Skip to main content
SpringerLink
Log in

Elucidating the Photoluminescence Quenching in Ensulizole: an Artificial Water Soluble Sunscreen

  • Original Article
  • Published:
Journal of Fluorescence Aims and scope Submit manuscript

Abstract

Employing natural or artificial sunscreens is essential to protect the skin from ultraviolet radiations that cause premature aging and develop melanoma and other forms of skin cancer. The 2-Phenylbenzimidazole-5-sulfonic acid, commonly known as ensulizole is a water-soluble artificial sunscreen that absorb UV-B (280 nm − 315 nm) radiations and protects the skin against the harmful effects of these radiations. We have measured steady-state photoluminescence (SSPL) spectra and photoluminescence (PL) kinetics of this compound in various conditions. Steady-state absorption indicates a strong absorption feature at 303 nm and a weak one at 316 nm that have been identified as π → π* and n → π* transitions, respectively. The spectra of PL induced by these absorptions indicate that the PL of ensulizole is less Stokes-shifted in polar solvents and more Stokes-shifted in non-polar solvents. The average PL lifetime of ensulizole is longer in non-polar solvents than in polar solvents and it exhibits the shortest PL lifetime in aqueous medium that maximize its transition efficiency in water. This suggests in non-polar solvents intersystem crossing is the dominant mode of relaxation of the excited ππ* state. Furthermore, an increase of pH of ensulizole solution decreases the PL intensity and the lifetime. Stern-Volmer equation is employed to evaluate bimolecular quenching rate constant kq. The evaluation result suggests the diffusional dynamic mode of PL quenching is operative.

Graphical Abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Scheme 1
Scheme 2
Fig. 3
Fig. 4

Similar content being viewed by others

Data Availability

All data generated or analyzed during this study are included.

Code Availability

All data were obtained using word, origin and Chemdraw.

References

  1. Bais AF, Lucas RM, Bornman JF, Williamson CE, Sulzberger B, Austin AT, Wilson SR, Andrady AL, Bernhard G, McKenzie RL (2018) Environmental effects of ozone depletion, UV radiation and interactions with climate change: UNEP Environmental Effects Assessment Panel, update 2017. Photochem Photobiol Sci 17:127–179

    CAS  PubMed  PubMed Central  Google Scholar 

  2. Bernhard GH, Neale RE, Barnes PW, Neale P, Zepp RG, Wilson SR, Andrady AL, Bais AF, McKenzie R, Aucamp P (2020) Environmental effects of stratospheric ozone depletion, UV radiation and interactions with climate change: UNEP Environmental Effects Assessment Panel, update 2019. Photochem Photobiol Sci 19:542–584

    CAS  PubMed  PubMed Central  Google Scholar 

  3. Kao M-H, Venkatraman RK, Sneha M, Wilton M, Orr-Ewing AJ (2021) Influence of the solvent environment on the ultrafast relaxation pathways of a sunscreen molecule diethylamino hydroxybenzoyl hexyl benzoate. J Phys Chem A 125:636–645

    CAS  PubMed  Google Scholar 

  4. Bacardit A, Cartoixà X (2020) Revisiting the role of irradiance in the determination of sunscreens’ sun protection factor. J Phys Chem Lett 11:1209–1214

    CAS  PubMed  Google Scholar 

  5. Serrano Jareño MA, Moreno J (2013) Erythemal ultraviolet solar radiation doses received by young skiers. Photochem Photobiol Sci 12:1976–1983

    Google Scholar 

  6. Baker LA, Clark SL, Habershon S, Stavros VG (2017) Ultrafast transient absorption spectroscopy of the sunscreen constituent Ethylhexyl triazone. J Phys Chem Lett 8:2113–2118

    CAS  PubMed  Google Scholar 

  7. Inbaraj JJ, Bilski P, Chignell CF (2002) Photophysical and photochemical studies of 2-phenylbenzimidazole and UVB sunscreen 2‐phenylbenzimidazole‐5‐sulfonic acid. Photochem Photobiol 75:107–116

