A Ratiometric Naphthalimide-Based Fluorescent Chemosensor via Excimer-Monomer Switching for the Sensitive Detection of Copper (II) Ions

Document Type : Original Article

Author

Department of Organic Colorants, Institute for Color Science and Technology, P.O. Box: 16765-654, Tehran, Iran

Abstract

A newly designed diaza-18-crown-6 ether featuring two fluorogenic 1,8-naphthalimide side arms has been developed. This synthesized fluorescent dye (BNDA) presented a dual OFF-ON / ON-OFF response arising from switching between monomer and excimer emissions in the presence of copper ions. The binding behavior of BNDA with Cu2+ was thoroughly examined using fluorescence spectroscopy. The binding constant of BNDA with Cu2+ was determined through the Benesi–Hildebrand plot, yielding values of 5.57 × 106 M−1, indicating selective and sensitive interactions. This probe exhibited exceptional selectivity for copper ions, with a notably low detection limit of 29 nM, as well as a wide linear range of 2.9×10-4 – 4 µM response. To ascertain its practical application, BNDA was successfully applied for determining copper ions in real environmental samples of tap water, black tea, and human hair. Its good reversibility, stable response, and wide pH of 4.2 to 7.5, along with a strong linear range, make it a promising candidate for sensitive detection of Cu2+.

