Citation: Cheng Xiaohong, Xu Ke, Qu Shaohua, Ruan Zhijun. Ratiometric Fluorescent Probe for Homocysteine and Cysteine Based on the Aldehyde Functionalized Coumarin and Successful Bioimaging Application[J]. Chinese Journal of Organic Chemistry, ;2019, 39(10): 2835-2842. doi: 10.6023/cjoc201904020 shu

Ratiometric Fluorescent Probe for Homocysteine and Cysteine Based on the Aldehyde Functionalized Coumarin and Successful Bioimaging Application

a.
Hubei Key Laboratory of Low Dimensional Optoelectronic Materials and Devices, Hubei University of Arts and Science, Xiangyang 441053, Hubei
b.
College of chemistry and Chemical Engineering, Huanggang Normal University, Huanggang 438000, Hubei

Corresponding author: Cheng Xiaohong, chengxiaohong0807@126.com
Received Date: 9 April 2019
Revised Date: 14 May 2019
Available Online: 6 October 2019
Fund Project: the Natural Science Foundation of Hubei Province 2018CFB454the National Natural Science Foundation of China 21704032Project supported by the National Natural Science Foundation of China (No. 21704032), the Natural Science Foundation of Hubei Province (No. 2018CFB454) and the Hubei Superior and Distinctive Discipline Group of "Mechatronics and Automobiles" (No. XKQ2019038)the Hubei Superior and Distinctive Discipline Group of "Mechatronics and Automobiles" XKQ2019038

Figures(8)

