Synthesis of Graphene Quantum Dots Decorated With Se, Eu and Ag As Photosensitizer and Study of Their Potential to Use in Photodynamic Therapy

Abstract

GQDs decorated with europium (Eu), silver (Ag) and selenium (Se) at molar ratios of 0.1%, 0.3% and 0.5% were produced for the first time at different temperatures of 180 °C, 200 °C and 220 °C. Surface passivation was carried out with polyethylene glycol (PEG) to increase the intensity of photoluminescence (PL) of the produced samples. The prepared quantum dots were characterized by X-Ray diffraction (XRD), Fourier transformed infrared spectroscopy (FTIR), transmission electron microscopy (TEM), PL and ultraviolet-visible spectroscopy. GQDs synthesized at 180 °C and decorated with Se (0.3%) had maximum PL intensity along with long lasted afterglow over 90 min compared with other samples. Excitation wavelength at 360 nm produced maximum emission at 600–900 nm and resulted in high singlet oxygen (1O 2) generation which makes it a good candidate for photodynamic therapy applications.

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Data Availability

All data generated or analyzed during this study are included in this published article.

References

  1. 1.

    Tavakkoli F, Zahedifar M, Sadeghi E (2018) Effect of LaF3: Ag fluorescent nanoparticles on photodynamic efficiency and cytotoxicity of Protoporphyrin IX photosensitizer. Photodiagn Photodyn Ther 21:306–311

    CAS  Article  Google Scholar 

  2. 2.

    Davanzo NN, Pellosi DS, Franchi LP, Tedesco AC (2017) Light source is critical to induce cell death by photodynamic therapy using chloro-aluminiumphtalocyanine albumin-based nanoparticles. Photodiagn Photodyn Ther 19:181–183

    CAS  Article  Google Scholar 

  3. 3.

    Eshghi H, Sazgarnia A, Rahimizadeh M, Attaran N, Bakavoli M, Soudmand S (2013) Protoporphyrin IX–gold nanoparticle conjugates as an efficient photosensitizer in cervical cancer therapy. Photodiagn Photodyn Ther 10(3):304–312

    CAS  Article  Google Scholar 

  4. 4.

    Allison RR, Mota HC, Bagnato VS, Sibata CH (2008) Bio-nanotechnology and photodynamic therapy—state of the art review. Photodiagn Photodyn Ther 5(1):19–28

    CAS  Article  Google Scholar 

  5. 5.

    Du D, Wang K, Wen Y, Li Y, Li YY (2016) Photodynamic graphene quantum dot: reduction condition regulated photoactivity and size dependent efficacy. ACS Appl Mat interfaces 8(5):3287–3294. glioblastoma

    CAS  Article  Google Scholar 

  6. 6.

    Lucky SS, Soo KC, Zhang Y (2015) Nanoparticles in photodynamic therapy. Chem Rev 115(4):1990–2042

    CAS  Article  Google Scholar 

  7. 7.

    Kholikov K, Ilhom S, Sajjad M, Smith ME, Monroe JD, San O, Er AO (2018) Improved singlet oxygen generation and antimicrobial activity of sulphur-doped graphene quantum dots coupled with methylene blue for photodynamic therapy applications. Photodiagn Photodyn Ther 24:7–14

    CAS  Article  Google Scholar 

  8. 8.

    Castano AP, Demidova TN, Hamblin MR (2004) Mechanisms in photodynamic therapy: part one—photosensitizers, photochemistry and cellular localization. Photodiagn Photodyn Ther 1(4):279–293

    CAS  Article  Google Scholar 

  9. 9.

    Allison RR, Sibata CH (2010) Oncologic photodynamic therapy photosensitizers: a clinical review. Photodiagn Photodyn Ther 7(2):61–75

    CAS  Article  Google Scholar 

  10. 10.

    Ge J, Lan M, Zhou B, Liu W, Guo L, Wang H et al (2014) A graphene quantum dot photodynamic therapy agent with high singlet oxygen generation. Nat Commun 5:4596

    CAS  Article  Google Scholar 

  11. 11.

    Wu F, Yue L, Su H, Wang K, Yang L, Zhu X (2018) Carbon dots@ platinum Porphyrin composite as Theranostic Nanoagent for efficient photodynamic Cancer therapy. Nanoscale Res Lett 13(1):357

    Article  Google Scholar 

  12. 12.

