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Synthesis, characterization, photophysical, and photochemical properties of novel phthalocyanines containing thymoxy groups as bioactive units

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Abstract

In this study, new 4-chloro-5-(2-isopropyl-5-methylphenoxy)phthalonitrile compound, containing bioactive thymoxy group, and its metal-free phthalocyanine and metallo-phthalocyanine derivatives were synthesized for the first time. Their structures were determined by spectroscopic methods such as FTIR, UV–Vis, 1H-, and 13C-NMR (for phthalonitrile derivative), MALDI-TOF mass spectrometry (for phthalocyanine derivatives) and elemental analysis as well. The phthalocyanines showed excellent solubility in polar and nonpolar solvents without aggregation and absorb at long wavelengths with their high molar coefficient. In N,N-dimethylformamide, the effects of the type of central metal ions [metal-free, indium(III) acetate, lutetium(III) acetate, magnesium(II) or zinc(II)] in the phthalocyanine, containing bioactive thymoxy group, cavity on the spectroscopic, photophysical, and photochemical properties of the phthalocyanines were determined. These features are compared with each other. Lutetium(III) acetate phthalocyanine did not show any fluorescence, while metal-free phthalocyanine and indium(III) acetate phthalocyanine showed low fluorescence. It was determined that magnesium phthalocyanine significantly enriched the fluorescence, and zinc phthalocyanine had appropriate and sufficient fluorescence. Lutetium(III) acetate and zinc(II), especially indium(III) acetate phthalocyanines, could produce large amounts of singlet oxygen. Metal-free and magnesium phthalocyanines had the capacity to produce sufficient singlet oxygen (it means production of enough amount of singlet oxygen by a photosensitizer candidate during PDT applications). All phthalocyanines have sufficient and suitable photostability (it means an ideal photosensitizer should be stable under light irradiation until complete its PDT activation, and it should be decomposed after its PDT activation so that it does not accumulate in the body). With these determined properties, magnesium(II), especially indium(III) acetate and zinc(II) phthalocyanines, may be suitable candidates as type II photosensitizers for photodynamic therapy applications. Lutetium(III) acetate phthalocyanine may be a photosensitizer candidate in photocatalytic applications.

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References

  1. Crucius G (2013) Synthesen nichtperipher glykokonjugierter Zink (II) phthalocyanine. Universitätsbibliothek Tübingen

  2. Josefsen LB, Boyle RW (2012) Unique diagnostic and therapeutic roles of porphyrins and phthalocyanines in photodynamic therapy, imaging and theranostics. Theranostics 2:916

    Article  PubMed  PubMed Central  Google Scholar 

  3. Hamblin MR, Hasan T (2004) Photodynamic therapy: a new antimicrobial approach to infectious disease? Photochem Photobiol Sci 3:436–450

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  4. Patrice T (2003) Photodynamic therapy. Royal Society of Chemistry, London

    Book  Google Scholar 

  5. Hirth A, Michelsen U, Wöhrle D (1999) Photodynamische tumortherapie. Chem unserer Zeit 33:84–94

    Article  Google Scholar 

  6. Whitacre CM, Feyes DK, Satoh T, Grossmann J, Mulvihill JW et al (2000) Photodynamic therapy with the phthalocyanine photosensitizer Pc 4 of SW480 human colon cancer xenografts in athymic mice. Clin Cancer Res 6:2021–2027

    CAS  PubMed  Google Scholar 

  7. Allen CM, Sharman WM, Van Lier JE (2001) Current status of phthalocyanines in the photodynamic therapy of cancer. J Porphyr Phthalocyanines 5:161–169

    Article  CAS  Google Scholar 

  8. Dolmans DE, Fukumura D, Jain RK (2003) Photodynamic therapy for cancer. Nat Rev Cancer 3:380–387

    Article  CAS  PubMed  Google Scholar 

  9. Brasseur N (2003) Sensitizers for PDT: phthalocyanines. In: Patrice T (ed) Photodynamic therapy, vol 2. The Royal Society of Chemistry, London, pp 105–118

    Google Scholar 

  10. Flom SR (2003) Nonlinear optical properties of phthalocyanines. In: Kadish KM, Smith KM, Guilard R (eds) The porphyrin handbook. Application of phthalocyanines. Elsevier Academic Press, California, pp 179–190

    Chapter  Google Scholar 

  11. Tanaka M (2009) Phthalocyanines – high performance pigments and their applications. In: Faulkner EB, Schwartz RJ (eds) High performance pigments. John Wiley and Sons, Weinheim, pp 275–291

    Chapter  Google Scholar 

  12. Wöhrle D, Schnurpfeil G (2003) Porphyrins and Phthalocyanines in Macromolecules-110. In: The Porphyrin Handbook. Academic Press, Amsterdam

  13. Mckeown N, Weinreb S (2004) Science of Synthesis. Houben-Weyl Methods of Molecular Transformations–Hetarenes and Related Ring Systems. 17: 1237

  14. Seikel E (2012) Axial funktionalisierte Metallophthalocyanine und-porphyrazine als Funktionsmoleküle für optoelektronische Anwendungen. Philipps-Universität Marburg

  15. Wöhrle D, Eskes M, Shigehara K, Yamada A (1993) A Simple synthesis of 4, 5-disubstituted 1, 2-dicyanobenzenes and 2, 3, 9, 10, 16, 17, 23, 24-octasubstituted phthalocyanines. Synthesis 1993:194–196

    Article  Google Scholar 

  16. Atalay Ş, Çoruh U, Akdemir N, Ağar E (2004) C–H⋯ π interactions in 4, 5-bis (2-isopropyl-5-methylphenoxy) phthalonitrile. Acta Crystallogr Sect E: Struct Rep Online 60:o303–o305

