Cyanide-Directed Aromatic Nucleophilic Substitution of Hydrogen Reaction for Constructing Novel Naphthalimide Colorimetric Probe: Highly Sensitive Detection of Cyanide in Food and Water Samples

doi:10.6023/cjoc202507013

Abstract

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

Cite this article

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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Fig. & Tab. 9

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

Scheme 2. The synthetic route of probe Nap-CHCN

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

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

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

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

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

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

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

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