    CAS  PubMed  Google Scholar 

  8. Herzog B, Amorós-Galicia L, Sohn M, Hofer M, Quass K, Giesinger J (2019) Analysis of photokinetics of 2′-ethylhexyl-4-methoxycinnamate in sunscreens. Photochem Photobiol Sci 18:1773–1781

    CAS  PubMed  Google Scholar 

  9. Dondi D, Albini A, Serpone N (2006) Interactions between different solar UVB/UVA filters contained in commercial suncreams and consequent loss of UV protection. Photochem Photobiol Sci 5:835–843

    CAS  PubMed  Google Scholar 

  10. Lewicka ZA, William WY, Oliva BL, Contreras EQ, Colvin VL (2013) Photochemical behavior of nanoscale TiO2 and ZnO sunscreen ingredients. J Photochem Photobiol A 263:24–33

    CAS  Google Scholar 

  11. Wright CY, du Preez DJ, Martincigh BS, Allen MW, Millar DA, Wernecke B, Blesic S (2020) A comparison of solar ultraviolet radiation exposure in urban canyons in Venice, Italy and Johannesburg, South Africa. Photochem Photobiol 96:1148–1153

    CAS  PubMed  Google Scholar 

  12. Sansomchai P, Jumpatong K, Lapinee C, Utchariyajit K (2021) Melientha suavis Pierre. Extract: antioxidant and sunscreen properties for future cosmetic development. CMUJ Nat Sci 20:e2021008

    Google Scholar 

  13. Löfgren S (2017) Solar ultraviolet radiation cataract. Exp Eye Res 156:112–116

    PubMed  Google Scholar 

  14. Urbach F (2001) The historical aspects of sunscreens. J Photochem Photobiol B 64:99–104

    CAS  PubMed  Google Scholar 

  15. Hockberger PE (2002) A history of ultraviolet photobiology for humans, animals and microorganisms. Photochem Photobiol 76:561–579

    CAS  PubMed  Google Scholar 

  16. Lorenzen M, Racicot V, Strack D, Chapple C (1996) Sinapic acid ester metabolism in wild type and a sinapoylglucose-accumulating mutant of Arabidopsis. Plant Physiol 112:1625–1630

    CAS  PubMed  PubMed Central  Google Scholar 

  17. Ghazi S, Couteau C, Coiffard L (2010) What level of protection can be obtained using sun protective clothing? Determining effectiveness using an in vitro method. Int J Pharm 397:144–146

    CAS  PubMed  Google Scholar 

  18. Lowe N (2006) An overview of ultraviolet radiation, sunscreens, and photo-induced dermatoses. Dermatol Clin 24:9–17

    CAS  PubMed  Google Scholar 

  19. Lodén M, Beitner H, Gonzalez H, Edström D, Åkerström U, Austad J, Buraczewska-Norin I, Matsson M, Wulf H (2011) Sunscreen use: controversies, challenges and regulatory aspects. Br J Dermatol 165:255–262

    PubMed  Google Scholar 

  20. Jansen R, Osterwalder U, Wang SQ, Burnett M, Lim HW (2013) Photoprotection: part II. Sunscreen: development, efficacy, and controversies. J Am Acad Dermatol 69:867.e1-867.e14

  21. Mancebo SE, Hu JY, Wang SQ (2014) Sunscreens: a review of health benefits, regulations, and controversies. Dermatol Clin 32:427–438

    CAS  PubMed  Google Scholar 

  22. Jansen R, Wang SQ, Burnett M, Osterwalder U, Lim HW (2013) Photoprotection: part I. Photoprotection by naturally occurring, physical, and systemic agents. J Am Acad Dermatol 69:853.e1-853.e12

    CAS  Google Scholar 

  23. Holmes AM, Kempson IM, Turnbull T, Paterson D, Roberts MS (2020) Penetration of zinc into human skin after topical application of nano zinc oxide used in commercial sunscreen formulations. ACS Appl Bio Mater 3:3640–3647

