Wuhan University Journal of Natural Sciences

, Volume 24, Issue 5, pp 409–416 | Cite as

Pyrazole-Triazine Conjugate as Highly Selective and Sensitive Fluorescence Probe for Silver (I) Detection and Its Imaging in Living Cells

  • Yanhong Liu
  • Bingqiong Yu
  • Qingya Zhu
  • Kun YanEmail author
Chemistry and Physics


A new fluorescence probe 2,2′-(6-(4-(diethylamino) phenyl)-1,3,5-triazine-2,4-diyl)bis(1H-pyrazole-1,3-diyl) diacetate (EATPA) based on 1, 3, 5-triazine was designed and synthesized. It exhibited distinct fluorescence quenching in the presence of silver ions that can be used for highly sensitive and selective detection of Ag+. Fluorescence titration and Job’s plot analysis revealed the formation of [Ag(EATPA)2]+ entity with high binding constant (1.43×104 L/mol) and low detection limit (0.882 µmol/L). Furthermore, live-cell imaging experiments demonstrated that EATPA is potentially applicable for the tracking of Ag+ in living cells.

Key words

fluorescence probe silver ions fluorescence quenching detection limit cell imaging 

CLC number

O 61 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. [1]
    Fu F, Wang Q. Removal of heavy metal ions from wastewaters: A review [J]. Journal of Environmental Management, 2011, 92(3): 407–418.CrossRefGoogle Scholar
  2. [2]
    Sud D, Mahajan G, Kaur M P. Agricultural waste material as potential adsorbent for sequestering heavy metal ions from aqueous solutions—A review [J]. Bioresource Technology, 2008, 99(14): 6017–6027.CrossRefGoogle Scholar
  3. [3]
    Ratte H T. Bioaccumulation and toxicity of silver compounds: A review [J]. Environmental Toxicology and Chemistry, 2010, 18(1): 89–108.CrossRefGoogle Scholar
  4. [4]
    Wood C M, Playle R C, Hogstrand C. Physiology and modeling of mechanisms of silver uptake and toxicity in fish [J]. Environmental Toxicology and Chemistry, 2010, 18(1): 71–83.CrossRefGoogle Scholar
  5. [5]
    Kim T N, Kim J O, Wu J, et al. Antimicrobial effects of metal ions (Ag+, Cu2+ Zn2+) in hydroxyapatite [J]. Journal of Materials Science: Materials in Medicine, 1998, 9(3): 129–134.Google Scholar
  6. [6]
    Yamanaka M, Hara K, Kudo J. Bactericidal actions of a silver ion solution on Escherichia coli, studied by energy-filtering transmission electron microscopy and proteomic analysis [J]. Applied and Environmental Microbiology, 2005, 71(11): 7589–7593.CrossRefGoogle Scholar
  7. [7]
    Nandre J P, Patil S R, Sahoo S K, et al. A chemosensor for micro- to nano-molar detection of Ag+ and Hg2+ ions in pure aqueous media and its applications in cell imaging [J]. Dalton Transactions, 2017, 46(41): 14201–14209.CrossRefGoogle Scholar
  8. [8]
    Wang Y J, Liu J G, Tan H Y, et al. A colorimetric and farred fluorescent probe for the highly sensitive detection of silver (I) [J]. RSC Advances, 2017, 7(88): 55567–55570.CrossRefGoogle Scholar
  9. [9]
    Chen B, Liu J, Yang T, et al. Development of a portable device for Ag+ sensing using CdTe QDs as fluorescence probe via an electron transfer process [J]. Talanta, 2019, 191: 357–363.CrossRefGoogle Scholar
  10. [10]
    Chamsaz M, Arbab-Zavar M H, Akhondzadeh J. Triple-phase single-drop microextraction of silver and its determination using graphite-furnace atomic-absorption spectrometry [J]. Analytical Sciences, 2008, 24(6): 709–801.CrossRefGoogle Scholar
  11. [11]
    Mikelova R, Baloun J, Petrlova J, et al. Electrochemical determination of Ag-ions in environment waters and their action on plant embryos [J]. Bioelectrochemistry, 2007, 70 (2): 508–518.CrossRefGoogle Scholar
