Advertisement

Distinctive effects on fluorescence quantum yields of 4-substituted N-methylphthalimides by inclusion complexation with β-cyclodextrins

  • Yoshimi SueishiEmail author
  • Yuki Matsumoto
  • Junko Sohama
  • Yoshihiro Osawa
  • Hideki Okamoto
Original Article
  • 30 Downloads

Abstract

The inclusion constants K for the complexation of 4-substituted N-methylphthalimides with β-cyclodextrins [β-CD and 2,6-di-O-methylated β-CD (DM-β-CD)] were determined from the fluorescence spectra that were enhanced by the inclusion. The structures of the 1:1 inclusion complexes were characterized using 2D ROESY NMR measurements. 4-Substituted N-methylphthalimides showed higher stability for the inclusion complexes formed with the methylated β-CD compared with those with native β-CD (KDM-β-CD/Kβ-CD = 1.2–2.1); this is attributed to the enhanced hydrophobic interaction due to the methylation of the rim OH groups. 4-Substituted N-methylphthalimides having donor–acceptor (D–A) characteristics showed large blue shifts of the fluorescence maxima. In addition, we determined the fluorescence quantum yields (Φ values) for the inclusion complexes using quantum measurement apparatus equipped with a half-moon unit. The Φ values of the D–A N-methylphthalimides were significantly enhanced by the inclusion of β-CDs. The results suggested that the hydrogen-bonding interaction of the OH groups of the β-CD rim with N-methylphthalimides is not operative and that the enhancement of the quantum yield upon inclusion is attributable to the local polarity around the phthalimides inside the hydrophobic CD cavity.

Keywords

N-Methylphthalimide β-Cyclodextrin Inclusion complexation Quantum yield Substituent effect 

Notes

Supplementary material

10847_2018_877_MOESM1_ESM.docx (960 kb)
Supplementary material 1 (DOCX 960 KB)

References

  1. 1.
    Soujanya, T., Fessenden, R.W., Samanta, A.: Role of nonfluorescent twisted intramolecular charge transfer state on the photophysical behavior of aminophthalimide dyes. J. Phys. Chem. 100, 3507–3512 (1996)CrossRefGoogle Scholar
  2. 2.
    Morimoito, A., Yatsuhashi, T., Shimada, T., Biczok, L., Tryk, D.A., Inoue, H.: Radiationless deactivation of an intramolecular charge transfer excited State through hydrogen bonding: effect of molecular structure and hard-soft anionic character in the excited state. J. Phys. Chem. A 105, 10488–10496 (2001)CrossRefGoogle Scholar
  3. 3.
    Feringa, B.L.: Molecular Switches. Wiley, Weinheim (2001)CrossRefGoogle Scholar
  4. 4.
    Okamoto, H., Kohno, M., Satake, K., Kimura, M.: An azacrowned phthalimide as a metal-ion sensitive and solvatofluorochromic fluorophores: fluorescence properties and a mimic integrated logic operation. Bull. Chem. Soc. Jpn 78, 2180–2187 (2005)CrossRefGoogle Scholar
  5. 5.
    Dsouza, R.N., Pischel, U., Nau, W.M.: Fluorescent dyes their supramolecular host/guest complexes with macrocycles in aqueous solution. Chem. Rev. 111, 7941–7980 (2011)CrossRefGoogle Scholar
  6. 6.
    Griesbeck, A.G., Ongel, B., Atar, M.: New phthalimide-methionine dyad-based fluorescence probes for reactive oxygen species: singlet oxygen, hydrogen peroxide, and hypochlorite. J. Phys. Org. Chem. 30, e3741 (2017)CrossRefGoogle Scholar
  7. 7.
    Saenger, W.: Cyclodextrin inclusion compounds in research and industry. Angew. Chem. Int. Ed. Engl. 19, 344–362 (1980)CrossRefGoogle Scholar
  8. 8.
    Wagner, B.D., Fitzpatrick, S.J.: A comparison of the host-guest inclusion complexes of 1,8-ANS and 2,6-ANS in parent and modified cyclodextrins. J. Incl. Phenom. Macrocycl. Chem. 38, 467–478 (2000)CrossRefGoogle Scholar
  9. 9.
    Sueishi, Y., Inazumi, N., Hanaya, T.: NMR spectroscopic characterization of inclusion complexes of hydroxy-substituted naphthalenes with native and modified β-cyclodextrins. J. Incl. Phenom. Macrocycl. Chem. 64, 135–141 (2009)CrossRefGoogle Scholar
  10. 10.
    Wintgens, V., Amiel, C.: New 4-amino-N-alkylphthalimides as fluorescence probes for β-cyclodextrin inclusion complexes as hydrophobic microdomains of amphiphilic systems. J. Photochem. Photobiol. A 168, 217–226 (2004)CrossRefGoogle Scholar
  11. 11.
    Sueishi, Y., Fujita, T., Nakatani, S., Inazumi, N., Osawa, Y.: The enhancement of fluorescence quantum yields on anilinonaphthalene sulfonic acids by inclusion of various cyclodextrins and cucurbit[7]uril. Spectroc. Acta Pt. A-Mol. Biomol. Spectrsc. 114, 344–349 (2013)CrossRefGoogle Scholar
  12. 12.
    Markezich, R.L., Zamek, O.S.: Reaction of fluoride and nitrite ions with 4-nitrophthalimides. J. Org. Chem. 42, 3431–3434 (1977)CrossRefGoogle Scholar
  13. 13.
    Velapoldi, R.A., Tonnesen, H.H.: Corrected emission spectra and quantum yields for a series of fluorescent compounds in the visible spectra region. J. Fluoresc. 14, 465–472 (2004)CrossRefGoogle Scholar
  14. 14.
    Job, P.: Formation and stability of inorganic complexes in solution. Ann. Chim. 9, 113–203 (1928)Google Scholar
  15. 15.
    Scott, R.L.: Some comments on the Benesi-Hildebrand equation. Recl Trav. Chim. Pays-Bas 75, 787–789 (1956)CrossRefGoogle Scholar
  16. 16.
    Kosower, E.M., Dodiuk, H.: Intramolecular donor-acceptor systems. 3. A third type of emitting singlet state for N-alkyl-6-N-arylamino-2-naphthalenesulfonates. Solvent modulation of substituent effects on charge-transfer emissions. J. Am. Chem. Soc. 100, 4173–4179 (1978)CrossRefGoogle Scholar
  17. 17.
    Sueishi, Y., Yoshioka, C., Hishikawa, H., Yamamoto, S.: Effects of pressure on two types of complexations of 4-dimethylaminoazobenzene with β-cyclodextrin. Z. Phys. Chem. 216, 1261–1266 (2002)CrossRefGoogle Scholar
  18. 18.
    Namor, A.F.D., Traboulssi, R., Lewis, D.F.V.: Host properties of cyclodextrins toward anion constituents of antigenic determinants. A thermodynamic study in water and in N,N-dimethylformamide. J. Am. Chem. Soc. 112, 8442–8447 (1990)CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  • Yoshimi Sueishi
    • 1
    Email author
  • Yuki Matsumoto
    • 1
  • Junko Sohama
    • 1
  • Yoshihiro Osawa
    • 2
  • Hideki Okamoto
    • 1
  1. 1.Department of Chemistry, Faculty of ScienceOkayama UniversityOkayamaJapan
  2. 2.Otsuka Electronics Co. Ltd.Kouka-shiJapan

Personalised recommendations