    CAS  Google Scholar 

  24. Erickson B (2020) More evidence sunscreens are absorbed through skin. Chem Eng News 98:16–16

    Google Scholar 

  25. Kasting JF, Siefert JL (2002) Life and the evolution of Earth’s atmosphere. Science 296:1066–1068

    CAS  PubMed  Google Scholar 

  26. Enchev V, Angelov I, Mantareva V, Markova N (2015) 2-Carbamido-1, 3-indandione–a Fluorescent Molecular Probe and Sunscreen Candidate. J Fluoresc 25(6):1601–1614

    CAS  PubMed  Google Scholar 

  27. Kanavy HE, Gerstenblith MR (2011) Ultraviolet radiation and melanoma. In J Cutan Med Surg 4:222–228

    Google Scholar 

  28. Burnett ME, Wang SQ (2011) Current sunscreen controversies: a critical review. Photodermatol Photoimmunol Photomed 27:58–67

    CAS  PubMed  Google Scholar 

  29. Tan EM, Hilbers M, Buma WJ (2014) Excited-state dynamics of isolated and microsolvated cinnamate-based UV-B sunscreens. J Phys Chem Lett 5:2464–2468

    CAS  PubMed  Google Scholar 

  30. Kockler J, Oelgemöller M, Robertson S, Glass BD (2012) Photostability of sunscreens. J Photochem Photobiol C 13:91–110

    CAS  Google Scholar 

  31. Karsili TN, Marchetti B, Ashfold MN, Domcke W (2014) Ab initio study of potential ultrafast internal conversion routes in oxybenzone, caffeic acid, and ferulic acid: Implications for sunscreens. J Phys Chem A 118:11999–12010

    CAS  PubMed  Google Scholar 

  32. Baker LA, Horbury MD, Greenough SE, Coulter PM, Karsili TN, Roberts GM, Orr-Ewing AJ, Ashfold MN, Stavros VG (2015) Probing the ultrafast energy dissipation mechanism of the sunscreen oxybenzone after UVA irradiation. J Phys Chem Lett 6:1363–1368

    CAS  PubMed  Google Scholar 

  33. Krishnan R, Nordlund TM (2008) Fluorescence dynamics of three UV-B sunscreens. J Fluoresc 18:203–217

    CAS  PubMed  Google Scholar 

  34. Bastien N, Millau J-F, Rouabhia M, Davies RJH, Drouin R (2010) The sunscreen agent 2-phenylbenzimidazole-5-sulfonic acid photosensitizes the formation of oxidized guanines in cellulo after UV-A or UV-B exposure. J Invest Dermatol 130:2463–2471

    CAS  PubMed  Google Scholar 

  35. Narla S, Lim HW (2020) Sunscreen: FDA regulation, and environmental and health impact. Photochem Photobiol 19:66–70

    CAS  Google Scholar 

  36. Gasparro FP (2000) Sunscreens, skin photobiology, and skin cancer: the need for UVA protection and evaluation of efficacy. Environ Health Perspect 108:71–78

    CAS  PubMed  PubMed Central  Google Scholar 

  37. Abdel-Ghany MF, Ayad MF, Mikawy NN (2018) Sensitive synchronous spectrofluorimetric study of certain sunscreens using fluorescence enhancers in cosmeceutical formulations. J Fluoresc 28:491–504

    CAS  PubMed  Google Scholar 

  38. Diffey BL, Tanner PR, Matts PJ, Nash JF (2000) In vitro assessment of the broad-spectrum ultraviolet protection of sunscreen products. J Am Acad Dermatol 43:1024–1035

    CAS  PubMed  Google Scholar 

  39. Saeed S, Channar PA, Larik FA, Saeed A, Nadeem MA, Iqbal A (2019) Charge/energy transfer dynamics in CuO quantum dots attached to photoresponsive azobenzene ligand. J Phys Chem A 371:44–49

    CAS  Google Scholar 

  40. Saeed S, Yin J, Khalid MA, Channar PA, Shabir G, Saeed A, Nadeem MA, Soci C, Iqbal A (2019) Photoresponsive azobenzene ligand as an efficient electron acceptor for luminous CdTe quantum dots. J Phys Chem A 375:48–53

