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Progress in Chemistry 2021, Vol. 33 Issue (5): 868-882 DOI: 10.7536/PC200658 Previous Articles   Next Articles

• Original article •

Red/Near-Infrared Biothiol Fluorescent Probes

Yecheng Dang1, Yangzhen Feng1, Dugang Chen1,*()   

  1. 1 Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205, China
  • Received: Revised: Online: Published:
  • Contact: Dugang Chen
  • Supported by:
    National Natural Science Foundation of China(51703171); Graduate Innovative Fund of Wuhan Institute of Technology(CX2019003)
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Small molecular biothiols, including cysteine(Cys), homocysteine(Hcy), and glutathione(GSH), play an import role in physiological and pathological processes. The abnormal levels of biothiols in cells and organisms are closely relevant to various kinds of diseases. Therefore, the detection of biothiols is of great importance. In recent years, the fluorescent probe has shown favorable advantages compared to various other detecting techniques, owing to its facile operation, high temporal-spatial resolution, low destructiveness and visualization. Among the numerous reported thiol fluorescent probes, the probes with red/near-infrared(NIR) emission signal are especially concerned, because of the low background interferences, less disturbance by Raman scattering, deeper penetration depth and less photodamage to biological tissues. All these features endow the thiol fluorescent probes with better properties in cell imaging and great potential in in vivo imaging. Here, we mainly review the paper published in recent three years concerning a variety of thiol fluorescent probes with red or NIR emission. The probes are classified according to their fluorogens, with six kinds described here: rhodamine, BODIPY, cyanine, natural pigment(anthocyanidins and curcumin), donor-acceptor(D-A) conjugated molecules and fluorophores with aggregation induced-emission(AIE). We discuss the molecular design, fluorescent property, recognition mechanism and bioimaging application of each probe. At the same time, the unsolved problems and the prospect of biothiol fluorescent probes with long wavelength emission are also presented.

Contents

1 Introduction

2 Rhodamine-based biothiol fluorescent probes

3 BODIPY-based biothiol fluorescent probes

4 Cyanine-based biothiol fluorescent probes

4.1 Cy7-based biothiol fluorescent probes

4.2 Hemicyanines-based biothiol fluorescent probes

5 Natural pigments-based biothiol fluorescent probes

5.1 Anthocyanin-based biothiol fluorescent probes

5.2 Curcumin-based biothiol fluorescent probes

6 D-A compound-based biothiol fluorescent probes

7 AIE-based biothiol fluorescent probes

8 Conclusion and outlook

Key words: red emission, near-infrared, biothiol, fluorescent probe, imaging
Fig. 1 Molecular structures of cysteine, homocysteine and glutathione
Fig. 2 The structure of rhodamine
Fig. 3 Recognition mechanism of probe 1 with Cys/Hcy[30]
Fig. 4 A: Fluorescence imaging for Cys in MCF-7 cells with and without H2O2 treatment; B: Fluorescence imaging for Cys in D. magna. Reproduced from Ref. 30. Copyright 2019, American Chemical Society[30]
Fig. 5 Recognition mechanism of probe 2 with Cys/GSH[31]
Fig. 6 Recognition mechanism of probe 3 with GSH[32]
Fig. 7 Recognition mechanism of probe 4 with Cys[33]
Fig. 8 The structure of BODIPY
Fig. 9 Recognition mechanism of probe 5 with GSH[36]
Fig. 10 Recognition mechanism of probe 6 with GSH[37]
Fig. 11 Molecular structures of probes 7~9[38?~40]
Fig. 12 The structure of cyanine
Fig. 13 Recognition mechanism of probe 10 with GSH[44]
Fig. 14 Molecular structures of probes 11~13[45?~47]
Fig. 15 The structure of hemicyanines
Fig. 16 Recognition mechanism of probe 14 with GSH[49]
Fig. 17 Molecular structures of probes 15 and 16[50,51]
Fig. 18 Recognition mechanism of probe 17 with Cys[52]
Fig. 19 Recognition mechanism of probe 18 with Cys[53]
Fig. 20 The structure of anthocyanin
Fig. 21 Recognition mechanism of probe 19, 20 with Cys[55,56]
Fig. 22 The structure of curcumin
Fig. 23 Recognition mechanism of probes 21, 22 with biothiols[59,60]
Fig. 24 The structure of triphenylamine,dimethylamino,2-(3-cyano-4,5,5-trimethyl-5H-furan-2-ylidene)malononitrile,isophorone,dicyanoisophoro[61?~63]
Fig. 25 Recognition mechanism of probe 23 with Cys[64]
Fig. 26 Molecular structures of probes 24, 25[65,66]
Fig. 27 Molecular structures of probes 26, 27[67,68]
Fig. 28 The structure of tetraphenylene
Fig. 29 Schematic illustration of probe 28 with GSH[75]
Fig. 30 Two-photon excitation fluorescence imaging for GSH in fish larva. Reproduced from Ref. 75. Copyright 2019, American Chemical Society[75]
Fig. 31 Schematic illustration of probe 29 with Cys[76]
[1]
Wang B J, Liu R J, Fang J G, Wang Y W, Peng Y. Chem. Commun., 2019, 55(78):11762.

