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Twisting in the excited state of an N-methylpyridinium fluorescent dye modulated by nano-heterogeneous micellar systems

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Abstract

A push–pull N-methylpyridinium fluorescent dye with a pyrenyl group as the electron-donor portion was investigated within the nano-heterogeneous media provided by some micellar systems. The molecule was studied by stationary and time-resolved spectroscopic techniques in spherical micellar solutions and viscoelastic hydrogels, in order to throw light on the role played by twisting in its excited state deactivation. As proven by femtosecond fluorescence up-conversion and transient absorption experiments, the excited state dynamics of the molecule is ruled by charge transfer and twisting processes, which, from the locally excited (LE) state initially populated upon excitation, progressively lead to twisted (TICT) and planar (PICT) intramolecular charge transfer states. The inclusion within micellar aggregates was found to slow down and/or limit the rotation of the molecule with respect to what had previously been observed in water, while its confinement within the hydrophobic domains of the gel matrixes prevents any molecular torsion. The increasing viscosity of the medium, when passing from water to micellar systems, implies that the detected steady-state fluorescence comes from an excited state which is not fully relaxed, as is the case with the TICT state in micelles or the LE state in hydrogels, where the detected emission changes its usual orange colour to yellow.

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References

  1. B. Carlotti, G. Consiglio, F. Elisei, C. G. Fortuna, U. Mazzucato, A. Spalletti, J. Phys. Chem. A, 2014, 118, 3580.

    Article  CAS  PubMed  Google Scholar 

  2. P. Fromherz, A. Heilemann, J. Phys. Chem., 1992, 96, 6864.

    Article  CAS  Google Scholar 

  3. H. Görner, H. Gruen, J. Photochem., 1985, 28, 329.

    Article  Google Scholar 

  4. A. Battisti, S. Panettieri, G. Abbandonato, E. Jacchetti, F. Cardarelli, G. Signore, F. Beltram, R. Bizzarri, Anal. Bioanal. Chem., 2013, 405, 6223.

    Article  CAS  PubMed  Google Scholar 

  5. J. Bereiter-Hahn, K.-H. Seipel, M. Vöth, J. S. Ploem, Cell Biochem. Funct., 1983, 1, 147.

    Article  CAS  PubMed  Google Scholar 

  6. P. Fromherz, K. H. Dambacher, H. Ephardt, A. Lambacher, C. O. Müller, R. Neigl, H. Schaden, O. Schenk, T. Vetter, Ber. Bunsenges. Phys. Chem., 1991, 95, 1333.

    Article  CAS  Google Scholar 

  7. L. M. Loew, S. Scully, L. Simpson, A. S. Waggoner, Nature, 1979, 281, 497.

    Article  CAS  PubMed  Google Scholar 

  8. V. Diemer, H. Chaumeil, A. Defoin, P. Jacques, C. Carré, Tetrahedron Lett., 2005, 46, 4737.

    Article  CAS  Google Scholar 

  9. U. Narang, C. F. Zhao, J. D. Bhawalkar, F. V. Bright, P. N. Prasad, J. Phys. Chem., 1996, 100, 4521.

    Article  CAS  Google Scholar 

  10. C. F. Zhao, R. Gvishi, U. Narang, G. Ruland, P. N. Prasad, J. Phys. Chem., 1996, 100, 4526.

    Article  CAS  Google Scholar 

  11. C. G. Fortuna, C. Bonaccorso, F. Qamar, A. Anu, I. Ledoux, G. Musumarra, Org. Biomol. Chem., 2011, 9, 1608.

    Article  CAS  PubMed  Google Scholar 

  12. G. He, G. Wang, R. Meng, Y. Cui, Jpn. J. Appl. Phys., 2004, 43, 1357.

    Article  CAS  Google Scholar 

  13. C. G. Fortuna, G. Forte, V. Pittalà, A. Giuffrida, G. Consiglio, Comput. Theor. Chem., 2012, 985, 8.

    Article  CAS  Google Scholar 

  14. C. G. Fortuna, U. Mazzucato, G. Musumarra, D. Pannacci, A. Spalletti, J. Photochem. Photobiol., A, 2010, 216, 66.

    Article  CAS  Google Scholar 

  15. E. Marri, U. Mazzucato, C. G. Fortuna, G. Musumarra, A. Spalletti, J. Photochem. Photobiol., A, 2006, 79, 314.

    Article  CAS  Google Scholar 

  16. A. Mazzoli, A. Spalletti, B. Carlotti, C. Emiliani, C. G. Fortuna, L. Urbanelli, L. Tarpani, R. Germani, J. Phys. Chem. B, 2015, 119, 1483.

