Analytical and Bioanalytical Chemistry

, Volume 411, Issue 6, pp 1143–1157 | Cite as

A novel tryptamine-appended rhodamine-based chemosensor for selective detection of Hg2+ present in aqueous medium and its biological applications

  • Subhenjit Hazra
  • Chandan Bodhak
  • Sourav Chowdhury
  • Dwipanjan Sanyal
  • Subhro Mandal
  • Krishnananda Chattopadhyay
  • Animesh PramanikEmail author
Research Paper


A novel rhodamine–tryptamine conjugate–based fluorescent and chromogenic chemosensor (RTS) for detection of Hg2+ present in water was reported. After gradual addition of Hg2+ in aqueous methanol solution of RTS, a strong orange fluorescence and deep-pink coloration were observed. The probe showed high selectivity towards Hg2+ compared to other competitive metal ions. The 1:1 binding stoichiometry between RTS and Hg2+ was established by Job’s plot analysis and mass spectroscopy. Initial studies showed that the synthesized probe RTS possessed fair non-toxicity and effectively passed through cell walls of model cell systems, viz., human neuroblastoma (SHSY5Y) cells and cervical cells (HeLa) to detect intercellular Hg2+ ions, signifying its utility in biological system. The limit of detection (LOD) was found to be 2.1 nM or 0.42 ppb by fluorescence titration. Additionally, the potential relevance of synthesized chemosensor for detecting Hg2+ ions in environmental water samples has been demonstrated.

Graphical abstract


Chemosensor Rhodamine Hg2+ detection Cell imaging Flow cytometry 



S. H. thanks UGC, India, for Dr. D. S. Kothari post-doctoral fellowship (F.4-2/2006 (BSR)/CH/15-16/0226). C.B., S.C., and S.M. thank UGC, New Delhi, India, for Senior Research Fellowship (SRF). D.S. is thankful to DST India for DST Inspire Doctoral Fellowship. K.C. acknowledges DST-SERB India for financial support (DST SERB EMR/2016/000310). The authors are thankful to Mr. Arghyadeep Bhattacharyya, Prof. Nikhil Guchait (Department of Chemistry, University of Calcutta), and Tanmoy Dalui (Technical Expert, Central FACS Facility CSIR-IICB). The authors also acknowledge DST-PURSE, India, for HR-MS facility at the Department of Chemistry, University of Calcutta. The financial assistance and instrumental facilities of Centre of Advanced Study (CAS-V, UGC, New Delhi) at the Department of Chemistry, University of Calcutta, are gratefully acknowledged.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