doi: 10.1039/C9CC06468K
[2]
Chen D G, Long Z, Dang Y C, Chen L. Anal., 2018, 143(23):5779.

doi: 10.1039/C8AN01657G
[3]
Long Z, Chen L, Dang Y C, Chen D G, Lou X D, Xia F. Talanta, 2019, 204:762.

doi: S0039-9140(19)30689-7 pmid: 31357363
[4]
Tian M, Liu X Y, He H, Ma X Z, Liang C, Liu Y, Jiang F L. Anal. Chem., 2020, 92(14):10068.

doi: 10.1021/acs.analchem.0c01881
[5]
Yang Y T, Zhou T T, Jin M, Zhou K Y, Liu D D, Li X, Huo F J, Li W, Yin C X. J. Am. Chem. Soc., 2020, 142:1614.

doi: 10.1021/jacs.9b12629
[6]
Gates T M, Cysique L A, Siefried K J, Chaganti J, Moffat K J, Brew B J. AIDS, 2016, 30(4):591.

doi: 10.1097/QAD.0000000000000951
[7]
Wang L, Ren M G, Li Z H, Dai L X, Lin W Y. Anal. Methods, 2019, 11(34):4323.

doi: 10.1039/C9AY01167F
[8]
Wang S G, Yin H H, Huang Y, Guan X M. Anal. Chem., 2018, 90(13):8170.

doi: 10.1021/acs.analchem.8b01469
[9]
Chen S, Dong Z P, Cheng M, Zhao Y Q, Wang M Y, Sai N, Wang X, Liu H, Huang G W, Zhang X M. J. Neuroinflammation, 2017, 14:187.

doi: 10.1186/s12974-017-0963-x
[10]
Jiang Y Q, Ji X R, Zhang C Y, Xi Z, Sun L, Yi L. Org. Biomol. Chem., 2019, 17(36):8435.

doi: 10.1039/C9OB01535C
[11]
Zeng H H, Zhou Z Y, Liu F, Deng J, Huang S Y, Li G P, Lai P Q, Xie Y P, Xiao W. Anal., 2019, 144(24):7368.

doi: 10.1039/C9AN01518C
[12]
Jin X, Kang S, Tanaka S, Park S. Angew. Chem. Int. Ed., 2016, 55:7939.

doi: 10.1002/anie.201601026
[13]
Zhang Y D, Wang X, Bai X Y, Li P, Su D, Zhang W, Zhang W, Tang B. Anal. Chem., 2019, 91(13):8591.

doi: 10.1021/acs.analchem.9b01878
[14]
Du Q Q, Hu X, Zhang X D, Cao H Y, Huang Y M. Anal. Methods, 2019, 11(27):3446.

doi: 10.1039/C9AY00999J
[15]
Song K, Kai R, Lu C W, Gao L H, Wang G Y, Guo L Q. Sensor Actuat. B: Chem., 2016, 236:249.

doi: 10.1016/j.snb.2016.06.005
[16]
Yin C X, Xiong K M, Huo F J, Salamanca J C, Strongin R M. Angew. Chem. Int. Ed., 2017, 56(43):13188.

doi: 10.1002/anie.201704084
[17]
Peng H P, Jian M L, Huang Z N, Wang W J, Deng H H, Wu W H, Liu A L, Xia X H, Chen W. Biosens. Bioelectron., 2018, 105:71.