    CAS  Google Scholar 

  41. Siddique Z, Payne JL, Irvine JT, Jagadamma LK, Akhter Z, Samuel ID, Iqbal A (2020) Effect of halide-mixing on tolerance factor and charge-carrier dynamics in (CH 3 NH 3 PbBr 3 – x Cl x) perovskites powders. J Mater Sci 31:19415–19428

    Google Scholar 

  42. Teixeira RI, da Silva RB, Gaspar CS, de Lucas NC, Garden SJ (2021) Photophysical properties of fluorescent 2-(Phenylamino)‐1, 10‐phenanthroline derivatives. Photochem Photobiol 97:47–60

    CAS  PubMed  Google Scholar 

  43. Ji Y, Zhou L, Zhang Y, Ferronato C, Brigante M, Mailhot G, Yang X, Chovelon J-M (2013) Photochemical degradation of sunscreen agent 2-phenylbenzimidazole-5-sulfonic acid in different water matrices. Water Res 47:5865–5875

    CAS  PubMed  Google Scholar 

  44. Senesi N (1990) Molecular and quantitative aspects of the chemistry of fulvic acid and its interactions with metal ions and organic chemicals: Part I. The electron spin resonance approach. Anal Chim Acta 232:51–75

    CAS  Google Scholar 

  45. Bose D, Sarkar D, Chattopadhyay N (2010) Probing the binding interaction of a phenazinium dye with serum transport proteins: a combined fluorometric and circular dichroism study. Photochem Photobiol 86:538–544

    CAS  PubMed  Google Scholar 

  46. Koppal V, Melavanki R, Kusanur R, Patil N (2021) Analysis of fluorescence quenching of coumarin derivative under steady state and transient state methods. J Fluoresc. https://doi.org/10.1007/s10895-020-02663-3

    Article  PubMed  Google Scholar 

Download references

Acknowledgements

This work was performed within the Department of Chemistry Quaid-i-Azam University Islamabad. The authors gratefully acknowledge financial support by Higher Education Commission (HEC) Pakistan through research/equipment grants 20-3071/NRPU/R&D/HEC/13 and 6976/Federal/NRPU/R&D/HEC/2017.

Funding

This study was supported by Higher Education Commission (HEC) Pakistan through research/equipment grants 20-3071/NRPU/R&D/HEC/13 and 6976/Federal/NRPU/R&D/HEC/2017.

Author information

Authors and Affiliations

  1. Department of Chemistry, Quaid-I-Azam University, Islamabad, 45320, Pakistan

    Muhammad Mubeen, Muhammad Adnan Khalid, Maria Mukhtar, Saba Shahrum, Shanila Zahra & Azhar Iqbal

  2. Department of Materials Science and Engineering, Institute of Space Technology, 44000, Islamabad, Pakistan

    Saima Shabbir

Authors
  1. Muhammad Mubeen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Muhammad Adnan Khalid
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Maria Mukhtar
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Saba Shahrum
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Shanila Zahra
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Saima Shabbir
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Azhar Iqbal
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

All authors contribute to the study of conception and design. Muhammad Mubeen performed the experiments and wrote the initial draft of the manuscript. Muhammad Adnan Khalid, Maria Mukhtar, Saba Shahrum and Sanila Zahra helped to conduct the experiments and data acquisition. Saima Shabbir commented on the manuscript and revised. Azhar Iqbal perceived the idea, acquired the funding, and supervised the work and writing of the manuscript.

Corresponding author

Correspondence to Azhar Iqbal.

Ethics declarations

Conflicts of Interests/Competing Interests

There are no conflicts of interest to declare.

Ethics Approval

Not applicable.

Consent to Participate

Not applicable.

Consent of Publication

Not applicable.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mubeen, M., Khalid, M.A., Mukhtar, M. et al. Elucidating the Photoluminescence Quenching in Ensulizole: an Artificial Water Soluble Sunscreen. J Fluoresc 31, 1055–1063 (2021). https://doi.org/10.1007/s10895-021-02736-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10895-021-02736-x

Keywords

Search

Navigation