Citation: Hao-Ran Qu, Zi-You Zhang, Nan Wang, Qian Sun, Shan-Shan Liu, Wei-Bing Zhang, Jun-Hong Qian. Colorimetric and fluorimetric detection of cysteine: Unexpected Michael addition-elimination reaction[J]. Chinese Chemical Letters, ;2015, 26(10): 1249-1254. doi: 10.1016/j.cclet.2015.06.016 shu

Colorimetric and fluorimetric detection of cysteine: Unexpected Michael addition-elimination reaction

1.
1 Shanghai Key Laboratory of Functional Materials Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China;
2.
2 Shanghai Key Laboratory of Chemical Biology, School of Pharmacy, East China University of Science and Technology, Shanghai 200237, China

Corresponding author: Jun-Hong Qian,
Received Date: 25 February 2015
Available Online: 4 June 2015
Fund Project: This work was financially supported by National 973 Program (No. 2011CB910403) (No. 2011CB910403) Shanghai Municipal Natural Science Foundation (No. 15ZR1409000) (No. 15ZR1409000)the open fund of Shanghai Key Laboratory of Chemical Biology (No. SKLCB-2013-03). (No. SKLCB-2013-03)

The synthesis of three isomers based on Michael addition mechanism for the detection of sulfurcontaining species in aqueous solution is described. These compounds are constructed by conjugating an enone to a coumarin fluorophore. A substituted-phenyl (o, m, or p-) was appended at the carbonyl carbon to adjust the reactivity. The experimental results showed that (E)-7-(diethylamino)-3-(3-(3-hydroxyphenyl)-3-oxoprop-1-en-1-yl)-2H-chromen-2-one (m-QPS) and (E)-7-(diethylamino)-3-(3-(4-hydroxyphenyl)-3-oxoprop-1-en-1-yl)-2H-chromen-2-one (p-QPS) barely react with sulfur-containing nucleophiles, while (E)-7-(diethylamino)-3-(3-(2-hydroxyphenyl)-3-oxoprop-1-en-1-yl)-2H-chromen-2-one (o-QPS) exhibited a fast response toward sulfite, sulfide and thiols in DMSO/phosphate buffer (2:1). The above results are probably due to the intramolecular H-bonding activated Michael addition. More interestingly, cysteine triggered unusual photophysical responses of o-QPS:the original absorption (488 nm) and emission peaks (573 nm) underwent significant blue shifts initially and then recovered, which might be caused by the Michael addition and elimination reaction, respectively.
- Michael addition,
- Sulfur-containing compounds,
- Cysteine,
- Fluorescent probe
1. [1]
  [1] Z. Abedinzadeh, Sulfur-centered reactive intermediates derived from the oxidation of sulfur compounds of biological interest, Can. J. Physiol. Pharmacol. 79(2001) 166-170.
2. [2]
  [2] J.W. Calvert, S. Jha, S. Gundewar, et al., Hydrogen sulfide mediates cardioprotection through Nrf2 signaling, Circ. Res. 105(2009) 365-374.
3. [3]
  [3] S.C. Gupta, J.H. Kim, S. Prasad, B.B. Aggarwal, Regulation of survival, proliferation, invasion, angiogenesis, and metastasis of tumor cells through modulation of inflammatory pathways by nutraceuticals, Cancer Metastasis Rev. 29(2010) 405-434.
4. [4]
  [4] D.J. Zhou, L.B. Dai, H. Ni, G.L. Hui, S.G. Yuan, Preparation and characterization of polyphenylene sulfide-based chelating fibers, Chin. Chem. Lett. 25(2014) 221-225.
5. [5]
  [5] S.W. Benson, Thermochemistry and kinetics of sulfur-containing molecules and radicals, Chem. Rev. 78(1978) 23-35.
6. [6]
  [6] X.F. Yang, Z. Su, C.H. Liu, H.P. Qi, M.L. Zhao, A thiol-selective fluorogenic probe based on the cleavage of 4-methylumbelliferyl-20,40, 60-trinitropheyl ether, Anal. Bioanal. Chem. 396(2010) 2667-2674.
7. [7]
  [7] M. Zhang, M.X. Yu, F.Y. Li, et al., A highly selective fluorescence turn-on sensor for cysteine/homocysteine and its application in bioimaging, J. Am. Chem. Soc. 129(2007) 10322-10333.
8. [8]
  [8] Y.C. Chen, C.C. Zhu, Z.H. Yang, et al., A ratiometric fluorescent probe for rapid detection of hydrogen sulfide in mitochondria, Angew. Chem. Int. Ed. 52(2013) 1688-1691.
