Journal of the American Chemical Society
Page 4 of 5
Shao, N.; Jin, J.; Wang, H.; Zheng, J.; Yang, R.; Chan, W.; Abliz, Z. J.
Am. Chem. Soc. 2009, 132, 725.
(4) Chen, X.; Zhou, Y.; Peng, X.; Yoon, J. Chem. Soc. Rev. 2010, 39,
2120.
(5) (a) Sun, Y.-Q.; Chen, M.; Liu, J.; Lv, X.; Li, J.-f.; Guo, W. Chem.
Commun. 2011, 47, 11029. (b) Yi, L.; Li, H.; Sun, L.; Liu, L.; Zhang, C.;
Xi, Z. Angew. Chem. Int. Ed. 2009, 48, 4034. (c) Guy, J.; Caron, K.;
Dufresne, S.; Michnick, S. W.; Skene; Keillor, J. W. J. Am. Chem. Soc.
2007, 129, 11969.
(6) (a) 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. (b)
Lim, C. S.; Masanta, G.; Kim, H. J.; Han, J. H.; Kim, H. M.; Cho, B. R.
J. Am. Chem. Soc. 2011, 133, 11132. (c) Pires, M. P.; Chmielewski, J. Org.
Lett. 2008, 10, 837.
In conclusion, we have developed a ratiometric fluorescent
1
2
3
4
5
6
7
8
sensor for discrimination of GSH over Cys and Hcy. The sen-
sor operates by undergoing rapid displacement of chloride
with thiolate. The unique example of discrimination of GSH
from Cys/Hcy is attributed to amino group of Cys/Hcy fur-
ther replacing the thiolate to form amino substituted
BODIPY, which exhibited dramatically different photophysi-
cal properties compared to sulfur substituted BODIPY from
the reaction of GSH. This specific and interesting reaction
mechanism may inspire the exploration of new system for
the selective detection of biothiols.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(7) (a) Zhang, J.; Shibata, A.; Ito, M.; Shuto, S.; Ito, Y.; Mannervik,
B.; Abe, H.; Morgenstern, R. J. Am. Chem. Soc. 2011, 133, 14109. (b)
Shao, J.; Sun, H.; Guo, H.; Ji, S.; Zhao, J.; Wu, W.; Yuan, X.; Zhang, C.;
James, T. D. Chem. Sci. 2012, 3, 1049.
(8) (a) Tang, B.; Xing, Y.; Li, P.; Zhang, N.; Yu, F.; Yang, G. J. Am.
Chem. Soc. 2007, 129, 11666. (b) Zhang, M.; Yu, M.; Li, F.; Zhu, M.; Li,
M.; Gao, Y.; Li, L.; Liu, Z.; Zhang, J.; Zhang, D.; Yi, T.; Huang, C. J. Am.
Chem. Soc. 2007, 129, 10322.
(9) (a) Wang, P.; Liu, J.; Lv, X.; Liu, Y.; Zhao, Y.; Guo, W. Org. Lett.
2012, 14, 520. (b) Guo, Z.; Nam, S.; Park, S.; Yoon, J. Chem. Sci. 2012, 3,
2760. (c) Yang, X.; Guo, Y.; Strongin, R. M. Angew. Chem. Int. Ed.
2011, 50, 10690. (d) Wang, W.; Rusin, O.; Xu, X.; Kim, K. K.; Es-
cobedo, J. O.; Fakayode, S. O.; Fletcher, K. A.; Lowry, M.; Schowalter,
C. M.; Lawrence, C. M.; Fronczek, F. R.; Warner, I. M.; Strongin, R.
M. J. Am. Chem. Soc. 2005, 127, 15949. (e) Rusin, O.; St. Luce, N. N.;
Agbaria, R. A.; Escobedo, J. O.; Jiang, S.; Warner, I. M.; Dawan, F. B.;
Lian, K.; Strongin, R. M. J. Am. Chem. Soc. 2003, 126, 438.
(10) Guo, Y.; Yang, X.; Hakuna, L.; Barve, A.; Escobedo, J. O.; Low-
ry, M.; Strongin, R. M. Sensors 2012, 12, 5940.
