Near-Infrared Fluorescent Probe Based on Benzopyran Derivative for Highly Sensitive Detection of SO2 Derivative and Bioimaging

doi:10.6023/cjoc202510002

Abstract

A novel near-infrared (NIR) fluorescent probe DCA-Tcf is developed for the detection of sulfur dioxide derivatives ($\mathrm{HSO}_{3}^{-} / \mathrm{SO}_{3}^{2-}$) in biological systems and food samples in this paper. Utilizing 6-(diethylamino)-1,2-dihydrocyclopentene- [b]benzopyran as the fluorophore, and incorporating electron-withdrawing groups, the emission wavelength of the probe is red-shifted to 809 nm, which surpasses the typical 800 nm barrier for small-molecule probes. The emission wavelength (809 nm) can effectively enhance the tissue penetration depth and reduce the background fluorescence interference, making this probe more advantageous in biological imaging applications. Probe DCA-Tcf exhibits high selectivity, rapid response within 40 s, and a detection limit as low as 0.509 μmol/L toward $\mathrm{HSO}_{3}^{-} / \mathrm{SO}_{3}^{2-}$. DCA-Tcf has been applied successfully to the detection of $\mathrm{HSO}_{3}^{-}$ in real water and sugar samples, and demonstrates promising potential for application in fluorescence imaging of living cells. The DCA-Tcf developed in this study can become a powerful tool in the fields of food safety detection and bioimaging.

Key words: near-infrared emission, fluorescent probe, sulfur dioxide derivatives, bioimaging, food samples

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Lin Liu, Lulu Zhou, Tianyu Liang, Keli Zhong, Xiaomei Yan, Lijun Tang. Near-Infrared Fluorescent Probe Based on Benzopyran Derivative for Highly Sensitive Detection of SO₂ Derivative and Bioimaging[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 866-871.

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Fig. & Tab. 6

Scheme 1. (a) Advantages of DCA-Tcf over similar-structured probes; (b) Preparation process of sugar and actual water samples and application of DCA-Tcf fluorescence detection for ${\text{HSO}}_{3}^{－}$

Figure 1. (a) Fluorescence spectral changes of DCA-Tcf (10 μmol/L) in EtOH/PBS solution (V∶V=5∶5, pH=7.4) addition of various analytes (Br－, I－, $\mathrm{NO}_{2}^{-}$、$\mathrm{CO}_{3}^{2-}$、$\mathrm{HCO}_{3}^{-} 、 \mathrm{CH}_{3} \mathrm{COO}^{-} 、 \mathrm{HPO}_{4}^{2-} 、 \mathrm{~S}^{2-} 、 \mathrm{PO}_{4}^{3-} 、 \mathrm{CN}^{-} 、 \mathrm{SCN}^{-} 、 \mathrm{PPi} 、 \mathrm{SO}_{4}^{2-} 、 \mathrm{HSO}_{3}^{-} 、 \mathrm{~N}_{3}^{-} 、 \mathrm{Hcy} 、 \mathrm{GSH} 、 \mathrm{Cys} $ and $\mathrm{HSO}_{4}^{-}$, 500 μmol/L); (b) Fluorescence intensity changes at 809 nm of DCA-Tcf (10 μmol/L) solution addition of various analytes and further adding ${\text{HSO}}_{3}^{－}$ (λex=690 nm)

Figure 2. (a) Fluorescence spectral changes of DCA-Tcf (10 μmol/L) in EtOH/PBS solution (V∶V=5∶5, pH=7.4) upon the addition of varying concentrations of ${\text{HSO}}_{3}^{－}$ (0~500 μmol/L); (b) Time-dependent fluorescence intensity curve of DCA-Tcf solution at 809 nm after the addition of 500 μmol/L ${\text{HSO}}_{3}^{－}$ (λex=690 nm)

Figure 3. (a) Recognition mechanism of DCA-Tcf for ${\text{HSO}}_{3}^{－}$; (b) Optimized configurations and schematic diagrams of the frontier molecular orbital electronic transitions of DCA-Tcf and DCA-Tcf-${\text{HSO}}_{3}^{－}$ in the S1 state