9. [9]
  [9] Y.Q. Sun, M.L. Chen, J. Liu, et al., Nitroolefin-based coumarin as a colorimetric and fluorescent dual probe for biothiols, Chem. Commun. 47(2011) 11029-11031.
10. [10]
  [10] L. Li, H.Y. Li, L. Sun, et al., A highly sensitive fluorescence probe for fast thiolquantification assay of glutathione reductase, Angew. Chem. Int. Ed. 48(2009) 4034-4037.
11. [11]
  [11] S.T. Huang, K.N. Ting, K.L. Wang, Development of a long-wavelength fluorescent probe based on quinone-methide-type reaction to detect physiologically significant thiols, Anal. Chim. Acta 620(2008) 120-126.
12. [12]
  [12] H. Chen, Z.L. Zou, S.L. Tan, et al., Efficient synthesis of water-soluble calix[4] arenes via thiol-ene"click" chemistry, Chin. Chem. Lett. 24(2013) 367-369.
13. [13]
  [13] W.M. Xuan, C.Q. Sheng, Y.T. Cao, W.H. He, W. Wang, Fluorescent probes for the detection of hydrogen sulfide in biological systems, Angew. Chem. Int. Ed. 51(2012) 2282-2284.
14. [14]
  [14] A.R. Lippert, E.J. New, C.J. Chang, Reaction-based fluorescent probes for selective imaging of hydrogen sulfide in living cells, J. Am. Chem. Soc. 133(2011) 10078-10080.
15. [15]
  [15] J.H. Lee, C.S. Lim, Y.S. Tian, J.H. Han, B.R. Cho, A two-photon fluorescent probe for thiols in live cells and tissues, J. Am. Chem. Soc. 132(2010) 1216-1217.
16. [16]
  [16] M.M. Pires, J. Chmielewski, Fluorescence imaging of cellular glutathione using a latent rhodamine, Org. Lett. 10(2008) 837-840.
17. [17]
  [17] X. Li, S.J. Qian, Q.J. He, et al., Design and synthesis of a highly selective fluorescent turn-on probe for thiol bioimaging in living cells, Org. Biomol. Chem. 8(2010) 3627-3630.
18. [18]
  [18] S.M. Ji, H.M. Guo, X.L. Yuan, et al., A highly selective off-on red-emitting phosphorescent thiol probe with large stokes shift and long luminescent lifetime, Org. Lett. 12(2010) 2876-2879.
19. [19]
  [19] S.P. Wang, W.J. Deng, D. Sun, et al., A colorimetric and fluorescent merocyaninebased probe for biological thiols, Org. Biomol. Chem. 7(2009) 4017-4020.
20. [20]
  [20] W. Jiang, Q.Q. Fu, H.Y. Fan, J. Ho, W. Wang, A highly selective fluorescent probe for thiophenols, Angew. Chem. 119(2007) 8597-8600.
21. [21]
  [21] J. Bouffard, Y. Kim, T.M. Swage, R. Weissleder, S.A. Hilderbrand, A highly selective fluorescent probe for thiol bioimaging, Org. Lett. 10(2008) 37-40.
22. [22]
  [22] J.Y. Shao, H.M. Guo, S.M. Ji, J.Z. Zhao, Styryl-BODIPY based red-emitting fluorescent OFF-ON molecular probe for specific detection of cysteine, Biosens. Bioelectron. 26(2011) 3012-3017.
23. [23]
  [23] B.A. Krizek, B.T. Amann, V.J. Kilfoil, D.L. Merkle, J.M. Berg, A consensus zinc finger peptide:design, high-affinity metal binding, a pH-dependent structure, and a His to Cys sequence variant, J. Am. Chem. Soc. 113(1991) 4518-4523.
24. [24]
  [24] H.P. Wu, C.C. Huang, T.L. Cheng, W.L. Tseng, Sodium hydroxide as pretreatment and fluorosurfactant-capped gold nanoparticles as sensor for the highly selective detection of cysteine, Talanta 76(2008) 347-352.
25. [25]
  [25] N. Shao, J.Y. Jin, S.M. Cheung, et al., A spiropyran-based ensemble for visual recognition and quantification of cysteine and homocysteine at physiological levels, Angew. Chem. 118(2006) 5066-5070.
26. [26]
  [26] X.L. Pei, H.Y. Tian, W.B. Zhang, A.M. Brouwer, J.H. Qian, Colorimetric and fluorescent determination of sulfide and sulfite with kinetic discrimination, Analyst 139(2014) 5290-5296.