doi: 10.1016/j.bios.2018.01.021
[18]
Wang Y, Zhang C H, Zheng Y H, Ge Y, Yu X Y. Anal. Lett., 2019, 52(9):1487.

doi: 10.1080/00032719.2018.1548020
[19]
Dang Y C, Chen L, Yuan L, Li J B, Chen D G. ChemistrySelect, 2020, 5:584.

doi: 10.1002/slct.v5.2
[20]
Kailass K, Sadovski O, Capello M, Kang Y A, Fleming J B, Hanash S M, Beharry A A. Chem. Sci., 2019, 10(36):8428.

doi: 10.1039/C9SC00283A
[21]
Hou L L, Ning P, Feng Y, Ding Y Q, Bai L, Li L, Yu H Z, Meng X M. Anal. Chem., 2018, 90(12):7122.

doi: 10.1021/acs.analchem.8b01631
[22]
Ren T B, Xu W, Zhang W, Zhang X X, Wang Z Y, Xiang Z, Yuan L, Zhang X B. J. Am. Chem. Soc., 2018, 140(24):7716.

doi: 10.1021/jacs.8b04404
[23]
Fang X N, Zheng Y Z, Duan Y K, Liu Y, Zhong W W. Anal. Chem., 2019, 91(1):482.

doi: 10.1021/acs.analchem.8b05303
[24]
Kim K H, Singha S, Jun Y W, Reo Y J, Kim H R, Ryu H G, Bhunia S, Ahn K H. Chem. Sci., 2019, 10(39):9028.

doi: 10.1039/C9SC02287B
[25]
Wu Y L, Huang S L, Wang J, Sun L H, Zeng F, Wu S Z. Nat. Commun., 2018, 9:3983.

doi: 10.1038/s41467-018-06499-1
[26]
Liu X J, Zhang Q Y, Wang F L, Jiang J H. Anal., 2019, 144(20):5980.

doi: 10.1039/C9AN01303B
[27]
Wang R C, Chen J, Gao J, Chen J A, Xu G, Zhu T L, Gu X F, Guo Z Q, Zhu W H, Zhao C C. Chem. Sci., 2019, 10(30):7222.

doi: 10.1039/C9SC02093D
[28]
Wang L L, Du W, Hu Z J, Uvdal K, Li L, Huang W. Angew. Chem. Int. Ed., 2019, 58(40):14026.

doi: 10.1002/anie.v58.40
[29]
Chen X Q, Pradhan T, Wang F, Kim J S, Yoon J. Chem. Rev., 2012, 112(3):1910.

doi: 10.1021/cr200201z
[30]
Yang M W, Fan J L, Sun W, Du J J, Peng X J. Anal. Chem., 2019, 91(19):12531.

doi: 10.1021/acs.analchem.9b03386
[31]
Liu J, Liu M X, Zhang H X, Wei X H, Wang J J, Xian M, Guo W. Chem. Sci., 2019, 10(43):10065.

doi: 10.1039/C9SC02618E
[32]
Umezawa K, Yoshida M, Kamiya M, Yamasoba T, Urano Y. Nat. Chem., 2017, 9(3):279.

doi: 10.1038/nchem.2648
[33]
Xia S, Zhang Y B, Fang M X, Mikesell L, Steenwinkel T E, Wan S L, Phillips T, Luck R L, Werner T, Liu H Y. ChemBioChem, 2019, 20(15):1986.

doi: 10.1002/cbic.v20.15
[34]
Porubský M, Gurská S, Stanková J, Hajdúch M, Džubák P, Hlaváč J. RSC Adv., 2019, 9(43):25075.

doi: 10.1039/C9RA03472B
[35]
Kowada T, Maeda H, Kikuchi K. Chem. Soc. Rev., 2015, 44(14):4953.

doi: 10.1039/C5CS00030K
[36]
Chen J A, Zhang Z Y, Gao J, Tan J H, Gu X F. Tetrahedron Lett., 2019, 60(18):1226.

doi: 10.1016/j.tetlet.2019.03.051
[37]
Huang C M, Qian Y. Spectrochimica Acta Part A: Mol. Biomol. Spectrosc., 2019, 217:68.