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References

  1. Lakowicz JR, editor. Principles of fluorescence spectroscopy. Boston, MA: springer US; 2006 Sep 15. https://doi.org/10.1007/978-0-387-46312-4_19
  2. Gao YY, He J, Li XH, Li JH, Wu H, Wen T, Li J, Hao GF, Yoon J. Fluorescent chemosensors facilitate the visualization of plant health and their living environment in sustainable agriculture. Chem Soc Rev. 2024; 53(13):6992-7090. https://doi.org/10.1039/ D3CS 00504F.
  3. Bojinov V, Georgiev N. Molecular sensors and molecular logic gates. J University Chem Technol Metall. 2011 Mar 1;46(1). https://doi.org/10.1007/ 128_2010_96. 112. 
  4. Khan J. Synthesis and applications of fluorescent chemosensors: a review. J Fluor. 2024; 34(6):2485-94. https://doi.org/10.1007/s10895-023-03455-1
  5. Zhao Y, Mei Y, Sun J, Tian Y. A supramolecular fluorescent chemosensor enabling specific and rapid quantification of norepinephrine dynamics. J Am Chem Soc. 2025; 147(6):5025-34. https://doi.org/10.1039/D3 CS00504F. 
  6. Gurusamy S, Sankarganesh M, Sathish V, Rajakumar K, Mathavan A. Fluorescence chemosensor for anion recognition, solvatochromism and protein binding studies based on Schiff-base derivative. J Mol Struct. 2024; 1312:138542. https://doi.org/10.1016/j.molstruc. 2024.138542.
  7. Zhang K, Tian X, Xu P, Zhu Y, Guang S, Xu H. Multi-ion detection chemosensor based on rhodamine for turn-on fluorescence sensing and bioimaging of Fe3+, Al3+, Cr3+, and Hg2+ under different channels. Spectrochimica Acta Part A: Mol Biomol Spect. 2024; 318:124484.  https://doi.org/10.1016/j.saa.2024.124484
  8. Mohammad Abu-Taweel G, Alharthi SS, Al-Saidi HM, Babalghith AO, Ibrahim MM, Khan S. Heterocyclic organic compounds as a fluorescent chemosensor for cell imaging applications: a review. Critical Rev Anal Chem. 2024; 54(7):2538-53. https://doi.org/10.1080/10 408347.2023.2186695.
  9. Chowdhury S, Rooj B, Dutta A, Mandal U. Review on recent advances in metal ions sensing using different fluorescent probes. J Fluor. 2018; 28(4):999-1021. https://doi.org/10.1007/s10895-018-2263-y.
  10. Li CR, Yang ZY, Li SL. 1, 8-Naphthalimide derived dual-functioning fluorescent probe for “turn-off” and ratiometric detection of Cu2+ based on two distinct mechanisms in different concentration ranges. J Lumines. 2018; 198:327-36. https://doi.org/10.1016/j. jlumin.2018.02.031.
  11. Alaei P, Rouhani S, Gharanjig K, Ghasemi J. A new polymerizable fluorescent PET chemosensor of fluoride (F−) based on naphthalimide–thiourea dye. Spectrochim Acta Part A: Mol Biomol Spect. 2012; 90:85-92. https://doi.org/10.1016/j.saa.2012.01.008.
  12. Brewer GJ. Copper in Wilson’s and Alzheimer’s diseases, copper-lowering therapy in cancer and other diseases, and copper deficiency. In Mol Genetic Nutritional Aspects Major Trace Mineral. 2017;115-129. Academic Press https://doi.org/10.1016/ B978-0-12-802168-2.00010-5.
  13. Montes S, Rivera-Mancia S, Diaz-Ruiz A, Tristan-Lopez L, Rios C. Copper and copper proteins in Parkinson’s disease. Oxidative Medicine Cellular Longevity. 2014; 2014(1):147251. https://doi.org/10. 1155/2014/147251
  14. Sowada N, Stiller B, Kubisch C. Increased copper toxicity in Saccharomyces cerevisiae lacking VPS35, a component of the retromer and monogenic Parkinson disease gene in humans. Biochemical and biophysical research communications. 2016; 476(4):528-33. http:// dx. doi.org/10.1016/j.bbrc.2016.05.157.
  15. Li J, Yim D, Jang WD, Yoon J. Recent progress in the design and applications of fluorescence probes containing crown ethers. Chem Soc Rev. 2017;46 (9):2437-58. https://doi.org/10.1039/C6CS00619A.
  16. Sprenger T, Schwarze T, Holdt HJ, Hentsch A, Nazaré M. Benzo‐Crown‐Ether Functionalized O‐BODIPY Probes for Cations–A Selective Fluorescent Probe for Ba2+. Chem A Eur J. 2024; 30(45):e202401928. https://doi.org/10.1002/chem.202401928.
  17. Polyakova AS, Panchenko PA, Efremenko AV, Feofanov AV, Fedorov YV, Fedorova OA. A naphthalimide-based fluorescent and colorimetric probe for the detection of mercury (II) ions in aqueous solutions and in living cells. Mendel Commun. 2024; 34(3):418-20. https://doi.org/10.1016/j.mencom.2024. 04.034.
  18. Hosseinnezhad M, Gharanjig K, Fathi M. Synthesis of an organic dye based on indoline for use in dye-sensitized solar cells. J Color Sci Tech. 2025;19(1):101-112. https://doi.org/10.30509/jcst.2025.167615.1267. [In Persian]
  19. Xu H, Xiao Y, Liu YG, Sun W. Research progress on naphthalimide fluorescent probes. Adv Sensor Res. 2024; 3(2):2300032. https://doi.org/10.1002/adsr.202 300032.