ASSOCIATED CONTENT
Supporting Information
Synthesis details and characterization of compounds 1a-f, 2a,
1b-Cys and 1b-N. Time-dependent fluorescence response of
1a in the presence of Cys and Hcy. Absorption and emission
spectra of 1a with increasing amount of Cys and GSH. Time-
dependent fluorescence response of 1b and 1c in the pres-
ence of GSH, Cys and Hcy. This material is available free of
AUTHOR INFORMATION
Corresponding Author
ACKNOWLEDGMENT
(11) Hoyle, C. E.; Lowe, A. B.; Bowman, C. N. Chem. Soc. Rev. 2010,
39, 1355.
We thank Prof. R. Boulatov (UIUC) for his useful discussion
and revision of the manuscript, and Prof. P. Wang (TIPC,
CAS) for providing HeLa cells. We are grateful for financial
support from the National Natural Science Foundation of
China (21102155, 21222210, 91027041), the Chinese Academy of
Sciences (100 talents program) and the Ministry of Science
and Technology of China (2013CB933801).
(12) (a) Boens, N.; Leen, V.; Dehaen, W. Chem. Soc. Rev. 2012, 41,
1130. (b) Kobayashi, T.; Komatsu, T.; Kamiya, M.; Campos, C.;
González-Gaitán, M.; Terai, T.; Hanaoka, K.; Nagano, T.; Urano, Y. J.
Am. Chem. Soc. 2012, 134, 11153. (c) Guo, H.; Jing, Y.; Yuan, X.; Ji, S.;
Zhao, J.; Li, X.; Kan, Y. Org. Biomol. Chem. 2011, 9, 3844. (d) Do-
maille, D. W.; Zeng, L.; Chang, C. J.; J. Am. Chem. Soc. 2010, 132, 1194.
(e) Ulrich, G.; Ziessel, R.; Harriman, A. Angew. Chem. Int. Ed. 2008,
47, 1184. (f) Loudet, A.; Burgess, K. Chem. Rev. 2007, 107, 4891.
(13) (a) Rohand, T.; Baruah, M.; Qin, W.; Boens, N.; Dehaen, W.
Chem. Commun. 2006, 266. (b) Rohand, T.; Qin, W.; Boens, N.;
Dehaen, W. Eur. J. Org. Chem. 2006, 2006, 4658.
(14) (a) Wu, J.; Liu, W.; Ge, J.; Zhang, H.; Wang, P. Chem. Soc. Rev.
2011, 40, 3483. (b) Kurishita, Y.; Kohira, T.; Ojida, A.; Hamachi, I. J.
Am. Chem. Soc. 2010, 132, 13290.
(15) (a) Cao, X.; Lin, W.; Zheng, K.; He, L. Chem. Commun. 2012,
48, 10529. (b) Lippert, A. R.; New, E. J.; Chang, C. J. J. Am. Chem. Soc.
2011, 133, 10078.
REFERENCES
(1) Meister, A. J. Biol. Chem. 1988, 263, 17205.
(2) (a) Lu, S. Mol. Aspects Med. 2009, 30, 42. (b) Refsum, H.;
Ueland, P. M.; Nygard, O.; Vollset, S. E. Annu. Rev. Med. 1998, 49, 31.
(3) (a) McMahon, B. K.; Gunnlaugsson, T. J. Am. Chem. Soc. 2012,
134, 10725. (b) Guo, Y.; Wang, H.; Sun, Y.; Qu, B. Chem. Commun.
2012, 48, 3221. (c) Deng, R.; Xie, X.; Vendrell, M.; Chang, Y. -T..; Liu,
X. J. Am. Chem. Soc. 2011, 133, 20168. (d) Kim, G.-J.; Lee, K.; Kwon, H.;
Kim, H.-J. Org. Lett. 2011, 13, 2799. (e) Zhu, B.; Zhang, X.; Li, Y.;
Wang, P.; Zhang, H.; Zhuang, X. Chem. Commun. 2010, 46, 5710. (f)
Li, Y.; Wu, P.; Xu, H.; Zhang, H.; Zhong, X. Analyst 2010, 136, 196. (g)
(16) Becker, P. S.; Cohen, C. M.; Lux, S. E. J. Bio. Chem. 1986, 261,
4620.
ACS Paragon Plus Environment