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

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

通讯作者: Jun-Hong Qian,

基金项目:
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)

摘要: 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.

关键词:

English

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: 20 June 2015
Fund Project:

Abstract: 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.

Key words:

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.[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] J.W. Calvert, S. Jha, S. Gundewar, et al., Hydrogen sulfide mediates cardioprotection through Nrf2 signaling, Circ. Res. 105(2009) 365-374.[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] 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.[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] 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.[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] S.W. Benson, Thermochemistry and kinetics of sulfur-containing molecules and radicals, Chem. Rev. 78(1978) 23-35.[5] S.W. Benson, Thermochemistry and kinetics of sulfur-containing molecules and radicals, Chem. Rev. 78(1978) 23-35.
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.[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] 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.[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] 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.[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] 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.[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] 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.[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] 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.[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] 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.[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] 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.[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] 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.[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] 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.[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] M.M. Pires, J. Chmielewski, Fluorescence imaging of cellular glutathione using a latent rhodamine, Org. Lett. 10(2008) 837-840.[16] M.M. Pires, J. Chmielewski, Fluorescence imaging of cellular glutathione using a latent rhodamine, Org. Lett. 10(2008) 837-840.
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.[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] 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.[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] 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.[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] 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.[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] 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.[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] 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.[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] 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.[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] 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.[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] 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.[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] 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.[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] 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.[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] 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.[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] G.J. Kim, K. Lee, H. Kwon, H.T. Kim, Ratiometric fluorescence imaging of cellular glutathione, Org. Lett. 13(2011) 2799-2801.[29] G.J. Kim, K. Lee, H. Kwon, H.T. Kim, Ratiometric fluorescence imaging of cellular glutathione, Org. Lett. 13(2011) 2799-2801.

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

通讯作者: Jun-Hong Qian,

English

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

Corresponding author: Jun-Hong Qian,

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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

通讯作者: Jun-Hong Qian,

English

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

Corresponding author: Jun-Hong Qian,

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

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