A Fluorescent Probe for Selective Detection of GSH

doi:10.7517/j.issn.1674-0475.2017.04.015

Abstract

Abstract:

We developed a ratiometric fluorescent probe based on BODIPY which can detect GSH selectively. We did UV-Vis and fluorescence experiments and found that the UV-Vis and fluorescence spectra of probe 1 with GSH exhibited obvious red shifts. Probe 1 exhibited high selectivity and the detection inhibited the interference of Cys and was not interfered by other amino acids. The fluorescence titration experiments showed that probe 1 realized the quantitative detection of GSH with detection limit of 3.3×10^-8 mol/L. The probe was successfully applied to the detection of GSH in living cells.

Key words: BODIPY, fluorescent probe, GSH

WANG Yuan, CHEN Xiaoxiao, LIU Xueliang, CHEN Yuzhe, NIU Liya, WU Lizhu, YANG Qingzheng. A Fluorescent Probe for Selective Detection of GSH[J]. Imaging Science and Photochemistry, 2017, 35(4): 536-545.

References

[1] Shahrokhian S. Lead phthalocyanine as a selective carrier for preparation of a cysteine-selective electrode[J]. Analytical Chemistry, 2001, 73: 5972-5978.
[2] Townsend D M, Tew K D, Tapiero H. The importance of glutathione in human disease[J]. Biomedicine & Pharmacotherapy, 2003, 57: 145-155.
[3] Lu S C. Regulation of glutathione synthesis[J]. Molecular Aspects of Medicine, 2009, 30: 42-59.
[4] Jung H, Chen X, Kim J, Yoon J. Recent progress in luminescent and colorimetric chemosensors for detection of thiols[J]. Chemical Society Reviews, 2013, 42: 6019-6031.
[5] Niu L Y, Chen Y Z, Zheng H R, Wu L Z, Tung C H, Yang Q Z. Design strategies of fluorescent probes for selective detection among biothiols[J]. Chemical Society Reviews, 2015, 44: 6143-6160.
[6] Hewage H S, Anslyn E V. Pattern-based recognition of thiols and metals using a single squaraine indicator[J]. Journal of the American Chemical Society, 2009, 131: 13099-13106.
[7] Yi L, Li H, Sun L, Liu L, Zhang C, Xi Z. A highly sensitive fluorescence probe for fast thiol-quantification assay of glutathione reductase[J]. Angewandte Chemie International Edition, 2009, 48: 4034-4037.
[8] Umezawa K, Yoshida M, Kamiya M, Yamasoba T, Urano Y. Rational design of reversible fluorescentprobes for live-cell imaging and quantification of fast glutathione dynamics[J]. Nature Chemistry, 2017, 9: 279-286.
[9] Pires M M, Chmielewski J. Fluorescence imaging of cellularglutathione using a latent rhodamine[J]. Organic Letters, 2008, 10: 837-840.
[10] Cao X, Lin W, Yu Q. A ratiometric fluorescent probe for thiols based on a tetrakis(4-hydroxyphenyl)porphyrin-coumarin scaffold[J]. The Journal of Organic Chemistry, 2011, 76: 7423-7430.
[11] Zheng Z, Chen P, Xie M, Wu C, Luo Y, Wang W, Jiang J, Liang G. Cell environment-differentiated self-assembly of nanofibers[J]. Journal of the American Chemical Society, 2016, 138: 11128-11131.
[12] Zhang J, Shibata A, Ito M, Shuto S, Ito Y, Mannervik B, Abe H, Morgenstern R. Synthesis and characterization of a series of highly fluorogenic substrates for glutathione transferases, a general strategy[J]. Journal of the American Chemical Society, 2011, 133: 14109-14119.