    Article  CAS  Google Scholar 

  17. Nyokong T (2007) Effects of substituents on the photochemical and photophysical properties of main group metal phthalocyanines. Coord Chem Rev 251:1707–1722

    Article  CAS  Google Scholar 

  18. Becker HG, Böttcher H, Dietz F, Rehorek D, Roewer G et al. (1983) Einführung in die Photochemie. Thieme Stuttgart

  19. Klessinger M (1989) Physikalische organische Chemie. Verlag Chemie

  20. Grofcsik A, Baranyai P, Bitter I, Csokai V, Kubinyi M et al (2004) Triple state properties of tetrasubstituted zinc phthalocyanine derivatives. J Mol Struct 704:11–15

    Article  CAS  Google Scholar 

  21. Kumbhar PP, Dewang PM (2001) Eco-friendly pest management using monoterpenoids. I. Antifungal efficacy of thymol derivatives. J Sci Ind Res 60:645–648

    CAS  Google Scholar 

  22. Li Y, Wen J-m, Du C-j, Hu S-m, Chen J-x et al (2017) Thymol inhibits bladder cancer cell proliferation via inducing cell cycle arrest and apoptosis. Biochem Biophys Res Commun 491:530–536

    Article  CAS  PubMed  Google Scholar 

  23. Botelho M, Nogueira N, Bastos G, Fonseca S, Lemos T et al (2007) Antimicrobial activity of the essential oil from Lippia sidoides, carvacrol and thymol against oral pathogens. Braz J Med Biol Res 40:349–356

    Article  CAS  PubMed  Google Scholar 

  24. Braga PC, Dal Sasso M, Culici M, Bianchi T, Bordoni L, Marabini L (2006) Anti-inflammatory activity of thymol: inhibitory effect on the release of human neutrophil elastase. Pharmacology 77:130–136

    Article  CAS  PubMed  Google Scholar 

  25. Aeschbach R, Löliger J, Scott B, Murcia A, Butler J et al (1994) Antioxidant actions of thymol, carvacrol, 6-gingerol, zingerone and hydroxytyrosol. Food Chem Toxicol 32:31–36

    Article  CAS  PubMed  Google Scholar 

  26. Ma C, Tian D, Hou X, Chang Y, Cong F et al (2005) Synthesis and characterization of several soluble tetraphenoxy-substituted copper and zinc phthalocyanines. Synthesis 2005:741–748

    Article  Google Scholar 

  27. Sobotta L, Lijewski S, Dlugaszewska J, Nowicka J, Mielcarek J, Goslinski T (2019) Photodynamic inactivation of Enterococcus faecalis by conjugates of zinc(II) phthalocyanines with thymol and carvacrol loaded into lipid vesicles. Inorg Chim Acta 489:180–190

    Article  CAS  Google Scholar 

  28. Görlach B, Dachtler M, Glaser T, Albert K, Hanack M (2001) Synthesis and separation of structural isomers of 2(3),9(10),16(17),23(24)-tetrasubstituted phthalocyanines. Chem A Eur J 7:2459–2465

    Article  Google Scholar 

  29. Atajanov R, Huraibat B, Odabaş Z, Özkaya AR (2023) Electrochemical, spectroelectrochemical, and electrocatalytic properties of novel soluble phthalocyanines containing peripheral thymoxy and chloride units. Inorg Chim Acta 547:121360

    Article  CAS  Google Scholar 

  30. Fernandez JM, Bilgin MD, Grossweiner LI (1997) Singlet oxygen generation by photodynamic agents. J Photochem Photobiol B 37:131–140

    Article  CAS  Google Scholar 

  31. Kubiak R, Janczak J, Śledź M, Bukowska E (2007) Comparative study of beryllium, magnesium and zinc phthalocyanine complexes with 4-picoline. Polyhedron 26:4179–4186

    Article  CAS  Google Scholar 

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Acknowledgements

We are grateful to the Research Foundation of Marmara University, Commission of Scientific Research (BAPKO) for their support of this research as part of the project: FEN-C-YLP-120418-0164. In addition, we are very grateful to Assoc. Prof. Dr. Mehmet Pişkin for his skillful and fruitful collaboration.

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Authors and Affiliations

  1. Department of Chemistry, Marmara University, 34722, Kadıköy, Istanbul, Turkey

    Rovshen Atajanov & Zafer Odabaş

  2. Department of Chemistry, Gebze Technical University, 41400, Gebze, Kocaeli, Turkey

    Khaoula Khezami & Mahmut Durmuş

  3. Topkapı Campus, İstinye University, 31010, Zeytinburnu, Istanbul, Turkey

    Khaoula Khezami

  4. Mads Clausen Institute, SDU CAPE, University of Southern Denmark, 6400, Sønderborg, Denmark

    Rovshen Atajanov

Authors
  1. Rovshen Atajanov
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  2. Khaoula Khezami
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  3. Mahmut Durmuş
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  4. Zafer Odabaş
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Contributions

RA performed the synthesis, purification, and characterization of the starting compound and phthalocyanines in the article and write the manuscript. KK performed the photophysical and photochemical characterization of the phthalocyanines in the article. MD and ZO reviewed the manuscript.

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Correspondence to Zafer Odabaş.

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Atajanov, R., Khezami, K., Durmuş, M. et al. Synthesis, characterization, photophysical, and photochemical properties of novel phthalocyanines containing thymoxy groups as bioactive units. Transit Met Chem 48, 79–89 (2023). https://doi.org/10.1007/s11243-023-00525-y

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  • DOI: https://doi.org/10.1007/s11243-023-00525-y

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