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Spectroscopic Investigation of Coumarin Based Novel Fluorescent TURN OFF Sensor for the Selective Detection of Fe3+: In-vitro Live Cell Imaging Application

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Abstract

The novel TURN-OFF fluorescent sensors 4-(Benzo[1,3]dioxol-5-yloxymethyl)-7-hydroxy-chromen-2-one (4BHC) and 4-(6-Bromo-benzo[1,3]dioxol-5-yloxymethyl)-7-hydroxy-chromen-2-one (4BBHC) are designed and synthesized for the spectrofluorometric detection of the biologically important Fe3+ ions, which has sensitive and selective fluorescence quenching over other competitive metal ions. The effectiveness of the sensors and rapid response are validated through UV–Visible, and fluorescence spectral changes. These spectral changes could be due to the formation of coordination bond between ligand and metal ion. The binding stoichiometry of both sensors with Fe3+ ions is studied with the help of Job’s plot, which gives a 1:2 coordination ratio; this is further confirmed through DFT, IR and NMR studies. The association constants of 4BHC and 4BBHC are calculated through Benesie-Hildebrand plots, and they are found to be 6 × 104 M−1 and 11.2 × 104 M−1 respectively. Following, LOD is calculated to define the range of sensitivity of the proposed sensors and is found to be 3.43 μM and 2.14 μM respectively. The chemical hardness parameter suggested that both sensors are soft molecules. In addition, low cytotoxicity levels of 4BHC and 4BBHC led to the demonstration of their efficacy in In-Vitro imaging of Fe3+ ions inside living cells, which ensures that these sensors are promising candidates for bioimaging.

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Availability of Data and Materials

The study's data, according to the authors, are included in the publication and its Supplementary file. If any alternative format is required for the raw data files, they can be obtained in a fair amount of time from the corresponding author upon request.

References

  1. Bakhtiari G, Moradi S, Soltanali S (2014) A novel method for the synthesis of coumarin laser dyes derived from 3-(1H-benzoimidazol-2-yl) coumarin-2-one under microwave irradiation. Arab J Chem 7:972–975

    Article  CAS  Google Scholar 

  2. Dichiara M, Prezzavento O, Marrazzo A, Pittala V, Salerno L, Rescifina A, Amata E (2017) Recent advances in drug discovery of phototherapeutic non-porphyrinic anticancer agents. Eur J Med Chem 142:459–485

    Article  CAS  PubMed  Google Scholar 

  3. Wang R, Han Y, Sun B, Zhao Z, Opoku-Damoah Y, Cheng H, Zhang H, Zhou J, Ding Y (2018) Deep tumor penetrating bioparticulates inspired burst intracellular drug release for precision chemo-phototherapy. Small 14:1703110

    Article  Google Scholar 

  4. Xue J, Xu J, Ren J, Liang Q, Ou Q, Wang R, Shuai Z, Qiao J (2021) Intermolecular charge-transfer aggregates enable high-efficiency near-infrared emissions by nonadiabatic coupling suppression. Sci China Chem 64:1786–1795

    Article  CAS  Google Scholar 

  5. You Y, Nam W (2012) Photofunctional triplet excited states of cyclometalated Ir (III) complexes: beyond electroluminescence. Chem Soc Rev 41:7061–7084

    Article  CAS  PubMed  Google Scholar 

  6. Yao C-X, Zhao N, Liu J-C, Chen L-J, Liu J-M, Fang G-Z, Wang S (2020) Recent progress on luminescent metal-organic framework-involved hybrid materials for rapid determination of contaminants in environment and food. Polymers 12:691

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  7. Lu Y, Berry SM, Pfister TD (2001) Engineering novel metalloproteins: design of metal-binding sites into native protein scaffolds. Chem Rev 101:3047–3080

    Article  CAS  PubMed  Google Scholar 

  8. Atkinson A, Winge DR (2009) Metal acquisition and availability in the mitochondria. Chem Rev 109:4708–4721

    Article  CAS  PubMed  Google Scholar 

  9. Dai S, Schwendtmayer C, Schurmann P, Ramaswamy S, Eklund H (2000) Redox signaling in chloroplasts: cleavage of disulfides by an iron-sulfur cluster. Science 287:655–658

    Article  CAS  PubMed  Google Scholar 

  10. Kaplan CD, Kaplan J (2009) Iron acquisition and transcriptional regulation. Chem Rev 109:4536–4552

    Article  CAS  PubMed  Google Scholar 

  11. Theil EC, Goss DJ (2009) Living with iron (and oxygen): questions and answers about iron homeostasis. Chem Rev 109:4568–4579