    Hui L, Huang J, Chen G, Zhu Y, Yang L (2015) Antibacterial property of graphene quantum dots (both source material and bacterial shape matter). ACS Appl Mater interfaces 8(1):20–25

    Article  Google Scholar 

  13. 13.

    Dong Y, Lin J, Chen Y, Fu F, Chi Y, Chen G (2014) Graphene quantum dots, graphene oxide, carbon quantum dots and graphite nanocrystals in coals. Nanoscale 6(13):7410–7415

    CAS  Article  Google Scholar 

  14. 14.

    Roeinfard M, Zahedifar M, Darroudi M, Khorsand Zak A, Sadeghi E (2020) Preparation and characterization of selenium-decorated graphene quantum dots with high afterglow for application in photodynamic therapy. Luminescence 35(6):891–896

    CAS  Article  Google Scholar 

  15. 15.

    Tabish TA, Scotton CJ, Ferguson DCJ, Lin L, der Veen AV, Lowry S et al (2018) Biocompatibility and toxicity of graphene quantum dots for potential application in photodynamic therapy. Nanomedicine 13(15):1923–1937

    CAS  Article  Google Scholar 

  16. 16.

    Zhu Y, Wang G, Jiang H, Chen L, Zhang X (2015) One-step ultrasonic synthesis of graphene quantum dots with high quantum yield and their application in sensing alkaline phosphatase. Chem Commun 51(5):948–951

    CAS  Article  Google Scholar 

  17. 17.

    Zhu S, Zhang J, Qiao C, Tang S, Li Y, Yuan W et al (2011) Strongly green-photoluminescent graphene quantum dots for bioimaging applications. Chem Commun 47(24):6858–6860

    CAS  Article  Google Scholar 

  18. 18.

    Jovanović SP, Syrgiannis Z, Marković ZM, Bonasera A, Kepić DP, Budimir MD et al (2015) Modification of structural and luminescence properties of graphene quantum dots by gamma irradiation and their application in a photodynamic therapy. ACS Appl Mater interfaces 7(46):25865–25874

    Article  Google Scholar 

  19. 19.

    Zhao F, Gu W, Zhou J, Liu Q, Chong Y (2019) Solar-excited graphene quantum dots for bacterial inactivation via generation of reactive oxygen species. J Environ Sci Health Part C 37(2):67–80

    Article  Google Scholar 

  20. 20.

    Kuo WS, Shao YT, Huang KS, Chou TM, Yang CH (2018) Antimicrobial amino-functionalized nitrogen-doped graphene quantum dots for eliminating multidrug-resistant species in dual-modality photodynamic therapy and bioimaging under two-photon excitation. ACS Appl Mater interfaces 10(17):14438–14446

    CAS  Article  Google Scholar 

  21. 21.

    Kumar S, Ojha AK, Ahmed B, Kumar A, Das J, Materny A (2017) Tunable (violet to green) emission by high-yield graphene quantum dots and exploiting its unique properties towards sun-light-driven photocatalysis and supercapacitor electrode materials. Mater Today Commun 11:76–86

    CAS  Article  Google Scholar 

  22. 22.

    Shen J, Zhu Y, Yang X, Zong J, Zhang J, Li C (2012) One-pot hydrothermal synthesis of graphene quantum dots surface-passivated by polyethylene glycol and their photoelectric conversion under near-infrared light. New J Chem 36(1):97–101

    CAS  Article  Google Scholar 

  23. 23.

    Peng J, Gao W, Gupta BK, Liu Z, Romero-Aburto R, Ge L et al (2012) Graphene quantum dots derived from carbon fibers. Nano lett 12(2):844–849

    CAS  Article  Google Scholar 

  24. 24.

    Naik JP, Sutradhar P, Saha M (2017) Molecular scale rapid synthesis of graphene quantum dots (GQDs). J Nanostruct Chem 7(1):85–89

    CAS  Article  Google Scholar 

  25. 25.

    Dong Y, Shao J, Chen C, Li H, Wang R, Chi Y et al (2012) Blue luminescent graphene quantum dots and graphene oxide prepared by tuning the carbonization degree of citric acid. Carbon 50(12):4738–4743

    CAS  Article  Google Scholar 

  26. 26.

    Bansal S, Singh J, Kumari U, Kaur IP, Barnwal RP, Kumar R et al (2019) Development of biosurfactant-based graphene quantum dot conjugate as a novel and fluorescent theranostic tool for cancer. Int J Nanomed 14:809–818

    Article  Google Scholar 

  27. 27.