27. [27]
  [27] H.Y. Tian, J.H. Qian, Q. Sun, et al., A coumarin-based fluorescent probe for differential identification of sulfide and sulfite in CTAB micelle solution, Analyst 139(2014) 3373-3377.
28. [28]
  [28] H.Y. Tian, J.H. Qian, Q. Sun, H.Y. Bai, W.B. Zhang, Colorimetric and ratiometric fluorescent detection of sulfite in water via cationic surfactant-promoted addition of sulfite to a,b-unsaturated ketone, Anal. Chim. Acta 788(2013) 165-170.
29. [29]
  [29] G.J. Kim, K. Lee, H. Kwon, H.T. Kim, Ratiometric fluorescence imaging of cellular glutathione, Org. Lett. 13(2011) 2799-2801.
1. [1]
  Yudi Cheng , Xiao Wang , Jiao Chen , Zihan Zhang , Jiadong Ou , Mengyao She , Fulin Chen , Jianli Li . A near-infrared fluorescent probe for visualizing transformation pathway of Cys/Hcy and H₂S and its applications in living system. Chinese Chemical Letters, 2024, 35(5): 109156-. doi: 10.1016/j.cclet.2023.109156
2. [2]
  Chuan-Zhi Ni , Ruo-Ming Li , Fang-Qi Zhang , Qu-Ao-Wei Li , Yuan-Yuan Zhu , Jie Zeng , Shuang-Xi Gu . A chiral fluorescent probe for molecular recognition of basic amino acids in solutions and cells. Chinese Chemical Letters, 2024, 35(10): 109862-. doi: 10.1016/j.cclet.2024.109862
3. [3]
  Tao Liu , Xuwei Han , Xueyi Sun , Weijie Zhang , Ke Gao , Runan Min , Yuting Tian , Caixia Yin . An activated fluorescent probe to monitor NO fluctuation in Parkinson’s disease. Chinese Chemical Letters, 2025, 36(3): 110170-. doi: 10.1016/j.cclet.2024.110170
4. [4]
  Huamei Zhang , Jingjing Liu , Mingyue Li , Shida Ma , Xucong Zhou , Aixia Meng , Weina Han , Jin Zhou . Imaging polarity changes in pneumonia and lung cancer using a lipid droplet-targeted near-infrared fluorescent probe. Chinese Chemical Letters, 2024, 35(12): 110020-. doi: 10.1016/j.cclet.2024.110020
5. [5]
  Fan Zheng , Runsha Xiao , Shuai Huang , Zhikang Chen , Chen Lai , Anyao Bi , Heying Yao , Xueping Feng , Zihua Chen , Wenbin Zeng . Accurate visualization colorectal cancer by monitoring viscosity variations with a novel mitochondria-targeted fluorescent probe. Chinese Chemical Letters, 2025, 36(2): 109876-. doi: 10.1016/j.cclet.2024.109876
6. [6]
  Zhixiao Xiong , Shanni Qiu , Yuyu Wang , Houna Duan , Yi Xiao , Yufang Xu , Weiping Zhu , Xuhong Qian . Photocalibrated NO release from the zinc ion fluorescent probe based on naphthalimide and its application in living cells. Chinese Chemical Letters, 2025, 36(4): 110002-. doi: 10.1016/j.cclet.2024.110002
7. [7]
  Hui Zhang , Rong Feng , Wanyi Yu , Hongbei Wei , Tianhong Wu , Peng Zhang , Wenhai Bian , Xin Li , Di Gao , Guojun Weng , Zhe Yang , Tony D. James , Xiaolong Sun . Evaluating the global thiols redox state in living cells using a reducing sulfur species responsive fluorescence switching platform. Chinese Chemical Letters, 2025, 36(4): 110528-. doi: 10.1016/j.cclet.2024.110528
8. [8]
  Chuanfeng Fan , Jian Gao , Yingkai Gao , Xintong Yang , Gaoning Li , Xiaochun Wang , Fei Li , Jin Zhou , Haifeng Yu , Yi Huang , Jin Chen , Yingying Shan , Li Chen . A non-peptide-based chymotrypsin-targeted long-wavelength emission fluorescent probe with large Stokes shift and its application in bioimaging. Chinese Chemical Letters, 2024, 35(10): 109838-. doi: 10.1016/j.cclet.2024.109838
9. [9]
  Lei Shen , Hongmei Liu , Ming Jin , Jinchao Zhang , Caixia Yin , Shuxiang Wang , Yutao Yang . “Three-in-one” strategy of trifluoromethyl regulated blood-brain barrier permeable fluorescent probe for peroxynitrite and antiepileptic evaluation of edaravone. Chinese Chemical Letters, 2024, 35(10): 109572-. doi: 10.1016/j.cclet.2024.109572