216_2018_1546_MOESM1_ESM.pdf (1.5 mb)
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  1. 1.
    Zheng J, Yang R, Shi M, Wu C, Fang X, Li Y, et al. Rationally designed molecular beacons for bioanalytical and biomedical applications. Chem Soc Rev. 2015;44(10):3036–55.Google Scholar
  2. 2.
    Yang Z, Cao J, He Y, Yang JH, Kim T, Peng X, et al. Macro-/micro-environment-sensitive chemosensing and biological imaging. Chem Soc Rev. 2014;43(13):4563–601.Google Scholar
  3. 3.
    Wu D, Sedgwick AC, Gunnlaugsson T, Akkaya EU, Yoon J, James TD. Fluorescent chemosensors: the past, present and future. Chem Soc Rev. 2017;46(23):7105–23.Google Scholar
  4. 4.
    Domaille DW, Que EL, Chang CJ. Synthetic fluorescent sensors for studying the cell biology of metals. Nat Chem Biol. 2008;4(3):168–75.Google Scholar
  5. 5.
    Kolanowski JL, Liu F, New EJ. Fluorescent probes for the simultaneous detection of multiple analytes in biology. Chem Soc Rev. 2018;47(1):195–208.Google Scholar
  6. 6.
    Nolan EM, Lippard SJ. Tools and tactics for the optical detection of mercuric ion. Chem Rev. 2008;108(9):3443–80.Google Scholar
  7. 7.
    Saleem M, Rafiq M, Hanif M. Organic material based fluorescent sensor for Hg2+: a brief review on recent development. J Fluoresc. 2017;27(1):31–58.Google Scholar
  8. 8.
    Zarlaida F, Adlim M. Gold and silver nanoparticles and indicator dyes as active agents in colorimetric spot and strip tests for mercury (II) ions: a review. Microchim Acta. 2017;184(1):45–58.Google Scholar
  9. 9.
    Chen G, Guo Z, Zeng G, Tang L. Fluorescent and colorimetric sensors for environmental mercury detection. Analyst. 2015;140(16):5400–43.Google Scholar
  10. 10.
    Culzoni MJ, De La Peña AM, Machuca A, Goicoechea HC, Babiano R. Rhodamine and BODIPY chemodosimeters and chemosensors for the detection of Hg2+, based on fluorescence enhancement effects. Anal Methods. 2013;5(1):30–49.Google Scholar
  11. 11.
    Bag B, Pal A. Rhodamine-based probes for metal ion-induced chromo-/fluorogenic dual signaling and their selectivity towards Hg (II) ion. Org Biomol Chem. 2011;9(12):4467–80.Google Scholar
  12. 12.
    Bothra S, Upadhyay Y, Kumar R, Kumar SA, Sahoo SK. Chemically modified cellulose strips with pyridoxal conjugated red fluorescent gold nanoclusters for nanomolar detection of mercuric ions. Biosens Bioelectron. 2017;90:329–35.Google Scholar
  13. 13.
    Patil R, Fegade U, Kaur R, Sahoo SK, Singh N, Kuwar A. Highly sensitive and selective determination of Hg2+ by using 3-((2-(1H-benzo[d]imidazol-2-yl)phenylimino)methyl)benzene-1,2-diol as fluorescent chemosensor and its application in real water sample. Supramol Chem. 2015;27(7–8):527–32.Google Scholar
  14. 14.
    Renzoni A, Zino F, Franchi E. Mercury levels along the food chain and risk for exposed populations. Environ Res. 1998;77(2):68–72.Google Scholar
  15. 15.
    Benoit JM, Fitzgerald WF, Damman AW. The biogeochemistry of an ombrotrophic bog: evaluation of use as an archive of atmospheric mercury deposition. Environ Res. 1998;78(2):118–33.Google Scholar
  16. 16.
    Baldi F, Filippelli M, Olson GJ. Biotransformation of mercury by bacteria isolated from a river collecting cinnabar mine waters. Microb Ecol. 1989;17(3):263–74.Google Scholar
  17. 17.
    Vergilio CS, Carvalho CE, Melo EJ. Mercury-induced dysfunctions in multiple organelles leading to cell death. Toxicol in Vitro. 2015;29(1):63–71.Google Scholar
  18. 18.
    Harada M. Minamata disease: methylmercury poisoning in Japan caused by environmental pollution. Crit Rev Toxicol. 1995;25(1):1–24.Google Scholar
  19. 19.
    Zahir F, Rizwi SJ, Haq SK, Khan RH. Low dose mercury toxicity and human health. Environ Toxicol Pharmacol. 2005;20(2):351–60.Google Scholar
  20. 20.
    Rooney JP. The retention time of inorganic mercury in the brain-a systematic review of the evidence. Toxicol Appl Pharmacol. 2014;274(3):425–35.Google Scholar
  21. 21.
    Mutter J, Naumann J, Sadaghiani C, Schneider R, Walach H. Alzheimer disease: mercury as pathogenetic factor and apolipoprotein E as a moderator. Neuroendocrinol Lett. 2004;25(5):331–9.Google Scholar
  22. 22.
    Bera K, Das AK, Nag M, Basak S. Development of a rhodamine–rhodanine-based fluorescent mercury sensor and its use to monitor real-time uptake and distribution of inorganic mercury in live zebrafish larvae. Anal Chem. 2014;86(5):2740–6.Google Scholar
  23. 23.
    Silbergeld EK, Silva IA, Nyland JF. Mercury and autoimmunity: implications for occupational and environmental health. Toxicol Appl Pharmacol. 2005;207(2):282–92.Google Scholar
  24. 24.
    Zalups RK, Ahmad S. Homocysteine and the renal epithelial transport and toxicity of inorganic mercury: role of basolateral transporter organic anion transporter 1. J Am Soc Nephrol. 2004;15(8):2023–31.Google Scholar
  25. 25.