    Wu X, Tian F, Wang W, Chen J, Wu M, Zhao JX (2013) Fabrication of highly fluorescent graphene quantum dots using L- glutamic acid for in vitro/in vivo imaging and sensing. J Mater Chem C 1(31):4676–4684

    CAS  Article  Google Scholar 

  28. 28.

    Thakur M, Kumawat MK, Srivastava R (2017) Multifunctional graphene quantum dots for combined photothermal and photodynamic therapy coupled with cancer cell tracking applications. RSC Adv 7(9):5251–5261

    CAS  Article  Google Scholar 

  29. 29.

    Anooj ES, Praseetha PK (2019) Synthesis and characterization of graphene quantum dots from nutmeg seeds and its biomedical application. Int J Recent Tech Eng (IJRTE) 7:144–151

    Google Scholar 

  30. 30.

    Mahesh S, Lekshmi CL, Renuka KD (2017) New paradigms for the synthesis of graphene quantum dots from sustainable bioresources. New J Chem 41(17):8706–8710

    CAS  Article  Google Scholar 

  31. 31.

    Habiba K, Encarnacion-Rosado J, Garcia-Pabon K, Villalobos-Santos JC, Makarov VI, Avalos JA et al (2016) Improving cytotoxicity against cancer cells by chemo-photodynamic combined modalities using silver-graphene quantum dots nanocomposites. Int J Nanomed 11:107–119

    CAS  Article  Google Scholar 

  32. 32.

    Suk JS, Xu Q, Kim N, Hanes J, Ensign LM (2016) PEGylation as a strategy for improving nanoparticle-based drug and gene delivery. Adv Drug Deliv Rev 99(Pt A):28–51

    CAS  Article  Google Scholar 

  33. 33.

    Zhu TC, Finlay JC (2008) The role of photodynamic therapy (PDT) physics. Med phys 35(7Part 1):3127–3136

    CAS  Article  Google Scholar 

  34. 34.

    Murphy MP (2008) How mitochondria produce reactive oxygen species. Biochem J 417(1):1–13

    Article  Google Scholar 

  35. 35.

    Zahedifar M, Sadeghi E, Shanei MM, Sazgarnia A, Mehrabi M (2016) Afterglow properties of CaF2: Tm nanoparticles and its potential application in photodynamic therapy. J Lumin 171:254–258

    CAS  Article  Google Scholar 

  36. 36.

    Xu H, Sun X, Yao J, Zhang J, Zhang Y, Chen H et al (2015) The decomposition of protoporphyrin IX by ultrasound is dependent on the generation of hydroxyl radicals. Ultrason Sonochem 27:623–630

    CAS  Article  Google Scholar 

  37. 37.

    Hai X, Feng J, Chen X, Wang J (2018) Tuning the optical properties of graphene quantum dots for biosensing and bioimaging. J Mater Chem B 6(20):3219–3234

    CAS  Article  Google Scholar 

  38. 38.

    Nafiujjaman M, Revuri V, Park HK, Kwon IK, Cho KJ, Lee YK (2016) Enhanced photodynamic properties of graphene quantum dot conjugated Ce6 nanoparticles for targeted cancer therapy and imaging. Chem Lett 45(8):997–999

    CAS  Article  Google Scholar 

Download references

Acknowledgements

The authors are grateful to research council of the University of Kashan for providing financial support to undertake this work (Grant number 785216).

Funding

This work has been supported by research council, University of Kashan, grant number 785216.

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M. Zahedifar and M. Darroudi conceived of the presented idea and supervised the project. M. Roeinfard and A. Khorsand Zak fabricated the samples. E. Sadeghi and M. Roeinfard carried out the characterization tests and studied the optical properties to verify the applicability of the produced samples in photodynamic therapy. M. Zahedifar wrote the manuscript with support from E. Sadeghi.

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Correspondence to M. Zahedifar.

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Roeinfard, M., Zahedifar, M., Darroudi, M. et al. Synthesis of Graphene Quantum Dots Decorated With Se, Eu and Ag As Photosensitizer and Study of Their Potential to Use in Photodynamic Therapy. J Fluoresc 31, 551–557 (2021). https://doi.org/10.1007/s10895-020-02674-0

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Keywords

  • Graphene quantum dot
  • Photoluminescence
  • Afterglow
  • Polyethylene glycol
  • Photodynamic therapy