Citation: Wang Shaojing, Li Changwei, Li Jin, Chen Bang, Guo Yuan. Novel Coumarin-Based Fluorescent Probes for Detecting Fluoride Ions in Living Cells[J]. Acta Chimica Sinica, ;2017, 75(4): 383-390. doi: 10.6023/A17010029 shu

Novel Coumarin-Based Fluorescent Probes for Detecting Fluoride Ions in Living Cells

Key Laboratory of Synthetic and Natural Functional Molecular Chemistry, Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710127

Corresponding author: Guo Yuan, guoyuan@nwu.edu.cn
Received Date: 19 January 2017

Fund Project: the National Natural Science Foundation of China 21072158the Preferential Financing of Science and Technology Activities in Returned Overseas Graduates in Shaanxi Province 20151190the National Natural Science Foundation of China 21472148

Figures(9)

Fluoride, the smallest anion, is one of the most important anions in the human body which is involved in many diseases and many life activities can be displayed by its situation. It is necessary to detect fluoride ions and determine its concentration in organism. Compared to the traditional detection methods, fluorescence probes exhibit high sensitivity, high selectivity and potential for real-time detection. Because coumarin derivatives have strong emission in the visible region, high quantum yield, high photostability and excellent bioactivity, we choose them as fluorophore to prepare new fluorescent probes. Based on the mechanism of intramolecular charge transfer (ICT), the fluorescent probes CS1, CS2 and CS3 that are coumarin-based derivatives were designed, synthesized and utilized in fluoride ions detection. Their structures were confirmed by ¹H NMR, ¹³C NMR, IR and HRMS. Meanwhile, the crystals of CS3 were obtained by slow evaporation of an ether solution at room temperature over a period of a few days. The detection limits of CS1, CS2 and CS3 for fluoride ions were respectively determined as 21.77, 3.52 and 1.99 μmol/L, indicating that probes have a good sensitivity to the detection of fluoride. The selectivity experiment results demonstrated that the three probes were highly selective for fluoride ions over other competitive. The recognition mechanism of the fluorescent response to fluoride ions was verified by HRMS and NMR experiment in this work. A lot of detailed experiment results indicated that the fluorescent response of probes to fluoride ions attributed to the specific fluoride promoted Si-O cleavage. The study of the effect of probes on viability of cells were carried out using the methylthiazolyldiphenyl-tetrazolium bromide (MTT) assay. The experimental results indicated that the three probes had low cytotoxicity. Then the three probes were successfully used to fluorescent detect and image fluoride ions in MCF-7 cells by fluorescence spectrum and confocal fluorescence microscopic imaging, respectively.
- coumarin,
- fluoride ions,
- fluorescent probe,
- intramolecular charge transfer,
- cell imaging
1. [1]
  Gale, P. A. Chem. Soc. Rev. 2010, 39, 3746. doi: 10.1039/c001871f
2. [2]
  Bowman-James, K. Acc. Chem. Res. 2005, 38, 671. doi: 10.1021/ar040071t
3. [3]
  Gale, P. A. Acc. Chem. Res. 2006, 39, 465. doi: 10.1021/ar040237q
4. [4]
  Zhou, Y.; Zhang, J. F.; Yoon, J. Chem. Rev. 2014, 114, 5511. doi: 10.1021/cr400352m
5. [5]
  Suksai, C.; Tuntulani, T. Top. Curr. Chem. 2005, 255, 163.
6. [6]
  Gale, P. A. Chem. Commun. 2011, 47, 82. doi: 10.1039/C0CC00656D
7. [7]