    Zalups RK, Lash LH. Cystine alters the renal and hepatic disposition of inorganic mercury and plasma thiol status. Toxicol Appl Pharmacol. 2006;214(1):88–97.Google Scholar
  26. 26.
    Hazra S, Balaji S, Banerjee M, Ganguly A, Ghosh NN, Chatterjee A. A PEGylated-rhodamine based sensor for “turn-on” fluorimetric and colorimetric detection of Hg2+ ions in aqueous media. Anal Methods. 2014;6(11):3784–90.Google Scholar
  27. 27.
    EPA U. Mercury update: impact on fish advisories. EPA Fact Sheet EPA-823-F-01-011, Office of Water, Washington, DC. 2001.Google Scholar
  28. 28.
    Amde M, Yin Y, Zhang D, Liu J. Methods and recent advances in speciation analysis of mercury chemical species in environmental samples: a review. Chem Speciat Bioavailab. 2016;28(1–4):51–65.Google Scholar
  29. 29.
    Asadpour-Zeynali K, Amini R. A novel voltammetric sensor for mercury (II) based on mercaptocarboxylic acid intercalated layered double hydroxide nanoparticles modified electrode. Sensors Actuators B Chem. 2017;246:961–8.Google Scholar
  30. 30.
    Ayranci R, Demirkol DO, Timur S, Ak M. Rhodamine-based conjugated polymers: potentiometric, colorimetric and voltammetric sensing of mercury ions in aqueous medium. Analyst. 2017;142(18):3407–15.Google Scholar
  31. 31.
    Cubuk S, Fırlak M, Taşci N, Yetimoğlu EK, Kahraman MV. Phosphonic acid based polymeric fluorescent sensor for Hg (II) analysis. Sensors Actuators B Chem. 2016;224:640–7.Google Scholar
  32. 32.
    Thakur N, Kumar SA, Kumar KA, Pandey AK, Kumar SD, Reddy AV. Development of a visual optode sensor for onsite determination of Hg (II). Sensors Actuators B Chem. 2015;211:346–53.Google Scholar
  33. 33.
    Gao Y, Shi Z, Long Z, Wu P, Zheng C, Hou X. Determination and speciation of mercury in environmental and biological samples by analytical atomic spectrometry. Microchem J. 2012;103:1–4.Google Scholar
  34. 34.
    Beija M, Afonso CA, Martinho JM. Synthesis and applications of rhodamine derivatives as fluorescent probes. Chem Soc Rev. 2009;38(8):2410–33.Google Scholar
  35. 35.
    Chen Z, Chen J, Pan D, Li H, Yao Y, Lyu Z, et al. “Reactive” optical sensor for Hg2+ and its application in environmental aqueous media and biological systems. Anal Bioanal Chem. 2017;409(9):2429–35.Google Scholar
  36. 36.
    Fang Y, Zhou Y, Li JY, Rui QQ, Yao C. Naphthalimide-rhodamine based chemosensors for colorimetric and fluorescent sensing Hg2+ through different signaling mechanisms in corresponding solvent systems. Sensors Actuators B Chem. 2015;215:350–9.Google Scholar
  37. 37.
    Maniyazagan M, Mariadasse R, Jeyakanthan J, Lokanath NK, Naveen S, Premkumar K, et al. Rhodamine based “turn-on” molecular switch FRET-sensor for cadmium and sulfide ions and live cell imaging study. Sensors Actuators B Chem. 2017;238:565–77.Google Scholar
  38. 38.
    Li D, Li CY, Qi HR, Tan KY, Li YF. Rhodamine-based chemosensor for fluorescence determination of trivalent chromium ion in living cells. Sensors Actuators B Chem. 2016;223:705–12.Google Scholar
  39. 39.
    Yang Z, Bai X, Ma S, Liu X, Zhao S, Yang Z. A benzoxazole functionalized fluorescent probe for selective Fe3+ detection and intracellular imaging in living cells. Anal Methods. 2017;9(1):18–22.Google Scholar
  40. 40.
    Qiao B, Sun S, Jiang N, Zhang S, Peng X. A ratiometric fluorescent probe for determining Pd2+ ions based on coordination. Dalton Trans. 2014;43(12):4626–30.Google Scholar
  41. 41.
    Kim HN, Lee MH, Kim HJ, Kim JS, Yoon J. A new trend in rhodamine-based chemosensors: application of spirolactam ring-opening to sensing ions. Chem Soc Rev. 2008;37(8):1465–72.Google Scholar
  42. 42.
    Mukherjee S, Hazra S, Chowdhury S, Sarkar S, Chattopadhyay K, Pramanik A. A novel pyrrole fused coumarin based highly sensitive and selective fluorescence chemosensor for detection of Cu2+ ions and applications towards live cell imaging. J Photochem Photobiol A Chem. 2018;364:635–44.Google Scholar
  43. 43.
    Dhara A, Jana A, Guchhait N, Ghosh P, Kar SK. Rhodamine-based molecular clips for highly selective recognition of Al3+ ions: synthesis, crystal structure and spectroscopic properties. New J Chem. 2014;38(4):1627–34.Google Scholar
  44. 44.
    Dhara A, Guchhait N, Kar SK. A novel Cr3+ fluorescence turn-on probe based on rhodamine and isatin framework. J Fluoresc. 2015;25(6):1921–9.Google Scholar
  45. 45.
    Singharoy D, Chowdhury S, Mati SS, Ghosh S, Chattopadhyay K, Bhattacharya SC. Photoinduced electron transfer switching mechanism of a naphthalimide derivative with its solvatochromic behaviour: an experimental and theoretical study with in cell investigations. Chem Eur J. 2017;23(65):16516–24.Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of ChemistryUniversity of CalcuttaKolkataIndia
  2. 2.Protein Folding and Dynamics Laboratory, Structural Biology and Bio-informatics DivisionCSIR-Indian Institute of Chemical BiologyKolkataIndia

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