Abstract
To clarify the acyl substitution effect on the fluorescent property of Cypridina oxyluciferin analogs, which have the 4-(dimethylamino)phenyl group at C5, we compared the spectroscopic properties of benzamide 1b and its 2,6-dimethylphenyl derivative 1c in various solvents with those of acetamide 1a. Similarity of the fluorescence wavelengths of 1a–c indicates that the π-electronic conjugation in the excited singlet (S1) state is terminated at the acyl group and that the benzamide moiety in 1b has little effect on modulating the florescence color. The similar fluorescence solvatochromism of 1a–c reveals that their S1 states have a similar intramolecular charge transfer character. The fact that 1a–c have various fluorescence quantum yields and lifetimes depending on solvent polarity and hydrogen bonding interactions in solutions provides information about the decay processes competing with the fluorescence process in the S1 states. Among 1a–c, benzamide 1b exhibits the most sensitive variation of the fluorescence intensity depending on the solvent used. Similarity of the fluorescence spectra of 1a–c adsorbed in NaY zeolites was also observed, which indicates that the S1 states of 1a–c give mobile conformers in the NaY supercages. The relationship between the molecular structures of 1a–c and their spectroscopic properties will provide a guide for designing a new fluorophore based on Cypridina oxyluciferin.
Graphical Abstract
Similar content being viewed by others
References
O. Shimomura, Bioluminescence: Chemical Principles and Methods (World Scientific, Singapore, 2006)
T. Goto, Pure Appl. Chem. 17, 421–441 (1968)
F.H. Johnson, O. Shimomura, Methods Enzymol. 57, 331–364 (1978)
K. Teranishi, Bioorg. Chem. 35, 82–111 (2007)
T. Goto, H. Fukatsu, Tetrahedron Lett. 49, 4299–4302 (1969)
T. Hirano, Y. Gomi, T. Takahashi, K. Kitahara, F.Q. Chen, I. Mizoguchi, S. Kyushin, M. Ohashi, Tetrahedron Lett. 39, 5771–5774 (1992)
R. Saito, T. Hirano, H. Niwa, M. Ohashi, J. Chem. Soc. Perkin Trans. 2, 1711–1716 (1997)
T. Hirano, Y. Takahashi, H. Kondo, S. Maki, S. Kojima, H. Ikeda, H. Niwa, Photochem. Photobiol. Sci. 7, 197–207 (2008)
S. Hachiya, T. Inagaki, D. Hashizume, S. Maki, H. Niwa, T. Hirano, Tetrahedron Lett. 51, 1613–1615 (2010)
R. Saito, T. Hirano, S. Maki, H. Niwa, M. Ohashi, Bull. Chem. Soc. Jpn. 84, 90–99 (2011)
N.J. Turro, V. Ramamurthy, J.C. Scaiano, Modern Molecular Photochemistry of Organic Molecules, Chap 13 (University Science Books, Sausalito, 2010)
D.F. Eaton, Pure Appl. Chem. 7, 1107–1114 (1988)
M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery, Jr., J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, Ö. Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian 09, Revision A.1 (Gaussian, Inc., Wallingford, 2009)
A.D. Becke, J. Chem. Phys. 98, 5648–5652 (1993)
C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37, 785–789 (1988)
P.J. Stephens, F.J. Devlin, C.F. Chabalowski, M.J. Frisch, J. Phys. Chem. 98, 11623–11627 (1994)
C. Reichardt, Solvents and Solvent Effects in Organic Chemistry, 3rd edn. (Wiley-VCH, Weinheim, 2003)
E. Lippert, Z. Electrochem. 61, 962–975 (1957)
N. Mataga, Y. Kaifu, M. Koizumi, Bull. Chem. Soc. Jpn. 29, 465–470 (1956)
J.R. Lakowicz, Principles of Fluorescence Spectroscopy, 3rd edn. (Springer, New York, 2006)
F. Lahmani, E. Breheret, A. Zehnacker-Rentien, C. Amatore, A. Jutand, J. Photochem. Photobiol. A 70, 39–49 (1993)
M. Maus, W. Rettig, D. Bonafoux, R. Lapouyade, J. Phys. Chem. A 103, 3388–3401 (1999)
D.W. Breck, Zeolite Molecular Sieves–Structure, Chemistry and Use (Wiley, New York, 1974)
Acknowledgments
This work was supported by a Grant-in-Aid for Scientific Research C (no. 22550031) from the Japan Society for the Promotion of Science. Financial support was also provided by the Casio Science Promotion Foundation and the Iketani Science and Technology Foundation. We thank the Information Technology Center of the University of Electro-Communications for technical assistance in computing the quantum-chemical calculations.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Hirano, T., Nakagawa, T., Kodaka, A. et al. 5-[4-(Dimethylamino)phenyl]-2-benzamidopyrazines: fluorescent dyes based on Cypridina oxyluciferin. Res Chem Intermed 39, 233–245 (2013). https://doi.org/10.1007/s11164-012-0645-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11164-012-0645-3