10. [10]
  Han-Min Wang , Yan-Chen Li , Lu-Lu Sun , Ming-Ye Tang , Jia Liu , Jiahao Cai , Lei Dong , Jia Li , Yi Zang , Hai-Hao Han , Xiao-Peng He . Protein-encapsulated long-wavelength fluorescent probe hybrid for imaging lipid droplets in living cells and mice with non-alcoholic fatty liver. Chinese Chemical Letters, 2024, 35(11): 109603-. doi: 10.1016/j.cclet.2024.109603
11. [11]
  Jiajia Lv , Jie Gao , Hongyu Li , Zeli Yuan , Nan Dong . Rational design of hydroxytricyanopyrrole-based probes with high affinity and rapid visualization for amyloid-β aggregates in vitro and in vivo. Chinese Chemical Letters, 2024, 35(5): 108940-. doi: 10.1016/j.cclet.2023.108940
12. [12]
  Chao Liu , Chao Jia , Shi-Xian Gan , Qiao-Yan Qi , Guo-Fang Jiang , Xin Zhao . A luminescent one-dimensional covalent organic framework for organic arsenic sensing in water. Chinese Chemical Letters, 2024, 35(11): 109750-. doi: 10.1016/j.cclet.2024.109750
13. [13]
  Yunkang Tong , Haiqiao Huang , Haolan Li , Mingle Li , Wen Sun , Jianjun Du , Jiangli Fan , Lei Wang , Bin Liu , Xiaoqiang Chen , Xiaojun Peng . Cooperative bond scission by HRP/H₂O₂ for targeted prodrug activation. Chinese Chemical Letters, 2024, 35(12): 109663-. doi: 10.1016/j.cclet.2024.109663
14. [14]
  Quan Zhang , Shunjie Xing , Jingqian Han , Li Feng , Jianchun Li , Zhaosheng Qian , Jin Zhou . Organic pollutant sensing for human health based on carbon dots. Chinese Chemical Letters, 2025, 36(1): 110117-. doi: 10.1016/j.cclet.2024.110117
15. [15]
  Sixin Ai , Wenxiu Li , Huayong Zhu , Yang Wan , Weiying Lin . Viscosity-responsive signal amplification dual-modal probe triggered by cysteine/homocysteine for monitoring diabetic liver damages and repair processes. Chinese Chemical Letters, 2025, 36(3): 109904-. doi: 10.1016/j.cclet.2024.109904
16. [16]
  Xing Tian , Di Wu , Wanheng Wei , Guifu Dai , Zhanxian Li , Benhua Wang , Mingming Yu . A lipid droplets-targetable fluorescent probe for polarity detection in cells of iron death, inflammation and fatty liver tissue. Chinese Chemical Letters, 2024, 35(6): 108912-. doi: 10.1016/j.cclet.2023.108912
17. [17]
  Linfang Wang , Jing Liu , Minghao Ren , Wei Guo . A highly sensitive fluorescent HClO probe for discrimination between cancerous and normal cells/tissues. Chinese Chemical Letters, 2024, 35(6): 108945-. doi: 10.1016/j.cclet.2023.108945
18. [18]
  Yang Liu , Leilei Zhang , Kaixuan Liu , Ling-Ling Wu , Hai-Yu Hu . Penicillin G acylase-responsive near-infrared fluorescent probe: Unravelling biofilm regulation and combating bacterial infections. Chinese Chemical Letters, 2024, 35(11): 109759-. doi: 10.1016/j.cclet.2024.109759
19. [19]
  Pei Huang , Weijie Zhang , Junping Wang , Fangjun Huo , Caixia Yin . Rapid and specific fluorescent probe visualizes dynamic correlation of Cys and HClO in OGD/R. Chinese Chemical Letters, 2025, 36(1): 109778-. doi: 10.1016/j.cclet.2024.109778
20. [20]
  Lanyun Zhang , Weisi Wang , Yu-Qiang Zhao , Rui Huang , Yuxun Lu , Ying Chen , Liping Duan , Ying Zhou . Mechanism study of the molluscicide candidate PBQ on Pomacea canaliculata using a viscosity-sensitive fluorescent probe. Chinese Chemical Letters, 2025, 36(1): 109798-. doi: 10.1016/j.cclet.2024.109798

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(774)
HTML views(2)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142