[13] Shao J, Sun H, Guo H, Ji S, Zhao J,Wu, W, Yuan X, Zhang C, James T D. A highly selective red-emitting FRET fluorescent molecular probe derived from BODIPY for the detection of cysteine and homocysteine: an experimental and theoretical study[J]. Chemical Science, 2012, 3: 1049-1061.
[14] Isik M, Guliyev R, Kolemen S, Altay Y, Senturk B, Tekinay T, Akkaya E U. Designing an intracellular fluorescent probe for glutathione: two modulation sites for selective signal transduction[J]. Organic Letters, 2014, 16: 3260-3263.
[15] He L, Xu Q, Liu Y, Wei H, Tang Y, Lin W. Coumarin-based turn-on fluorescence probe for specific detection of glutathione over cysteine and homocysteine[J]. ACS Applied Materials & Interfaces, 2015, 7: 12809-12813.
[16] Liu Y, Lv X, Liu J, Sun Y Q, Guo W. Construction of a selective fluorescent probe for GSH based on a chloro-functionalized coumarin-enone dye platform[J]. Chemistry A European Journal, 2015, 21: 4747-4754.
[17] Yang X, Guo Y, Strongin R M. Conjugate addition/cyclization sequence enables selective and simultaneous fluorescence detection of cysteine and homocysteine[J]. Angewandte Chemie International Edition, 2011, 50: 10690-10693.
[18] Gao X, Li X, Li L, Zhou J, Ma H. A simple fluorescent off-on probe for the discrimination of cysteine fromglutathione[J]. Chemical Communications, 2015, 51: 9388-9390.
[19] Miao Q, Li Q, Yuan Q, Li L, Hai Z, Liu S, Liang G. Discriminative fluorescence sensing of biothiols in vitro and in living cells[J]. Analytical Chemistry, 2015, 87: 3460-3466.
[20] Zhang J, Wang J, Liu J, Ning L, Zhu X, Yu B, Liu X, Yao X, Zhang H. Near-infrared and naked-eye fluorescence probe for direct and highly selective detection of cysteine and its application in living cells[J]. Analytical Chemistry, 2015, 87: 4856-4863.
[21] Niu W, Guo L, Li Y, Shuang S, Dong C, Wong M. Highly selective two-photon fluorescent probe for ratiometric sensing and imaging cysteine in mitochondria[J]. Analytical Chemistry, 2016, 88: 1908-1914.
[22] Yue Y, Huo F, Ning P, Zhang Y, Chao J, Meng X, Yin C. Dual-site fluorescent probe for visualizing the metabolism of Cys in living cells[J]. Journal of the American Chemical Society, 2017, 139: 3181-3185.
[23] Hakuna L, Escobedo J, Lowry M, Barve A, McCallum N, Strongin R M. A photochemical method for determining plasma homocysteine with limited sample processing[J]. Chemical Communications, 2014, 50: 3071-3073.
[24] Lee H, Choi Y, Kim S, Yoon T, Guo Z, Lee S, Swamy K M K, Kim G, Lee J, Shin I, Yoon J. Selective homocysteine turn-on fluorescent probes and their bioimaging applications[J]. Chemical Communications, 2014, 50: 6967-6969.
[25] Loudet A, Burgess K. BODIPY dyes and their derivatives: syntheses and spectroscopic properties[J]. Chemical Reviews, 2007, 107: 4891-4932.
[26] Boens N, Leen V, Dehaen W. Fluorescent indicators based on BODIPY[J]. Chemical Society Reviews, 2012, 41: 1130-1172.
[27] Kowada T, Maeda H, Kikuchi K. BODIPY-based probes for the fluorescence imaging of biomolecules in living cells[J]. Chemical Society Reviews, 2015, 44: 4953-4972.
[28] Niu L Y, Guan Y S, Chen Y Z, Wu L Z, Tung C H, Yang Q Z, BODIPY-based ratiometroc fluorescent sensor for highly selective detection of glutathione over cystein and homocystein[J]. Journal of the American Chemical Society, 2012, 134: 18928-18931.
