A Fluorescent Sensor for Cu2+ Ion with High Selectivity and Sensitivity Based on ICT and PET

  • Hui Yang
  • Yuhang Wu
  • Fuli TianEmail author


A novel fluorescent sensor (L) based on 1,8-naphthalic anhydride has been developed which can selectively detect Cu2+ in CH3CN medium over other metal ions at 408 nm in the fluorescence spectra. When Cu2+ was added into L, L showed fluorescent turn-off by coordinating with Cu2+. A fresh absorption band was found at the position of 290 nm as was a red-shifted absorption band from 356 nm to 376 nm in UV-vis spectra which might be attributed to the intramolecular charge transfer (ICT). Meanwhile, L-Cu2+ showed fluorescence quenching via photoinduced electron transfer (PET). The complexation ratio was proposed to be 1:1 which was determined by Job’s plot, fluorescence titration and 1H NMR titration. The detection limit was 9.1 × 10−8 mol·L−1, a satisfying level to detect Cu2+ in the micromolar scale. Corresponding molecular geometries, orbital energies and electron contributions of sensor L were calculated by the DMol3 program package using the density functional theory.


1,8-naphthalic anhydride Fluorescent sensor Cu2+ ions Density functional theory 



We are grateful to the Nature Science Foundation of China for financial support (Nos. 21265010) and support from Wang Xiaojing and her team at Inner Mongolia University.