doi: 10.1016/j.saa.2019.03.042
[38]
Wang C J, Xia X, Luo J R, Qian Y. Dye. Pigment., 2018, 152:85.

doi: 10.1016/j.dyepig.2018.01.034
[39]
Xia X, Qian Y, Shen B X. J. Mater. Chem. B, 2018, 6(19):3023.

doi: 10.1039/C7TB03321D
[40]
Wang F F, Fan X Y, Liu Y J, Gao T, Huang R, Jiang F L, Liu Y. Dye. Pigment., 2017, 145:451.

doi: 10.1016/j.dyepig.2017.06.033
[41]
McNamara L E, Rill T A, Huckaba A J, Ganeshraj V, Gayton J, Nelson R A, Sharpe E A, Dass A, Hammer N I, Delcamp J H. Chem. Eur. J., 2017, 23(51):12494.

doi: 10.1002/chem.v23.51
[42]
Williams C G. Proc. R. Soc. Edinb., 1857, 3:370.

doi: 10.1017/S0370164600028558
[43]
Mishra A, Behera R K, Behera P K, Mishra B K, Behera G B. Chem. Rev., 2000, 100(6):1973.

doi: 10.1021/cr990402t
[44]
Xu Y, Li R X, Zhou X J, Li W Q, Ernest U, Wan H, Li L, Chen H Y, Yuan Z W. Talanta, 2019, 205:120125.

doi: 10.1016/j.talanta.2019.120125
[45]
Xu Z Q, Zhang M X, Xu Y, Liu S H, Zeng L T, Chen H Y, Yin J. Sens. Actuators, B, 2019, 290:676.
[46]
Xu Z Q, Huang X T, Han X, Wu D, Zhang B B, Tan Y, Cao M J, Liu S H, Yin J, Yoon J. Chem, 2018, 4(7):1609.

doi: 10.1016/j.chempr.2018.04.003
[47]
Yang X J, Wang Y Y, Zhao M X, Yang W. Spectrochimica Acta Part A: Mol. Biomol. Spectrosc., 2019, 212:10.

doi: 10.1016/j.saa.2018.12.042
[48]
Sun W, Guo S G, Hu C, Fan J L, Peng X J. Chem. Rev., 2016, 116(14):7768.

doi: 10.1021/acs.chemrev.6b00001
[49]
Ren M H, Wang L F, Lv X, Sun Y Q, Chen H, Zhang K Y, Wu Q, Bai Y R, Guo W. Anal., 2019, 144(24):7457.

doi: 10.1039/C9AN01852B
[50]
Yang Y, Wang Y Z, Feng Y, Cao C, Song X R, Zhang G L, Liu W S. J. Mater. Chem. B, 2019, 7(48):7723.

doi: 10.1039/c9tb01645g pmid: 31746929
[51]
Lin X, Hu Y L, Yang D L, Chen B. Dye. Pigment., 2020, 174:107956.

doi: 10.1016/j.dyepig.2019.107956
[52]
Wang H, Zhang Y X, Yang Y Y, He Z X, Wu C C, Zhang W, Zhang W, Liu J, Li P, Tang B. Chem. Commun., 2019, 55(65):9685.

doi: 10.1039/c9cc03814k
[53]
Zhang S P, Cai F Y, Hou B, Chen H, Gao C J, Shen X C, Liang H. New J. Chem., 2019, 43(17):6696.

doi: 10.1039/C9NJ00260J
[54]
Sinopoli A, Calogero G, Bartolotta A. Food Chem., 2019, 297:124898.

doi: 10.1016/j.foodchem.2019.05.172
[55]
Liu D J, Lv Y, Chen M, Cheng D, Song Z L, Yuan L, Zhang X B. J. Mater. Chem. B, 2019, 7:3970.

doi: 10.1039/C9TB00652D
[56]
Jiao S, He X, Xu L B, Ma P Y, Liu C M, Huang Y B, Sun Y, Wang X H, Song D Q. Sensor Actuat. B: Chem., 2019, 290:47.

doi: 10.1016/j.snb.2019.03.119
[57]
Rai M, Ingle A P, Pandit R, Paralikar P, Anasane N, Santos C A D. Expert. Rev. Anti-Infect. Ther., 2020, 18(4):367.