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  12. Narayanaswamy N, Govindaraju T (2012) Aldazine-based colorimetric sensors for Cu2+ and Fe3+. Sens Actuators, B Chem 161:304–310

    Article  CAS  Google Scholar 

  13. Kohgo Y, Ikuta K, Ohtake T, Torimoto Y, Kato J (2008) Body iron metabolism and pathophysiology of iron overload. Int J Hematol 88:7–15

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  14. 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 3:7–13

    Article  CAS  PubMed  Google Scholar 

  15. Ward DM, Cloonan SM (2019) mitochondrial iron in human health and disease. Annu Rev Physiol 81:453–482

    Article  CAS  PubMed  Google Scholar 

  16. Spangler B, Morgan CW, Fontaine SD (2016) A reactivity-based probe of the intracellular labile ferrous iron pool. Nat Chem Biol 12:680–685

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  17. Keyer K, Imlay JA (1996) Superoxide accelerates DNA damage by elevating free-iron levels. Proc Natl Acad Sci USA 93:13635–13640

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  18. Zhang G, Zheng H, Guo M, Du L, Liu G, Wang P (2016) Synthesis of polymeric fluorescent brightener based on coumarin and its performances on paper as light stabilizer, fluorescent brightener and surface sizing agent. Appl Surf Sci 367:167–173

    Article  CAS  Google Scholar 

  19. Mulla BBA, Nesaragi AR, Pujar MS, Kamble RR, Sidarai AH (2023) Experimental and theoretical spectroscopic investigation on coumarin based derivatives for non-linear optoelectronics application. J Fluoresc 1:161–175

    Article  Google Scholar 

  20. Martins S, Candeias A, Caldeira AT, Pereira A (2020) 7-(diethylamino)-4-methyl-3-vinylcoumarin as a new important intermediate to the synthesis of photosensitizers for DSSCs and fluorescent labels for biomolecules. Dyes Pigm 174:108026

    Article  CAS  Google Scholar 

  21. Zhang Y, Shi Y, Li Y (2016) Photoexcitation mechanisms of new D-π-A coumarin derivatives in linear and nonlinear optical processes. J Mater Sci: Mater Electron 27:7132–7140

    CAS  Google Scholar 

  22. Waskasi MM, Hashemianzadeh SM, Sarhangi OM (2011) Significant enhancement in efficiency of NKX-2807 Coumarin dye by applying external electric field in dye sensitizer solar cell: Theoretical study. Comput Theor Chem 978:33–40

    Article  CAS  Google Scholar 

  23. Mulla BB, Nesaragi AR, Kamble RR, Sidarai AH (2023) Exploration of coumarin derivative: experimental and computational modeling for dipole moment estimation and thermal sensing application. J Fluoresc. https://doi.org/10.1007/s10895-023-03364-3

    Article  PubMed  Google Scholar 

  24. Li B, Tian J, Zhang D, Tian F (2017) A novel colorimetric fluorescence sensor for Fe3+ based on quinoline Schiff base. Luminescence 32:567–1573

    Article  Google Scholar 

  25. Ju P, Su Q, Liu Z, Li X, Guo B, Liu W, Li G, Wu Q (2019) A Salen-based covalent organic polymer as highly selective and sensitive fluorescent sensor for detection of Al3+, Fe3+ and Cu2+ ions. J Mater Sci 54:851–861

    Article  CAS  Google Scholar 

  26. Wang L, Yang X, Chen X, Zhou Y, Lu X, Yan C, Xu Y, Liu R, Qu J (2017) A novel fluorescence probe based on triphenylamine Schiff base for bioimaging and responding to pH and Fe3+. Mater Sci Eng, C 72:551–557

    Article  CAS  Google Scholar 

  27. Wang L, Bing Q, Li J, Wang G (2018) A new “ON-OFF” fluorescent and colorimetric chemosensor based on 1,3,4-oxadiazole derivative for the detection of Cu2+ ions. J Photochem Photobiol, A 360:86–94

    Article  Google Scholar 

  28. Wang L, Gong X, Bing Q, Wang G (2018) A new oxadiazole-based dual-mode chemosensor: Colorimetric detection of Co2+ and fluorometric detection of Cu2+ with high selectivity and sensitivity. Microchem J 142:279–287

    Article  CAS  Google Scholar 

  29. Zhu L, Gu C, He Y, Wang G (2014) Study on a highly selective fluorescent chemosensor for Cu2+ and its direct sensing for proton based on 1,3,4-oxadiazole. J Lumin 153:439–445