Sample	c/(μmol•L^－1)		Recovery/%	RSD/% (n=3)
Sample	Added	Found	Recovery/%	RSD/% (n=3)
Granulated sugar 1	5	5.12	102.41	0.18
	6	6.09	101.50	0.06
	7	6.97	99.57	0.08
Granulated sugar 2	5	4.88	97.60	0.09
	6	6.23	103.83	0.09
	7	7.19	102.71	0.15
Tap water	5	5.23	104.58	0.23
	6	6.43	107.17	0.40
	7	7.19	102.67	0.31
Lake water	5	4.94	98.81	0.30
	6	6.09	101.55	0.45
	7	7.14	101.97	0.15
River water	5	5.22	104.40	0.39
	6	6.14	102.27	0.18
	7	6.95	99.31	0.13

Table 1. Results of DCA-Tcf detection of ${\text{HSO}}_{3}^{－}$ concentration in white sugar, tap water, lake water, and river water

Figure 4. Fluorescence images of MCF-7 cells incubated with DCA-Tcf (10 μmol/L) and various concentrations of ${\text{HSO}}_{3}^{－}$at 37 ℃ Bright-field (a, d, g, j, m), dark-field (b, e, h, k, n), and overlay images (c, f, i, l, o).

References 22

[1]	Liu, H.; You, M.; Feng, X.; Chen, J.; Li, B.; Gao, Z.; Xing, H.; Cong, Z.; Zhou, B.; Zhu, J.; Jin, M. Sens. Actuators, B 2024, 400, 134870.
[2]	Ma, J.; Zhao, M.; Qin, C.; Kong, X.; Xie, H.; Zhang, X.; Jiao, Z.; Zhang, Z. Dyes Pigm. 2024, 229, 342993.
[3]	Tian, L.; Sun, X.; Zhou, L.; Zhong, K.; Li, S.; Yan, X.; Tang, L. Food Chem. 2023, 407, 135031.
[4]	Zhong, K.; Hu, L.; Du, W.; Sun, X.; Tang, L.; Yan, X.; Li, X.; Li, J. Food Res. Int. 2025, 201, 115613.
[5]	Yang, Y.; Yan, X.; Liang, T.; Tian, M.; Wu, C.; Tang, L.; Sun, X.; Zhang, J.; Li, Y.; Zhong, K. J. Hazard. Mater. 2024, 469, 134003.
[6]	Shang, Z.; Meng, Q.; Zhang, R.; Zhang, Z. Anal. Chim. Acta 2023, 1279, 341783.
[7]	Zhang, S.; Zheng, H.; Yang, L.; Li, Z.; Yu, M. Anal. Chem. 2023, 95, 5377.
[8]	Cui, R.; Liu, C.; Zhang, P.; Qin, K.; Ge, Y. Molecules 2023, 28, 515.
[9]	Liang, T.; Liu, S.; Shen, T.; Chen, X.; Li, X.; Yan, X.; Sun, X.; Tian, M.; Wu, C.; Sun, X.; Zhong, K.; Li, Y.; Liu, X.; Tang, L. Sens. Actuators, B 2024, 413, 135864.
[10]	Huang, X.; Li, J.; Guo, Y.; Tian, M.; Yan, X.; Tang, L.; Zhong, K. Talanta 2025, 282, 126977.
[11]	Liang, T.; Liu, S.; Jiang, Y.; Tian, M.; Wu, C.; Li, Y.; Shen, T.; Sun, X.; Zhong, K.; Tang, L. Sci. China: Chem. 2025, 68, 3835.
[12]	Liu, N.; Lin, Z.; Li, Y.; Wu, C.; Tian, M.; Tang, L. Tetrahedron 2024, 168, 134355.
[13]	Li, Y.; Wang, Y.; Niu, H.; Chen, X.; Li, Z.; Wang, Y. Chin. J. Org. Chem. 2023, 43, 1952 (in Chinese).
	(李宜芳, 王耀, 牛华伟, 陈秀金, 李兆周, 王永国, 有机化学, 2023, 43, 1952.)
[14]	Li, H.; Yue, L.; Huang, H.; Chen, Z.; Guo, Y.; Lin, W. J. Photochem. Photobiol., A 2023, 441, 114684.
[15]	Li, Y.; Huang, Y.; Huang, X.; Tang, L. J. Mol. Struct. 2024, 1299, 137168.
[16]	Yan, Q.; Yao, X.; Li, Y.; Zhong, K.; Tang, L.; Yan, X. Spectrochim. Acta, Part A 2023, 299, 122882.