  1. 1.
    Muthuraj B, Deshmukh R, Trivedi V (2014) Highly selective sensor detects Cu2+ and endogenous NO gas in Living Cell. J Am Chem Soc 6:6562–6569Google Scholar
  2. 2.
    Udhayakumari D, Velmathi S (2014) Highly fluorescent sensor for copper (II) ion based on commercially available compounds and live cell imaging. Sensor Actuat B-Chem 198:285–293CrossRefGoogle Scholar
  3. 3.
    Tapiero H, Townsend DM, Tew KD (2003) Trace elements in human physiology and pathology: copper. Biomed Pharmacother 57:386–398CrossRefPubMedPubMedCentralGoogle Scholar
  4. 4.
    Waggoner DJ, Bartnikas TB, Gitlin JD (1999) The role of copper in neurodegenerative disease. Neurobiol Dis 6:221–230CrossRefPubMedGoogle Scholar
  5. 5.
    Vulpe C, Levinson B, Whitney S, Packman S, Gitschier J (1993) Isolation of a candidate gene for Menkes disease and evidence that it encodes a copper transporting ATPase. Nat Genet 3:7–13CrossRefPubMedGoogle Scholar
  6. 6.
    Bull PC, Thomas GR, Rommens JM, Forbes JR, Cox DW (1993) The Wilson disease gene is a putative copper transporting P-type ATPase similar to the Menkes gene. Nat Genet 5:327–337CrossRefPubMedGoogle Scholar
  7. 7.
    Barnham KJ, Masters CL, Bush AI (2004) Neurodegenerative diseases and oxidative stress. Nat Rev Drug Discov 3:205–214CrossRefPubMedGoogle Scholar
  8. 8.
    Valentine JS, Hart PJ (2003) Misfolded CuZnSOD and amyotrophic lateral sclerosis. Proc Natl Acad Sci U S A 100:3617–3622CrossRefPubMedPubMedCentralGoogle Scholar
  9. 9.
    Bruijn LI, Miller TM, Cleveland DW (2004) Unraveling the mechanisms involved in motor neuron degeneration in ALS. Annu Rev Neurosci 27:723–749CrossRefPubMedGoogle Scholar
  10. 10.
    Brown DR, Kozlowski H (2004) Biological inorganic and bioinorganic chemistry of neurodegeneration based on prion and Alzheimer diseases. Dalton T (13):1907–1917Google Scholar
  11. 11.
    Georgopoulos PG, Roy A, Yonone-Lioy MJ, Opiekun RE, Lioy PJ (2001) Environmental copper: its dynamics and human exposure issues. J Toxicol Environ Health Part B 4:341–394CrossRefGoogle Scholar
  12. 12.
    Gonzales APS, Firmino MA, Nomure CS, Rocha FRP, Oliveira PV, Gaubeur I (2009) Peat as a natural solid-phase for copper Preconcentration and determination in a multicommuted flow system coupled to flame atomic absorption spectrometry. Anal Chim Acta 636:198–204CrossRefPubMedGoogle Scholar
  13. 13.
    Xu Z, Yoon J, Spring D (2010a) Fluorescent Chemosensors for Zn2+. Chem Soc Rev 39(6):1996–2006CrossRefPubMedGoogle Scholar
  14. 14.
    Qian X, Xiao Y, Xu Y, Guo X, Qian J, Zhu W (2010) “Alive” dyes as fluorescent sensors: fluorophore, mechanism, receptor and images in living cells. Chem Commun 46:6418–6436CrossRefGoogle Scholar
  15. 15.
    Liu Y, Lv X, Zhao Y, Chen M, Liu J, Wang P (2012) A Naphthalimide-rhodamine Ratiometric fluorescent sensor for Hg2+ based on fluorescence resonance energy transfer. Dyes Pigments 92:909–915CrossRefGoogle Scholar
  16. 16.
    Duke R, Veale E, Pfeffer F, Kruger P, Gunnlaugsson T (2010) Colorimetric and fluorescent anion sensor: an overview of recent developments in the use of 1,8-Naphthalimide-based Chemosensors. Chem Soc Rev 39:3936–3953CrossRefPubMedGoogle Scholar
  17. 17.
    Grabchev I, Staneva D, Dumas S, Chovelon J-M (2011) Metal ions and protons sensing properties of new fluorescent 4-N-Methylpiperazine-1,8-Naphthalime Determinated poly(propyleneamine) dendrimer. J Mol Struct 999:16–21CrossRefGoogle Scholar
  18. 18.
    Salmon L, Thuery P, Riviere E, Ephritikhine M (2006) Synthesis, structure, and magnetic behavior of a series of Trinuclear Schiff Base complexes of 5f (UIV,ThIV) and 3d (CuII,ZnII) ions. Inorg Chem 45:83–93CrossRefPubMedGoogle Scholar
  19. 19.
    Xu Y, Meng J, Meng L, Dong Y, Cheng Y, Zhu C (2010b) A highly selective fluorescence-based polymer sensor incorporating an (R,R)-salen moiety for Zn2+. Chem Eur J 16:898–903Google Scholar
  20. 20.
    Reddy TS, Reddy AR (2012) Synthesis and fluorescence study of 3-Aminoalkylamidonapthalimides. Photochem Photobiol A Chem 227:51–58CrossRefGoogle Scholar
  21. 21.
    Liu CJ, Yang ZY (2015) Novel optical selective Chromone Schiff Base Chemosensor for Al3+ ion. J Lumin 158:172–175CrossRefGoogle Scholar
  22. 22.
    Li ZQ, Zhou Y, Yin K, Yu Z, Li Y, Ren J (2014) A new fluorescence “turn-on” type Chemosensor for Fe3+ based on Naphthalimide and Coumarin. Dyes Pigments 105:7–11CrossRefGoogle Scholar
  23. 23.
    ] J. C. Qin, Z. Y. Yang (2015) A novel Ratiometric fluorescent sensor for detection of Fe3+ by rhodamine-Quinoline conjugate. J. Photoch Photobiol A 310:122–127Google Scholar
  24. 24.
    Wang GQ, Qin JC, Fan L, Li CR, Yang ZY (2016) A “turn-on” fluorescent sensor for highly selective recognition of Mg2+ based on new Schiff’s base derivative. J Photoch Photobiol A 314:29–34CrossRefGoogle Scholar
  25. 25.
    Kim KB, You DM, Jeon JH, Kim JH, Kim C (2014a) A fluorescent and colorimetric Chemsensor for selective detection of Aluminium in aqueous solution. Tetrahedron Lett 55:1347–1352CrossRefGoogle Scholar
  26. 26.
    Jiang XJ, Fu Y, Tang H (2014) A new highly selective fluorescent sensor for detection of Cd2+ and Hg2+ based on two different approaches in aqueous solution. Sensors Autuat B-Chem 190:844–850CrossRefGoogle Scholar
  27. 27.
    Kim H, Kang J, Kim KB, Song EJ, Kim C (2014b) A highly selective Quinoline-based fluorescent sensor for Zn2+. Spectrochim Acta A Mol Biomol Spectrosc 118:883–887CrossRefPubMedGoogle Scholar
  28. 28.
    Sung Hoon Kim, Seon-Yeong Gwon, Jin-Seok Bae, The synthesis and spectral properties of a stimuli-responsive D-π-a charge transfer dye. Spectrochim Acta A Mol Biomol Spectrosc, 2011, 78, 234–237CrossRefPubMedGoogle Scholar
  29. 29.
    Son YA, Park J (2012) Rhodamine 6G based new fluorophore Chemosensor toward Hg2+. Textile Coloration and Finishing 24:158–164CrossRefGoogle Scholar
  30. 30.
    Roy N, Dutta A, Mondal P (2015) A new turn-on fluorescent Chemosensor based on sensitive Schiff Base for Mn2+ ion. J Lumin 165:167–173CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.College of Chemistry and Chemical EngineeringInner Mongolia UniversityHohhotPeople’s Republic of China
  2. 2.Key Laboratory of Medicinal and Edible Plants Resources of Hainan ProvinceHainan Institute of Science and TechnologyHaikouPeople’s Republic of China

Personalised recommendations