  Featherstone, J. D. B. Community. Dent. Oral. Epidemiol. 1999, 27, 31. doi: 10.1111/com.1999.27.issue-1
8. [8]
  Bassin, E. B.; Wypij, D.; Davis, R. B.; Mittleman, M. A. Cancer Causes Control 2006, 17, 421. doi: 10.1007/s10552-005-0500-6
9. [9]
  Matsui, H.; Morimoto, M.; Horimoto, K.; Nishimura, Y. Toxicol. In Vitro 2007, 21, 1113. doi: 10.1016/j.tiv.2007.04.006
10. [10]
  Basha, P. M.; Madhusudhan, N. Neurochem. Res. 2010, 35, 1017. doi: 10.1007/s11064-010-0150-2
11. [11]
  Wade, C. R.; Broomsgrove, A. E. J.; Aldridge, S. Chem. Rev. 2010, 110, 3958. doi: 10.1021/cr900401a
12. [12]
  Barbier, O.; Arreola-Mendoza, L.; DelRazo, L. M. Chem.-Biol. Interact. 2010, 188, 319. doi: 10.1016/j.cbi.2010.07.011
13. [13]
  Singh, P.; Barjatiya, M.; Dhing, S.; Bhatnagar, R.; Kothari, S.; Dhar, V. Urol. Res. 2001, 29, 238. doi: 10.1007/s002400100192
14. [14]
  Duke, R. M.; Veale, E. B.; Pfeffer, F. M.; Kruger, P. E.; Gunnlaugsson, T. Chem. Soc. Rev. 2010, 39, 3936. doi: 10.1039/b910560n
15. [15]
  Hang, Y. P.; Wu, C. Y. Anal. Chim. Acta 2010, 661, 161. doi: 10.1016/j.aca.2009.12.018
16. [16]
  Somer, G.; Kalayci, S.; Basak, I. Talanta 2010, 80, 1129. doi: 10.1016/j.talanta.2009.08.037
17. [17]
  Tan, W. B.; Leng, T. H.; Lai, G. Q.; Li, Z. F.; Wu, J. F.; Shen, Y. J.; Wang, C. Y. Chin. J. Chem. 2016, 34, 809. doi: 10.1002/cjoc.v34.8
18. [18]
  Zhang, L.; Wang, L. M.; Zhang, G. J.; Yu, J. J.; Cai, X. F.; Teng, M. S.; Wu, Y. Chin. J. Chem. 2012, 30, 2823. doi: 10.1002/cjoc.v30.12
19. [19]
  Chen, Z. J.; Wang, L. M.; Zou, G. Zhang, L.; Zhang, J. L.; Cai, X. F.; Teng, M. S. Dyes Pigments 2012, 94, 410. doi: 10.1016/j.dyepig.2012.01.024
20. [20]
  Chen, W.; Li, Z.; Shi, W.; Ma, H. M. Chem. Commun. 2012, 48, 2809. doi: 10.1039/c2cc17768d
21. [21]
  Zhuo, J. B.; Yan, X. Q.; Wang, X. X.; Xie, L. L.; Yuan, Y. F. Chin. J. Org. Chem. 2015, 35, 1090(in Chinese).
22. [22]
  Wang, F.; Wu, J. S.; Zhuang, X. Q.; Zhang, W. J.; Liu, W. M. Sens. Actuators, B 2010, 146, 260. doi: 10.1016/j.snb.2010.02.007
23. [23]
  Qu, Y.; Hua, J.; Tian, H. Org. Lett. 2010, 12, 3320. doi: 10.1021/ol101081m
24. [24]
  Wang, J. Q.; Yang, L. Y.; Hou, C.; Cao, H. S. Org. Biomol. Chem. 2012, 10, 6271. doi: 10.1039/c2ob25903f
25. [25]
  Ke, I. S.; Myahkostupov, M.; Castellano, F. N. J. Am. Chem. Soc. 2012, 134, 15309. doi: 10.1021/ja308194w
26. [26]
  Fu, L.; Jiang, F. L.; Fortin, D.; Harvey, P. D.; Liu, Y. Chem. Commun. 2011, 47, 5503. doi: 10.1039/c1cc10784d
27. [27]
  Liu, X. M.; Zhao, Q.; Li, Y.; Song, W. C.; Li, Y. P.; Chang, Z.; Bu, X. H. Chin. Chem. Lett. 2013, 24, 962. doi: 10.1016/j.cclet.2013.06.032
28. [28]
  Lv, H. M.; Yang, X. F.; Zhong, Y. G.; Guo, Y.; Li, Z.; Li, H. Anal. Chem. 2014, 86, 1800. doi: 10.1021/ac4038027
29. [29]
  Zhao, Z. S.; Guo, X. D.; Li, S. Y.; Yang, G. Q. Acta Chim. Sinica 2016, 74, 593(in Chinese).
30. [30]
  Yu, H. B.; Li, H. L.; Zhang, X. F.; Xiao, Y.; Fang, P. J.; Lv, C. J.; Hou, W. Acta Chim. Sinica 2015, 73, 450(in Chinese).
31. [31]
  Duan, Y. W.; Yang, X. F.; Zhong, Y. G.; Guo, Y.; Li, Z.; Li, H. Anal. Chim. Acta 2015, 859, 59. doi: 10.1016/j.aca.2014.12.054
32. [32]
  Yang, Y.; Hang, Y. Y.; Zhang, G. X.; Zhao, R.; Zhang, D. Q. Acta Chim. Sinica 2016, 74, 871(in Chinese).
33. [33]
  Wu, Z. S.; Tang, X. J. Anal. Chem. 2015, 87, 8613. doi: 10.1021/acs.analchem.5b02578
34. [34]
  Li, L.; Ji, Y. Z.; Tang, X. J. Anal. Chem. 2014, 86, 10006. doi: 10.1021/ac503177n
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