  12. [12]
    Tan E, Yin P, Lang X F, et al. Functionalized gold nanoparticles as nanosensor for sensitive and selective detection of silver ions and silver nanoparticles by surface-enhanced Raman scattering [J]. Analyst, 2012, 137 (17): 3925–3928.CrossRefGoogle Scholar
  13. [13]
    Yang X J, Foley R, Low G K C. A modified digestion procedure for analysing silver in environmental water samples [J]. Analyst, 2002, 127(2): 315–318.CrossRefGoogle Scholar
  14. [14]
    Ding Y B, Tang Y Y, Zhu W H, et al. Fluorescent and colorimetric ion probes based on conjugated oligopyrroles [J]. Chemical Society Reviews, 2015, 44(5): 1101–1112.CrossRefGoogle Scholar
  15. [15]
    Wang X, Wang T X, Tian X J, et al. Europium complex doped luminescent solar concentrators with extended absorption range from UV to visible region [J]. Solar Energy, 2011, 85(9): 2179–2184.CrossRefGoogle Scholar
  16. [16]
    Paul P, Tyagi B, Bilakhiya A K, et al. Synthesis and characterization of rhodium complexes containing 2,4,6-Tris(2-pyridyl)-1,3,5-triazine and its metal-promoted hydrolytic products: Potential uses of the new complexes in electrocatalytic reduction of carbon dioxide [J]. Inorganic Chemistry, 1998, 37(22): 5733–5742.CrossRefGoogle Scholar
  17. [17]
    Lebreton S, Newcombe N, Bradley M. Antibacterial single-bead screening [J]. Tetrahedron, 2003, 59(51): 10213–10222.CrossRefGoogle Scholar
  18. [18]
    Hoog P D, Gamez P, Driessen W L, et al. New polydentate and polynucleating N-donor ligands from amines and 2,4,6-trichloro-1,3,5-triazine [J]. Tetrahedron Letters, 2002, 43(38): 6783–6786.CrossRefGoogle Scholar
  19. [19]
    Shellaiah M, Rajan Y C, Lin H C. Synthesis of novel triarylamine-based dendrimers with N4, N6-dibutyl-1,3,5-triazine-4,6-diamine probe for electron/energy transfers in H-bonded donor-acceptor-donor triads and as efficient Cu2+ sensors [J]. Journal of Materials Chemistry, 2012, 22(18): 8976–8987.CrossRefGoogle Scholar
  20. [20]
    Zhang Y, Zeng X, Mu L, et al. Rhodamine-triazine based probes for Cu2+ in aqueous media and living cells [J]. Sensors and Actuators B: Chemical, 2014, 204: 24–30.CrossRefGoogle Scholar
  21. [21]
    Zhu Y Z, Qiao M, Peng W C, et al. Rapid exfoliation of layered covalent triazine-based frameworks into N-doped quantum dots for the selective detection of Hg2+ ions [J]. Journal of Materials Chemistry A, 2017, 5: 9272–9278.CrossRefGoogle Scholar
  22. [22]
    Sang Q G, Yang J K. An efficient way for the recognition of zinc ion via the fluorescence enhancement [J]. Chinese Journal of Chemistry, 2012, 30(7): 1410–1414.CrossRefGoogle Scholar
  23. [23]
    Ge F Y, Yang C, Cai Z S. Fluorescence sensor performance of a new fluorescein derivate: [2-Morpholine-4-(6-chlorine-1,3,5-s-triazine)-amino]fluorescein [J]. Bulletin of the Korean Chemical Society, 2015, 36(11): 2703–2709.CrossRefGoogle Scholar
  24. [24]
    Nie L H, Ma H M, Li X H, et al. Recognition of thymine by triazine fluorescent probe through intermolecular multiple hydrogen bonding [J]. Biopolymers, 2010, 72(4): 274–281.CrossRefGoogle Scholar
  25. [25]
    Ma H M, Nie L N, Xiong S X. Recognition of guanine by a designed triazine based fluorescent probe through intermolecular multiple hydrogen bonding [J]. Supramolecular Chemistry, 2004, 16(5): 311–317.CrossRefGoogle Scholar
  26. [26]
    Ye Z Q, Chen J X, Wang G L, et al. Development of a terbium complex-based luminescent probe for imaging endogenous hydrogen peroxide generation in plant tissues [J]. Analytical Chemistry, 2011, 83(11): 4163–4169.CrossRefGoogle Scholar