[29] Niu L Y, Guan Y S, Chen Y Z, Wu L Z, Tung C H, Yang Q Z. A turn-on fluorescent sensor for the discriminationof cystein from homocystein and glutathione[J]. Chemical Communications, 2013, 49: 1294-1296.
[30] Yin J, Kwon Y,Kim D, Lee D, Kim G, Hu Y, Ryu G H, Yoon J. Cyanine-based fluorescent probe for highly selective detection of glutathione in cell cultures and live mouse tissues[J]. Journal of the American Chemical Society, 2014, 136: 5351-5358.
[31] Liu J, Sun Y Q, Huo Y, Zhang H, Wang L, Zhang P, Song D, Shi Y, Guo W. Simultaneous fluorescence sensing of Cys and GSH from different emission channels[J]. Journal of the American Chemical Society, 2014, 136: 574-577.
[32] Kim S Y, Hong K H, Kim D, Kwon H, Kim H J. Tunable heptamethine-azo dye conjugate as an NIR fluorescent probe for the selective detection of mitochondrial glutathione over cysteine and homocysteine[J]. Journal of the American Chemical Society, 2014, 136: 7018-7025.
[33] Wang X, Lv J, Yao X, Li Y, Huang F, Li M, Yang J, Ruan X, Tang B. Screening and investigation of a cyanine fluorescent probe for simultaneous sensing of glutathione and cysteine under single excitation[J]. Chemical Communications, 2014, 50: 15439-15442.
[34] Liu J, Sun Y Q, Zhang H, Huo Y, Shi Y, Guo W. Simultaneous fluorescent imaging of Cys/Hcy and GSH from different emission channels[J]. Chemical Science, 2014, 5: 3183-3188.
[35] Guan Y S, Niu L Y, Chen Y Z, Wu L Z, Tung C H, Yang Q Z. A near-infrared fluorescent sensor for selective detection of cysteine and its application in live cell imaging[J]. RSC Advances, 2014, 4: 8360-8364.
[36] Niu L Y, Zheng H R, Chen Y Z, Wu L Z, Tung C H, Yang Q Z. Fluorescent sensors for selective detection of thiols: expanding the intramolecular displacement based mechanism to new chromophores[J]. Analyst, 2014, 139: 1389-1395.
[37] Jia M Y, Niu L Y, Zhang Y, Yang Q Z, Tung C H, Guan Y F, Feng L. BODIPY-based fluorometric sensor for the simultaneous determination of Cys, Hcy and GSH in human serum[J]. ACS Applied Materials & Interfaces, 2015, 7: 5907-5914.
[38] Niu L Y, Yang Q Q, Zheng H R, Chen Y Z, Wu L Z, Tung C H, Yang Q Z. BODIPY-based fluorescent probe for thesimultaneous detection of glutathione and cysteine/homocysteine at different excitation wavelengths[J]. RSC Advances, 2015, 5: 3959-3964.
[39] Niu L Y, Jia M Y, Chen P Z, Chen Y Z, Zhang Y, Wu L Z, Duan X F, Tung C H, Guan Y F, Feng L, Yang Q Z. Colorimetric sensors with different reactivity for the quantitative determination of cysteine, homocysteine and glutathione in a mixture[J]. RSC Advances, 2015, 5: 13042-13045.
[40] Liu X L, Niu L Y, Chen Y Z, Zheng M L, Yang Y, Yang Q Z. A mitochondria-targeting fluorescent probe for the selective detection of glutathione in living cells[J]. Organic & Biomolecular Chemistry, 2017, 15: 1072-1075.
[41] Liu X L, Niu L Y, Chen Y Z, Yang Y, Yang Q Z. A multi-emissive fluorescent probe for the discrimination of glutathione and cysteine[J]. Biosensors and Bioelectronics, 2017, 90: 403-409.
[42] Rohand T, Qin W, Boens N, Dehaen W. Palladium-catalyzed coupling reactions for the functionalization of BODIPY dyes with fluorescence spanning the visible spectrum[J]. European Journal of Organic Chemistry, 2006, 20: 4658-4663.