Novel reactive probes (C1 and C2) towards homocysteine/cysteine (Hcy/Cys) were designed and synthesized, based on the unique nucleophilic nature of bio-thiols. In the presence of Hcy/Cys, probe C1 displayed remarkable fluorescence enhancement. Meanwhile, ratiometric fluorescent probe C2 was designed through subtle structure adjustment. Differently, compound C2 displayed dramatic blue-shift in both fluorescence (100 nm) and absorption (95 nm) spectra upon the addition of Hcy/Cys. By virtue of the specific nucleophilic reaction, probe C2 had outstanding selectivity towards Hcy over Cys, GSH and other amino acids. The detection limit of probe C2 was calculated to be as low as 2.8×10^-7 mol/L. Moreover, C2 was successfully applied to microscopic imaging for the detection of Hcy in HeLa cells with ratiometric fluorescent methods.
- chemosensor,
- bio-thiols,
- ratiometric fluorescence,
- intramolecular charge transfer,
- cell imaging
1. [1]
  (a) An, L.; Tang, Y.; Wang, S.; Li, Y.; Zhu, D. Macromol. Rapid Commun. 2006, 27, 993.
  (b) Zhao, D.; Du, J.; Chen, Y.; Ji, X.; He, Z.; Chan, W. H. Macromolecules 2008, 41, 5373.
2. [2]
  (a) Weerapana, E.; Wang, C.; Simon, G. M.; Richter, F.; Khare, S.; Dillon, M. B.; Bachovchin, D. A.; Mowen, K.; Baker, D.; Cravatt, B. F. Nature 2010, 468, 790.
  (b) Reiser, J.; Adair, B.; Reinheckel, T. J. Clin. Invest. 2010, 120, 3421.
  (c) Lin, J.; Lee, I. M.; Song, Y.; Cook, N. R.; Selhub, J.; Manson, J. E.; Buring, J. E.; Zhang, S. M. Cancer Res. 2010, 70, 2397.
3. [3]
  (a) Wang, J.; Hu, L. J.; Shen, J.; Jiang, J. Q.; Yu, K. Y., Sun, R. G. Chin. J. Org. Chem. 2018, 38, 760(in Chinese).
  (王军, 虎良军, 申婧, 姜吉泉, 郁科勇, 孙荣国, 有机化学, 2018, 38, 760.)
  (b) Ding, S.; Liu, M.; Hong, Y. Sci. China Chem. 2018, 61, 12.
  (c) Zhou, Y.; Yoon, J. Chem. Soc. Rev. 2012, 41, 52.
  (d) Jung, H. S.; Chen, X.; Kim, J. S.; Yoon, J. Chem. Soc. Rev. 2013, 42, 6019.
  (e) Yin, C.; Huo, F.; Zhang, J.; Martinez-Manez, R.; Yang, Y.; Lv, H.; Li, S. Chem. Soc. Rev. 2013, 42, 6032.
  (f) Yang, Y.; Zhao, Q.; Feng, W.; Li, F. Chem. Rev. 2012, 113, 192.
4. [4]
  (a) Zhang, M.; Xiao, H. F.; Han, Z. X.; Yang, L. Q.; Wu, X. Y. Chin. J. Org. Chem. 2018, 38, 926(in Chinese).
  (张敏, 肖慧丰, 韩志湘, 仰榴青, 吴向阳, 有机化学, 2018, 38, 926.)
  (b) Jiang, K.; Cao, L.; Hao, Z. F.; Chen, M. Y.; Cheng, J. L.; Li, X.; Xiao, Pi.; Chen, L.; Wang, Z. Y. Chin. J. Org. Chem. 2017, 37, 2221(in Chinese).
  (蒋凯, 曹梁, 郝志峰, 陈美燕, 程洁銮, 李晓, 肖萍, 陈亮, 汪朝阳, 有机化学, 2017, 37, 2221.)
  (c) Hou, S. H.; Qu, Z. G.; Zhong, K. L.; Bian, Y. J.; Tang, L. J. Chin. J. Org. Chem. 2016, 36, 768(in Chinese).
  (侯淑华, 曲忠国, 钟克利, 边延江, 汤立军, 有机化学, 2016, 36, 768.)
  (d) Srikun, D.; Miller, E. W.; Domaille, D. W.; Chang, C. J. J. Am. Chem. Soc. 2008, 130, 4596.
  (e) Komatsu, K.; Urano, Y.; Kojima, H.; Nagano, T. J. Am. Chem. Soc. 2007, 129, 13447.
  (f) Tremblay, M. S.; Halim, M.; Sames, D. J. Am. Chem. Soc. 2007, 129, 7570.
5. [5]
  Kimura, E.; Koike, T. Chem. Soc. Rev. 1998, 27, 179. doi: 10.1039/a827179z
6. [6]
  (a) Jung, H. S.; Han, J. H.; Pradhan, T.; Kim, S.; Lee, S. W.; Sessler, J. L.; Kim, T. W.; Kang, C.; Kim, J. S. Biomaterials 2012, 33, 945.
  (b) Yuan, L.; Lin, W.; Yang, Y. Chem. Commun. 2011, 47, 6275.
  (c) Jung, H. S.; Ko, K. C.; Kim, G. H.; Lee, A. R.; Na, Y. C.; Kang, C.; Lee, J. Y.; Kim, J. S. Org. Lett. 2011, 13, 1498.
  (d) Kwon, H.; Lee, K.; Kim. H.-J. Chem. Commun. 2011, 47, 1773.
  (e) Chen, X.; Ko, S. K.; Kim, M. J. Chem. Commun. 2010, 46, 2751.
7. [7]
  (a) Yang, T.; Guo, Z.; Shao, A.; Zhao, P.; Zhu, W. Chin. J. Appl. Chem. 2016, 33, 397(in Chinese).
  (杨婷婷, 郭志前, 邵安东, 赵平, 朱为宏, 应用化学, 2016, 33, 397.)
  (b) Lee, M. H.; Han, J. H.; Kwon, P. S.; Bhuniya, S.; Kim, J. Y.; Sessler, J. L.; Kang, C.; Kim, J. S. J. Am. Chem. Soc. 2012, 134, 1316.
  (c) Shao, J.; Sun, H.; Guo, H.; Ji, S.; Zhao, J.; Wu, W.; Yuan, X.; Zhang, C.; James, T. D. Chem. Sci. 2012, 3, 1049.