    Article  CAS  PubMed  Google Scholar 

  17. B. Carlotti, G. Consiglio, F. Elisei, C. G. Fortuna, U. Mazzucato, A. Spalletti, J. Phys. Chem. A, 2014, 118, 7782.

    Article  CAS  PubMed  Google Scholar 

  18. A. Mazzoli, B. Carlotti, G. Consiglio, C. G. Fortuna, G. Miolo, A. Spalletti, Photochem. Photobiol. Sci., 2014, 13, 939.

    Article  CAS  PubMed  Google Scholar 

  19. B. Carlotti, A. Cesaretti, C. G. Fortuna, A. Spalletti, F. Elisei, Phys. Chem. Chem. Phys., 2015, 17, 1877.

    Article  CAS  PubMed  Google Scholar 

  20. B. Carlotti, E. Benassi, A. Spalletti, C. G. Fortuna, F. Elisei, V. Barone, Phys. Chem. Chem. Phys., 2014, 16, 13984.

    Article  CAS  PubMed  Google Scholar 

  21. B. Carlotti, E. Benassi, V. Barone, G. Consiglio, F. Elisei, A. Mazzoli, A. Spalletti, ChemPhysChem, 2015, 16, 1440.

    Article  CAS  PubMed  Google Scholar 

  22. E. Benassi, B. Carlotti, M. Segado, A. Cesaretti, A. Spalletti, F. Elisei, V. Barone, J. Phys. Chem. B, 2015, 119, 6035.

    Article  CAS  PubMed  Google Scholar 

  23. A. Cesaretti, B. Carlotti, G. Consiglio, T. Del Giacco, A. Spalletti, F. Elisei, J. Phys. Chem. B, 2015, 119, 6658.

    Article  CAS  PubMed  Google Scholar 

  24. A. Cesaretti, B. Carlotti, R. Germani, A. Spalletti, F. Elisei, Phys. Chem. Chem. Phys., 2015, 17, 17214.

    Article  CAS  PubMed  Google Scholar 

  25. B. Carlotti, E. Benassi, A. Cesaretti, C. Fortuna, A. Spalletti, V. Barone, F. Elisei, Phys. Chem. Chem. Phys., 2015, 17, 20981.

    Article  CAS  PubMed  Google Scholar 

  26. C. G. Fortuna, V. Barresi, C. Bonaccorso, G. Consiglio, S. Failla, A. Trovato-Salinaro, G. Musumarra, Eur. J. Med. Chem., 2012, 47, 221.

    Article  CAS  PubMed  Google Scholar 

  27. V. P. Torchilin, Pharm. Res., 2007, 24, 1.

    Article  CAS  PubMed  Google Scholar 

  28. C. O. Rangel-Yagui, A. Pessoa Jr., L. C. Tavares, J. Pharm. Pharm. Sci., 2005, 8, 147.

    CAS  PubMed  Google Scholar 

  29. C. Ghatak, V. G. Rao, S. Mandal, S. Ghosh, N. Sarkar, J. Phys. Chem. B, 2012, 116, 3369.

    Article  CAS  PubMed  Google Scholar 

  30. A. Sanz-Medel, R. F. de la Campa, J. I. G. Alonso, Analyst, 1987, 112, 493.

    Article  CAS  Google Scholar 

  31. K. Bhattacharyya, Acc. Chem. Res., 2003, 36, 95.

    Article  CAS  PubMed  Google Scholar 

  32. S. K. Pal, D. Sukul, D. Mandal, S. Sen, K. Bhattacheryya, Chem. Phys. Lett., 2000, 327, 91.

    Article  CAS  Google Scholar 

  33. N. Sarkar, A. Datta, S. Das, K. Bhattacharyya, J. Phys. Chem., 1996, 100, 15483.

    Article  CAS  Google Scholar 

  34. K. Nishiyama, K. Takata, K. Watanabe, H. Shigematsu, Chem. Phys. Lett., 2012, 529, 39.

    Article  CAS  Google Scholar 

  35. R. Baumann, C. Ferrante, E. Kneuper, F. W. Deeg, C. Brauchle, J. Phys. Chem. A, 2003, 107, 2422.

    Article  CAS  Google Scholar 

  36. S. K. Pal, D. Sukul, D. Mandal, S. Sen, K. Bhattacharyya, J. Phys. Chem. B, 2000, 104, 2613.

    Article  CAS  Google Scholar 

  37. B. L. Bales, L. Messina, A. Vidal, M. Peric, J. Phys. Chem. B, 1998, 102, 1034.

    Article  Google Scholar 

  38. A. Cesaretti, B. Carlotti, C. Clementi, R. Germani, F. Elisei, Photochem. Photobiol. Sci., 2014, 13, 509.

    Article  CAS  PubMed  Google Scholar 

  39. A. Cesaretti, B. Carlotti, P. L. Gentili, C. Clementi, R. Germani, F. Elisei, Phys. Chem. Chem. Phys., 2014, 16, 23096.