  20. Chen M, Stitt H, Chu R, Kistemaker JC, Wood IA, Burn PL, Gentle IR, Shaw PE. Naphthalimide derivatives as film‐based fluorescent sensors for rapid detection of illicit drugs. Adv Sensor Res. 2025; 4(10):e00063. https://doi.org/10.1002/adsr.202500063.
  21. Chen M, Li Y, Tian H, Xie D, Zhu Y, Wu Y, Zhang X, Zhu M. A multi‐stimuli‐responsive fluorescence material based on 1,8‐naphthalimide. Luminescence. 2024; 39(8):e4868. https://doi.org/10.1002/bio.4868.
  22. Kaur G, Singh I, Tandon N, Tandon R, Bhat AA. 1,8‐Naphthalimide‐based chemosensors: a promising strategy for detection of metal ions in environmental and biological systems. ChemistrySelect. 2023; 8(44): e202301661. https://doi.org/10.1002/slct.202301661.
  23. Nie W, Hu L. Design of 1, 8‐naphthalimide‐based fluorescent functional molecules for biological application: A review. ChemistrySelect. 2024; 9(3): e202303779. https://doi.org/10.1002/slct.202303779
  24. Hosseinnezhad M, Nasiri S, Nutalapati V, Gharanjig K, Arabi AM. A review of the application of organic dyes based on naphthalimide in optical and electrical devices. Prog Color Colorant Coat. 2024; 17(4):417-33. https://doi.org/10.30509/pccc.2024.167247.1267
  25. Kaur G, Palta A, Kumar G, Paul K, Singh I. Fluorescent “turn-on” naphthalimide conjugate for the detection of CN− ion with potential applications in real water samples and molecular logic gate. Microchemical J. 2025; 209:112845. https://doi.org/10.1016/j.microc. 2025. 112845.
  26. Acikgoz O, Abelt C. Use of molecular logic gates for the tuning of chemosensor dynamic range. Molecules. 2024; 29(18):4330. https://doi.org/10.3390/molecules 29184330.
  27. Chen A, Kong F, Fu ZH, Qin JC. Relay recognition of Cu2+ and S2− using naphthalimide-based fluorescent probe and its applications in molecular logic gate and bioimaging. Chem Phys. 2024; 577:112132. https://doi. org/10.1016/j.chemphys.2023.112132.
  28. Seraj S, Rouhani S, Ranjbar Z, Esfahani SL. Fructose recognition using novel solid-state electro-optical nanosensor based on boronate-tagged fluorophore modified graphene oxide. Mater Chem Phys. 2021; 270:124842. https://doi.org/10.1016/j.matchemphys.2021.124842
  29. 28 Rouhani S, Gharagozlou M. A New reusable mercury-sensitive turn-on nano-chemosensor based on functionalized CoFe2O4@SiO2 magnetic nano-composite. https://doi.org/10.30509/pccc.2021.166735.
  30. Mahdiani M, Rouhani S, Zahedi P. Synthesis, solvatochromism and fluorescence quenching studies of naphthalene diimide dye by nano graphene oxide. J Fluor. 2023; 33(5):2003-14. https://doi.org/10.1007/s 10895- 023-03197-0.
  31. Seraj S, Rouhani S. A fluorescence quenching study of naphthalimide dye by graphene: mechanism and thermodynamic properties. J Fluor. 2017;27(5): 1877-83. https://doi.org/10.1007/s10895-017-2126-y.
  32. Wang HF, Wu SP. A pyrene-based highly selective turn-on fluorescent sensor for copper (II) ions and its application in living cell imaging. Sensor Actuators B: Chem. 2013;181:743-8. http://dx.doi.org/10.1016/j.snb. 2013.01.054.
  33. Lederer FJ, Graupner FF, Maerz B, Braun M, Zinth W. Excimer formation in 9, 10-dichloroanthracene–Solutions and crystals. Chem. Phys. 2014; 428:82-9. http://dx.doi.org/10.1016/j.chemphys.2013.11.005.
  34. Kollár J, Hrdlovič P, Chmela Š. Spectral properties of bichromophoric pyrene derivatives: Monomer vs. excimer fluorescence. J Photochem Photobiol A: Chem. 2010; 214(1):33-9. http://dx.doi.org/10.1016/j.jphoto-chem. 2010.06.003.
  35. Chatterjee S, Kar S, Lahiri S, Basu S. Steric-controlled excimer formation in naphthalene analogues of chalcone. Spectrochim Acta Part A: Mol Biomol Spect. 2004; 60(8-9):1713-8. http://dx.doi.org/10.1016/j.saa. 2003.09.011.
  36. Ferreira R, Baleizão C, Muñoz-Molina JM, Berberan-Santos MN, Pischel U. Photophysical study of bis(naphthalimide)-amine conjugates: toward molecular design of excimer emission switching. J Phys Chem A. 2011;115(6):1092-9. https://doi.org/10.1021/jp110470h
  37. Xu Z, Yoon J, Spring DR. A selective and ratiometric Cu2+ fluorescent probe based on naphthalimide excimer–monomer switching. Chem Commun. 2010; 46(15):2563-5. http://dx.doi.org/10.1016/j.jlumin.2012. 07.009.
  38. Konstantinova TN, Meallier P, Grabchev I. The synthesis of some 1, 8-naphthalic anhydride derivatives as dyes for polymeric materials. Dye Pigm. 1993; 22(3):191-8. http://dx.doi.org/10.1016/0143-7208(93) 87006-Z.

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