜色变化

Figure 4. Colorimetric response of Nap-CHCN immobilized test strips to CN－ concentration gradients; (b) Colorimetric response of Nap-CHCN immobilized test strips to OH－ concentration (TBAOH) gradients

图5. 探针Nap-CHCN与含氰化物食品样本提取液作用的紫外吸收光谱响应(插图为探针Nap-CHCN与食品提取液反应后溶液颜色变化对比图)

Figure 5. UV-vis absorption spectral response of probe Nap- CHCN with cyanide-containing food sample extracts (The inset shows the comparative color changes of the solution after the reaction between probe Nap-CHCN and food extract)

Sample	Spiked/ (μmol•L^－1)	Found/ (μmol•L^－1)	Recovery/%	RSD/%
Lake water	40	40.12	100.30	1.02
	50	51.12	102.24	0.95
	60	59.87	99.78	1.01
Tap water	40	39.89	99.73	0.96
	50	50.08	100.16	1.13
	60	60.14	100.23	1.15
Drinking water	40	40.09	100.23	1.13
	50	50.28	100.56	1.17
	60	61.01	101.68	1.18
Rain water	40	39.64	99.10	1.20
	50	51.36	102.72	1.10
	60	60.93	101.55	1.12

表1. 紫外-可见光谱法测定加标水样中CN－含量(n=3)

Table 1. Determination of cyanide (CN－) in spiked water samples by UV-Vis spectrophotometry (n=3)

图6. 真实水样中探针Nap-CHCN对CN－的紫外吸收检测误差

Figure 6. UV absorption detection deviation of probe Nap- CHCN for CN－ in authentic aqueous matrices

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