  27. [27]
    Tan M Q, Song B, Wang G L, et al. A new terbium (III) chelate as an efficient singlet oxygen fluorescence probe [J]. Free Radical Biology and Medicine, 2006, 40(9): 1644–1653.CrossRefGoogle Scholar
  28. [28]
    Kumar K S, Schafer B, Lebedkin S, et al. Highly luminescent charge-neutral europium (I) and terbium (I) complexes with tridentate nitrogen ligands [J]. Dalton Transactions, 2015, 44(35): 15611–15619.CrossRefGoogle Scholar
  29. [29]
    Xu L, Xu Y, Zhu W, et al. A highly selective and sensitive fluorescence “turn-on” probe for Ag+ in aqueous solution and live cells [J]. Dalton Transactions, 2012, 41(24): 7212–7217.CrossRefGoogle Scholar
  30. [30]
    Su P, Zhu Z, Wang J, et al. A biomolecule-based fluorescence chemosensor for sequential detection of Ag+ and H2S in 100% aqueous solution and living cells [J]. Sensors and Actuators B: Chemical, 2018, 273: 93–100.CrossRefGoogle Scholar
  31. [31]
    Zhang Y, Wang D, Sun C, et al. A simple 2,6-diphenylpyridine-based fluorescence “turn-on” chemosensor for Ag+ with a high luminescence quantum yield [J]. Dyes and Pigments, 2017, 141: 202–208.CrossRefGoogle Scholar
  32. [32]
    Cui W, Wang L, Xiang G, et al. A colorimetric and fluorescence “turn-off” chemosensor for the detection of silver ion based on a conjugated polymer containing 2,3-di(pyridin-2-yl)quinoxaline [J]. Sensors and Actuators B: Chemical, 2015, 207: 281–290.CrossRefGoogle Scholar
  33. [33]
    Li W T, Wu G Y, Qu W J, et al. A colorimetric and reversible fluorescent chemosensor for Ag+ in aqueous solution and its application in Implication logic gate [J]. Sensors and Actuators B: Chemical, 2017, 239: 671–678.CrossRefGoogle Scholar
  34. [34]
    Velmurugan K, Thamilselvan A, Antony R, et al. Imidazoloquinoline bearing thiol probe as fluorescent electrochemical sensing of Ag and relay recognition of proline [J]. Journal of Photochemistry and Photobiology A: Chemistry, 2017, 333: 130–141.CrossRefGoogle Scholar
  35. [35]
    Saitoh T, Ichikawa J. Bis(triarylmethylium)-mediated diaryl ether synthesis: Oxidative arylation of phenols with N, N-dialkyl-4-phenylthioanilines [J]. Journal of the American Chemical Society, 2005, 127(27): 9696–9697.CrossRefGoogle Scholar
  36. [36]
    Lo W S, Zhang J, Wong W T, et al. Highly luminescent Sm (I) complexes with intraligand charge-transfer sensitization and the effect of solvent polarity on their luminescent properties [J]. Inorganic Chemistry, 2015, 54(8): 3725–3727.CrossRefGoogle Scholar
  37. [37]
    Smolyar N N, Yutilov Y M. Cyclizations of monocyclic 5-nitropyridin-2(1H)-ones [J]. Russian Journal of Organic Chemistry, 2008, 44(8): 1205–1210.CrossRefGoogle Scholar
  38. [38]
    Brouwer A M. Standards for photoluminescence quantum yield measurements in solution (IUPAC Technical Report) [J]. Pure and Applied Chemistry, 2011, 83(12): 2213–2228.CrossRefGoogle Scholar
  39. [39]
    Zhang Q, Luo L, Xu H, et al. Design, synthesis, linear and nonlinear photophysical properties of novel pyrimidine-based imidazole derivatives [J]. New Journal of Chemistry, 2016, 40(4): 3456–3463.CrossRefGoogle Scholar

Copyright information

© Wuhan University and Springer-Verlag GmbH Germany 2019

Authors and Affiliations

  • Yanhong Liu
    • 1
  • Bingqiong Yu
    • 1
  • Qingya Zhu
    • 1
  • Kun Yan
    • 1
    Email author
  1. 1.College of Chemistry and Molecular SciencesWuhan UniversityWuhan, HubeiChina

Personalised recommendations