    Article  CAS  PubMed  Google Scholar 

  40. L. Brinchi, R. Germani, P. Di Profio, L. Marte, G. Savelli, R. Oda, D. Berti, J. Colloid Interface Sci., 2010, 346, 100.

    Article  CAS  PubMed  Google Scholar 

  41. L. Goracci, R. Germani, G. Savelli, D. M. Bassani, ChemBioChem, 2005, 6, 197.

    Article  CAS  PubMed  Google Scholar 

  42. G. Bartocci, F. Masetti, U. Mazzucato, A. Spalletti, I. Baraldi, F. Momicchioli, J. Phys. Chem., 1987, 91, 4733.

    Article  CAS  Google Scholar 

  43. B. Carlotti, A. Cesaretti, F. Elisei, Phys. Chem. Chem. Phys., 2012, 14, 823.

    Article  CAS  PubMed  Google Scholar 

  44. A. Cesaretti, B. Carlotti, P. L. Gentili, C. Clementi, R. Germani, F. Elisei, J. Phys. Chem. B, 2014, 118, 8601.

    Article  CAS  PubMed  Google Scholar 

  45. G. H. Golub and C. F. Van Loan, Matrix computations, Johns Hopkins University Press, Baltimore, MD, 3rd edn, 1996.

    Google Scholar 

  46. G. Strang, Introduction to linear algebra, Wellesley-Cambridge Press, Wellesley, MA, 1998.

    Google Scholar 

  47. J. Snellenburg, S. Laptenok, R. Seger, K. Mullen, I. Van Stokkum, J. Stat. Software, 2012, 49, 1.

    Article  Google Scholar 

  48. I. H. van Stokkum, D. S. Larsen, R. van Grondelle, Biochim. Biophys. Acta, 2004, 1657, 82.

    Article  PubMed  CAS  Google Scholar 

  49. A. Romani, C. Clementi, C. Miliani, B. G. Brunetti, A. Sgamellotti, G. Favaro, Appl. Spectrosc., 2008, 62, 1395.

    Article  CAS  PubMed  Google Scholar 

  50. P. J. Steinbach, R. Ionescu, C. R. Matthews, Biophys. J., 2002, 82, 2244.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  51. P. J. Steinbach, J. Chem. Inf. Comput. Sci., 2002, 42, 1476.

    Article  CAS  PubMed  Google Scholar 

  52. M. Penconi, P. L. Gentili, G. Massaro, F. Elisei, F. Ortica, Photochem. Photobiol. Sci., 2014, 13, 48.

    Article  CAS  PubMed  Google Scholar 

  53. P. L. Gentili, C. Clementi, A. Romani, Appl. Spectrosc., 2010, 64, 923.

    Article  CAS  PubMed  Google Scholar 

  54. M. R. di Nunzio, P. L. Gentili, A. Romani, G. Favaro, J. Phys. Chem. C, 2010, 114, 6123.

    Article  CAS  Google Scholar 

  55. P. L. Gentili, Dyes Pigm., 2014, 110, 235.

    Article  CAS  Google Scholar 

  56. P. L. Gentili, ChemPhysChem, 2011, 12, 739.

    Article  PubMed  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, Biology and Biotechnology and Centro di Eccellenza sui Materiali Innovativi Nanostrutturati (CEMIN), University of Perugia, via Elce di Sotto 8, 06123, Perugia, Italy

    A. Cesaretti, B. Carlotti, P. L. Gentili, R. Germani, A. Spalletti & F. Elisei

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  1. A. Cesaretti
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  2. B. Carlotti
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  3. P. L. Gentili
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  4. R. Germani
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  5. A. Spalletti
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  6. F. Elisei
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Correspondence to A. Cesaretti.

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Electronic supplementary information (ESI) available. See DOI: 10.1039/c5pp00388a

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Cesaretti, A., Carlotti, B., Gentili, P.L. et al. Twisting in the excited state of an N-methylpyridinium fluorescent dye modulated by nano-heterogeneous micellar systems. Photochem Photobiol Sci 15, 525–535 (2016). https://doi.org/10.1039/c5pp00388a

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