    Article  CAS  Google Scholar 

  30. Li Z, 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 Pigm 105:7–11

    Article  CAS  Google Scholar 

  31. Benesi HA, Hildebrand JH (1949) A Spectrophotometric Investigation of the Interaction of Iodine with Aromatic Hydrocarbons. J Am Chem Soc 71:2703–2707

    Article  CAS  Google Scholar 

  32. Gerlier D, Thomasset N (1986) Use of MTT colorimetric assay to measure cell activation. J Immunol Methods 94:57–63

    Article  CAS  PubMed  Google Scholar 

  33. Gong X, Ding X, Jiang N, Zhong T, Wang G (2020) Benzothiazole-based fluorescence chemosensors for rapid recognition and “turn-off” fluorescence detection of Fe3+ ions in aqueous solution and in living cells. Microchem J 152:104351

    Article  CAS  Google Scholar 

  34. Frisch M, Trucks G, Schlegel H, Scuseria G, Robb M, Cheeseman J, Montgomery J Jr, Vreven T, Scalmani G, Mennucci B (2003) Gaussian, revision B. Gaussian Inc., Pittsburg

    Google Scholar 

  35. Al-Sehemi AG, Pannipara M, Kalam A, Asiri AM (2016) A combined experimental and computational investigation on spectroscopic and photophysical properties of a coumarinyl chalcone. J Fluoresc 26:1357–1365

    Article  CAS  PubMed  Google Scholar 

  36. Karuk Elmas SN, Dincer ZE, Erturk AS, Bostanci A, Karagoz A, Koca M, Sadi G, Yilmaz I (2020) A novel fluorescent probe based on isocoumarin for Hg2+ and Fe3+ ions and its application in live-cell imaging. Spectrochim Acta Part A Mol Biomol Spectrosc 224:117402

    Article  CAS  Google Scholar 

  37. Sivaraman G, Sathiyaraja V, Chellappa D (2014) Turn-on fluorogenic and chromogenic detection of Fe(III) and its application in living cell imaging. J Lumin 145:480–485

    Article  CAS  Google Scholar 

  38. Zhao B, Liu T, Fang Y, Wang L, Kan W, Deng Q, Song B (2017) A new selective chemosensor based on phenanthro[9,10-d] imidazole-coumarin with sequential “on-off-on” fluorescence response to Fe3+ and phosphate anions and its application in live cell. Sens Actuators, B Chem 246:370–379

    Article  CAS  Google Scholar 

  39. Fan C, Huang X, Han L, Lu Z, Wang Z, Yi Y (2016) Novel colorimetric and fluorescent off–on enantiomers with high selectivity for Fe3+ imaging in living cells. Sens Actuators, B Chem 224:592–599

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We gratefully acknowledge the financial assistance aided by National Fellowship for Schedule Tribes (NFST), Ministry of Tribal affairs, India (Award no. 202021-NFST-KAR-02682) and also support by Karnatak University Scientific Instrumentation Centre (USIC) by providing the required instrumentation facilities.

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Authors and Affiliations

  1. Department of Studies in Physics, Karnatak University, Dharwad, 580003, Karnataka, India

    Kavyashree Nagappa Kummur, Mahesh Madar & Ashok H. Sidarai

  2. Department of Physics, KLE Dr.M.S Sheshgiri College of Engineering and Technology, Belagavi, 590008, Karnataka, India

    Malatesh S. Pujar

  3. Department of Chemistry, KLE Society’s PC Jabin College, Hubballi, 580031, Karnataka, India

    Mahanthesh Basangouda Patil

  4. Department of Physics, V.M.K. S.R Vastrad Arts, Science & V.S.Bellihal Commerce College, Hungund, 587118, Karnataka, India

    Mahesh Madar

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  1. Kavyashree Nagappa Kummur
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Contributions

The study's conceptions and design were a collaborative effort by all the authors. Kavyashree Nagappa Kummur performed the sample preparation, data collection, and formal analysis, while Mahanthesh Basangouda Patil synthesized the materials. Kavyashree Nagappa Kummur also wrote the first draft of the manuscript, Dr. Malatesh. S. Pujar and Mahesh Madar handled the computational work. Prof. Ashok H Sidarai oversaw the editing and review of the draft. All authors have read and given their approval for the final manuscript.

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Correspondence to Ashok H. Sidarai.

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Kummur, K.N., Pujar, M.S., Patil, M.B. et al. Spectroscopic Investigation of Coumarin Based Novel Fluorescent TURN OFF Sensor for the Selective Detection of Fe3+: In-vitro Live Cell Imaging Application. J Fluoresc (2024). https://doi.org/10.1007/s10895-023-03573-w

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