  (d) Lim C. S.; Masanta, G.; Kim, H. J.; Han, J. H.; Kim, H. M.; Cho, B. R. J. Am. Chem. Soc. 2011, 133, 11132.
  (e) Zhao, C.; Zhou, Y.; Lin, Q.; Zhu, L.; Feng, P.; Zhang, Y.; Cao, J. J. Phys. Chem. B 2010, 115, 642.
8. [8]
  (a) Secor, K.; Plante, J.; Avetta, C.; Glass, T. J. Mater. Chem. 2005, 15, 4073.
  (b) Zhou, Y.; Won, J.; Lee, J. Y.; Yoon, J. Chem. Commun. 2011, 47, 1997.
9. [9]
  (a) Xiong, L.; Zhao, Q.; Chen, H.; Wu, Y.; Dong, Z.; Zhou, Z.; Li, F. Inorg. Chem. 2010, 49, 6402.
  (b) Shiu, H. Y.; Chong, H. C.; Leung, Y. C.; Wong, M. K.; Che, C. M. Chem. Eur. J. 2010, 16, 3308.
  (c) Li, H.; Fan, J.; Wang, J.; Tian, M.; Du, J.; Sun, S.; Sun, P.; Peng, X. Chem. Commun. 2009, 45, 5904.
  (d) Lee, K. S.; Kim, T. K.; Lee, J. H.; Kim, H. J.; Hong, J. I. Chem. Commun. 2008, 44, 6173.
10. [10]
  Tsai, M. S.; Hsu, Y. C.; Lin, J. T.; Chen, H. C.; Hsu, C. P. J. Phys. Chem. C 2007, 111, 18785. doi: 10.1021/jp075653h
11. [11]
  Lee, K. S.; Kim, H. J.; Kim, G. H.; Shin, I.; Hong, J. I. Org. Lett. 2008, 10, 49. doi: 10.1021/ol7025763
12. [12]
  Williams, A. T. R.; Winfield, S. A.; Miller, J. N. Analyst 1983, 108, 1067. doi: 10.1039/an9830801067
13. [13]
  Wang, W.; Escobedo, J. O.; Lawrence, C. M.; Strongin, R. M. J. Am. Chem. Soc. 2004, 126, 3400. doi: 10.1021/ja0318838
14. [14]
  Seshadri, S.; Beiser, A.; Selhub, J.; Jacques, P. F.; Rosenberg, I. H.; D'Agostino, R. B.; Wilson, P. W. F.; Wolf, P. A. N. Engl. J. Med. 2002, 346, 476. doi: 10.1056/NEJMoa011613
15. [15]
  Dong, Y. S.; Liu, T. Q.; Wan, X. J.; Pei, H.; Wu, L. S.; Yao, Y. W. Sens. Actuator, B 2017, 241, 1139. doi: 10.1016/j.snb.2016.10.022
16. [16]
  Yuan, L.; Lin, W. Y.; Yang, Y. T. Chem. Commun. 2011, 47, 6275. doi: 10.1039/c1cc11316j
17. [17]
  Zhang, X.; Hang, Y. D.; Qu, W. S.; Yan, Y. C.; Zhao, P.; Hua, J. L. RSC Adv. 2016, 6, 20014. doi: 10.1039/C5RA25220B
18. [18]
  Chen, F.; Chen, Z.; Sun, Y.; Liu, H.; Han, D.; He, H.; Zhang, X.; Wang, S. RSC Adv. 2017, 7, 16387. doi: 10.1039/C6RA28712C
19. [19]
  Sun, Y.; Chen, M.; Liu, J.; Lv, X.; Li, J.; Guo, W. Chem. Commun. 2011, 47, 11029. doi: 10.1039/c1cc14299b
20. [20]
  Li, H.; Jin, L.; Kan, Y.; Yin, B. Sens. Actuator, B 2014, 196, 546. doi: 10.1016/j.snb.2014.02.052
21. [21]
  Qu, W. S.; Yang, L.; Hang, Y. D.; Zhang, X.; Qu, Y.; Hua, J. L. Sens. Actuator, B 2015, 211, 275. doi: 10.1016/j.snb.2015.01.117
22. [22]
  Liu, X.; Niu, L.; Chen, Y.; Yang, Y.; Yang, Q. Biosens. Bioelectron. 2017, 90, 403. doi: 10.1016/j.bios.2016.06.076
23. [23]
  Chen, X.; Ko, S. K.; Kim, M. J.; Shin, I.; Yoon, J. Chem. Commun. 2010, 46, 2751. doi: 10.1039/b925453f
24. [24]
  Jung, H. S.; Ko, K. C.; Kim, G. H.; Lee, A. R.; Na, Y. C.; Kang, C.; Lee, J. Y.; Kim, J. S. Org. Lett. 2011, 13, 1498. doi: 10.1021/ol2001864
25. [25]
  Shao, J.; Guo, H.; Ji, S.; Zhao, J. Biosens. Bioelectron. 2011, 26, 3012. doi: 10.1016/j.bios.2010.12.004
26. [26]
  Long, L.; Lin, W. Y.; Chen, B.; Gao, W.; Yuan, L. Chem. Commun. 2011, 47, 893. doi: 10.1039/C0CC03806G
27. [27]
  (a) Zhang, S.; Wright, J. E. I.; Bansal, G.; Cho, P.; Uludag, H. Biomacromolecules 2005, 6, 2800.
  (b) Shiu, H. Y.; Wong, M. K.; Che, C. M. Chem. Commun. 2011, 47, 4367.
28. [28]
  (a) Tatay, S.; Gavina, P.; Coronado, E.; Palomares, E. Org. Lett. 2006, 8, 3857.
  (b) Palomares, E.; Vilar, R.; Durrant, J. R. Chem. Commun. 2004, 40, 362.
29. [29]
  (a) Delley, B. J. Chem. Phys. 1990, 92, 508.
  (b) Delley, B. J. Chem. Phys. 2000, 113, 7756.
30. [30]
  Lin, Y.; Lin, W. Y.; Song, J. Z.; Yang, Y. T. Chem. Commun. 2011, 47, 12691. doi: 10.1039/c1cc15762k
31. [31]
  (a) Qian, Z.; Shan, X.; Chai, L.; Ma, J.; Chen, J.; Feng, H. ACS Appl. Mater. Interfaces 2014, 6, 6797.
  (b) Meng, Z.; Wu, S.; Zhong, L.; Zeng, M.; Sun, X.; Li, L.; Zhang, S. RSC Adv. 2018, 8, 38075.
  (c) Liao, S.; Zhao, X.; Zhu, F.; Chen, M.; Wu, Z.; Song, X.; Yang, H.; Chen, X. Talanta 2018, 180, 300.
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