[17]	Liu, L.; Chen, L.; Hu, X.; Zhong, K.; Zhang, J.; Tang, L. Chin. J. Org. Chem. 2024, 44, 2027 (in Chinese).
	(刘琳, 陈琳, 胡晓玲, 钟克利, 张璟琳, 汤立军, 有机化学, 2024, 44, 2027.)
[18]	Li, Y.; Sun, X.; Hu, X.; Ren, Y.; Zhong, K.; Yan, X.; Tang, L. Chin. J. Org. Chem. 2023, 43, 320 (in Chinese).
	(李阳阳, 孙小飞, 胡晓玲, 任源远, 钟克利, 燕小梅, 汤立军, 有机化学, 2023, 43, 320.)
[19]	Yang, Y.; Chen, L.; Hu, X.; Zhong, K.; Li, S.; Yan, X.; Zhang, J.; Tang, L. Chin. J. Org. Chem. 2023, 43, 308 (in Chinese).
	(杨雅馨, 陈琳, 胡晓玲, 钟克利, 李世迪, 燕小梅, 张璟琳, 汤立军, 有机化学, 2023, 43, 308.)
[20]	Liu, S.; Liang, T.; Tian, M.; Wu, C.; Tang, L.; Li, Y.; Zhong, K.; Sun, X.; Li, X.; Li, J. J. Food Eng. 2025, 399, 112614.
[23]	Li, J.; Tian, M.; Shen, T.; Sun, X.; Liang, T.; Tang, L.; Liu, X.; Yan, X.; Zhong, K. J. Hazard. Mater. 2024, 480, 136291.
[24]	Huang, Y.; Li, Y.; Huang, X.; Tang, L.; Yan, X. Dyes Pigm. 2024, 222, 111901.
[25]	Zhu, H.; Zhang, X.; Liu, C.; Zhang, Y.; Su, M.; Rong, X.; Wang, X.; Liu, M.; Zhang, X.; Sheng, W.; Zhu, B. Sens. Actuators, B 2022, 366, 131962.
[26]	Chen, Q.; Li, J.; Wang, Y.; Tian, M.; Liang, T.; Zhong, K.; Yan, X.; Tang, L. Dyes Pigm. 2025, 239, 112767.
[27]	Zhong, K.; Zhao, Y.; He, Y.; Liang, T.; Tian, M.; Wu, C.; Tang, L.; Sun, X.; Zhang, J.; Li, Y.; Li, J. Spectrochim. Acta, Part A 2024, 318, 124501.
[28]	Zhong, K.; Li, Y.; Hu, X.; Li, Y.; Tang, L.; Sun, X.; Li, X.; Zhang, J.; Meng, Y.; Ma, R.; Wang, S.; Li, J. Food Chem. 2024, 438, 137987.
[29]	Shang, Z.; Wu, M.; Meng, Q.; Jiao, Y.; Zhang, Z.; Zhang, R. J. Hazard. Mater. 2024, 465, 133165.
[30]	Ma, J.; Kong, X.; Zhao, M.; Jiao, Z.; Xie, H.; Si, W.; Li, H.; Zhang, Z. Anal. Chim. Acta 2024, 1320, 342993.
[31]	Chao, J.; Wang, Z.; Zhang, Y.; Huo, F.; Yin, C. Anal. Methods 2021, 13, 3535.
[32]	Luo, X. Y.; Xie, J.; Zhao, G. L.; Li, G. Y.; Qu, H. D.; Yang, Y. Z. J. Fluoresc. 2023, 33, 191.
[33]	Ren, H. X.; Huo, F. J.; Wu, X.; Liu, X. G.; Yin, C. X. Chem. Commun. 2021, 57, 655.
[34]	Wang, Z.; Zhang, T.; Huo, F. J.; Zhang, Y. B.; Chao, J. B. J. Mol. Struct. 2022, 1255, 132413.
[35]	Li, Y.; Sun, X.; Zhou, L.; Tian, L.; Zhong, K.; Zhang, J.; Yan, X.; Tang, L. J. Agric. Food Chem. 2022, 70, 10899.
[21]	Zhang, P.; Su, J.; Zhen, H.; Yu, T.; Wei, L.; Zheng, M.; Zeng, C.; Shu, W. Coord. Chem. Rev. 2025, 522, 216232.
[22]	Zhang, H.; Li, F.; Li, Q.; Liang, C.; Wei, Y.; Zhou, C.; Lai, Z.; Li, X.; Yang, F. Sens. Actuators, B 2024, 412, 135795.

基于苯并吡喃衍生物的近红外荧光探针用于二氧化硫衍生物的高灵敏检测与生物成像

Near-Infrared Fluorescent Probe Based on Benzopyran Derivative for Highly Sensitive Detection of SO₂ Derivative and Bioimaging

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