doi: 10.1080/14787210.2020.1730815
[58]
Luis P B, Boeglin W E, Schneider C. Chem. Res. Toxicol., 2018, 31(4):269.

doi: 10.1021/acs.chemrestox.7b00326
[59]
Chen D G, Yang J L, Dai J, Lou X D, Zhong C, Yu X L, Xia F. J. Mater. Chem. B, 2018, 6(32):5248.

doi: 10.1039/C8TB01340C
[60]
Chen D G, Long Z, Dang Y C, Chen L. Dye. Pigment., 2019, 166:266.

doi: 10.1016/j.dyepig.2019.03.051
[61]
Chen X Q, Zhou Y, Peng X J, Yoon J. Chem. Soc. Rev., 2010, 39(6):2120.

doi: 10.1039/b925092a
[62]
Chen M, Chen R, Shi Y, Wang J G, Cheng Y H, Li Y, Gao X D, Yan Y, Sun J Z, Qin A J, Kwok R T K, Lam J W Y, Tang B Z. Adv. Funct. Mater., 2018, 28(6):1704689.

doi: 10.1002/adfm.v28.6
[63]
Wang K, Leng T H, Liu Y J, Wang C Y, Shi P, Shen Y J, Zhu W H. Sensor Actuat. B: Chem., 2017, 248:338.

doi: 10.1016/j.snb.2017.03.127
[64]
Han C Y, Song B, Liang X, Pan H, Dong W. Anal. Methods, 2019, 11(19):2513.

doi: 10.1039/C9AY00708C
[65]
Chen D G, Long Z, Sun Y M, Luo Z J, Lou X D. J. Photochem. Photobiol. A: Chem., 2019, 368:90.

doi: 10.1016/j.jphotochem.2018.09.030
[66]
Dai Y P, Xue T Z, Zhang X X, Misal S, Ji H F, Qi Z J. Spectrochimica Acta Part A: Mol. Biomol. Spectrosc., 2019, 216:365.

doi: 10.1016/j.saa.2019.03.055
[67]
Zhang W, Liu J, Yu Y W, Han Q R, Cheng T, Shen J, Wang B X, Jiang Y L. Talanta, 2018, 185:477.

doi: S0039-9140(18)30350-3 pmid: 29759230
[68]
Zhou J L, Xu S, Dong X C, Zhao W L, Zhu Q G. Dye. Pigment., 2019, 167:157.

doi: 10.1016/j.dyepig.2019.04.020
[69]
Luo J D, Xie Z L, Lam J W Y, Cheng L, Tang B Z, Chen H Y, Qiu C F, Kwok H S, Zhan X W, Liu Y Q, Zhu D B. Chem. Commun., 2001, (18):1740.

pmid: 12240292
[70]
Mei J, Leung N L C, Kwok R T K, Lam J W Y, Tang B Z. Chem. Rev., 2015, 115(21):11718.

doi: 10.1021/acs.chemrev.5b00263
[71]
Cai X L, Liu B. Angew. Chem. Int. Ed., 2020, 59:9868.

doi: 10.1002/anie.v59.25
[72]
Pan L X, Cai Y J, Wu H Z, Zhou F, Qin A J, Wang Z M, Tang B Z. Mater. Chem. Front., 2018, 2(7):1310.

doi: 10.1039/C7QM00551B
[73]
Zhao Z, Gao S M, Zheng X Y, Zhang P F, Wu W T, Kwok R T K, Xiong Y, Leung N L C, Chen Y C, Gao X K, Lam J W Y, Tang B Z. Adv. Funct. Mater., 2018, 28(11):1705609.

doi: 10.1002/adfm.v28.11
[74]
Yamaguchi M, Ito S, Hirose A, Tanaka K, Chujo Y. Mater. Chem. Front., 2017, 1(8):1573.

doi: 10.1039/C7QM00076F
[75]
Gu Y, Zhao Z, Niu G L, Zhang R Y, Zhang H, Shan G G, Feng H T, Kwok R T K, Lam J W Y, Yu X Q, Tang B Z. ACS Appl. Bio Mater., 2019, 2(7):3120.

doi: 10.1021/acsabm.9b00447
[76]
Huang Y H, Mei J, Ma X. Dye. Pigment., 2019, 165:499.
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