Fluorescence Characteristics of Methoxycoumarins as Novel Fluorophores

Akira TAKADATE; Toshinobu MASUDA; Chiyomi MURATA; Toshiharu TANAKA; Mitsuru IRIKURA; Shujiro GOYA

doi:10.2116/analsci.11.97

Akira TAKADATE, Toshinobu MASUDA, Chiyomi MURATA, Toshiharu TANAKA, Mitsuru IRIKURA, Shujiro GOYA

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Keywords: Methoxycoumarin, fluorphore, fluorescence reagent, fluorescence emission mechanism, intramolecular charge-transfer

JOURNAL FREE ACCESS

1995 Volume 11 Issue 1 Pages 97-101

DOI https://doi.org/10.2116/analsci.11.97

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Published: February 10, 1995 Received: October 24, 1994 Available on J-STAGE: July 04, 2006 Accepted: December 07, 1994 Advance online publication: - Revised: -
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Date of correction: July 04, 2006 Reason for correction: - Correction: CITATION Details: Wrong : 1). T. Hinohara, K. Amano and K. Matsui, Nippon Kagaku Kaishi, 1976, 247.
2). I. Abe, J. Koga and N. Kuroki, Nippon Kagaku Kaishi, 1974, 1744.
3). A. Takadate, T. Tahara, H. Fujino and S. Goya, Chem. Pharm. Bull., 30, 4120 (1982).
4). A. Takadate, M. Irikura, T. Suehiro, H. Fujino and S. Goya, Chem. Pharm. Bull., 33, 1164 (1985).
5). A. Takadate, I. Yagashiro, M. Irikura, H. Fujino and S. Goya, Chem. Pharm. Bull., 37, 373 (1989).
6). A. Takadate, T. Masuda, C. Tajima, C. Murata, M. Irikura and S. Goya, Anal. Sci., 8, 663 (1992).
7). A. Takadate, T. Masuda, C. Murata, C. Haratake, A. Isobe, M. Irikura and S. Goya, Anal. Sci., 8, 695 (1992).
8). S. Goya, A. Takadate, H. Fujino, M. Otagiri and K. Uekama, Chem. Pharm. Bull., 30, 1363 (1982); A. Takadate, M. Irikura, Y. Ohkubo, S. Goya and M. Otagiri, Chem. Pharm. Bull., 35, 2104 (1987); M. Irikura, A. Takadate, S. Goya and M. Otagiri, Chem. Pharm. Bull., 39, 724 (1991).
9). T. Masuda, C. Murata, A. Takadate, T. Tanaka, M. Irikura and S. Goya, Abstract of papers, The 55th Symposium on Analytical Chemistry, Toyama, 1994,p. 251.
10). H. Gunther, J. Prestien and P. Joseph-Nathan, Org. Magn. Resonance, 7, 339 (1975).
11). A. H. Jackson and J. A. Martin, J. Chem. Soc. (C), 1966, 2222.
12). R. Adams(ed.), "Organic Reaction", Vol. VII, John Willey and Sons, Inc., New York, 1953, pp. 1-58.
13). E. C. Horning and M. G. Horning, J. Am. Chem. Soc., 69, 968 (1947).
14). R. Baker and J. L. Castro, J. Chem. Soc. Perkin Trans.1, 1990, 47; R. S. Mali, V. J. Yadav and R. N. Zaware, Indian J. Chem., 21B, 759 (1982); R. A. Glennon, S. M. Liebowitz, D. Leming-boot and J. A. Rosecrans, J. Med. Chem., 23, 990 (1980); F. S. H. Head and A. Robertson, J. Chem. Soc., 1930, 2434; W. Baker, J. F. W. McOmie and D. Miles, J. Chem. Soc., 1953, 820.
15). C. A. Parker and W. T. Rees, Analyst [London], 85, 587 (1960).
16). K. Yagi, Z. Yoshida and T. Tabata, "Keikou (Fluo-rescence, in Japanese)", 4th ed., pp. 27-42, Nankoudou, Tokyo, 1964.
17). T. H. Lowry and K. S. Richardson, "Mechanism and Theory in Organic Chemistry", 2nd ed., pp. 130-134, Harper & Row, Publishers, New York, 1981.
18). C. Hamada, M. Iwasaki, S. Goya, K. Zaitsu and Y. Ohkura, The 100th Annual Meeting of Pharmaceutical Society of Japan, Tokyo, April 1980, p. 567; C. Hamada, M. Iwasaki, N. Kuroda and Y. Ohkura, J. Chromatogr. Biomed. Appl., 341, 426 (1985).
19). Mp 147-148°C. NMR (CDCl₃)δ:3.88 (3H,s, C_6^- OCH₃),4.77(2H,s,C_3^-COCH_2^-),7.07(1H,s,C_{5^-H), 7.28 (1H,d,C_7^-H), 7.34 (1H,d,C_8^-H),8.59 (1H,s,C_{4^-H). MS m/z:296(M⁺),298(M⁺+2).
20). Mp 96-97°C. NMR (CDCl₃)δ:0.88 (3H,t,laurate-CH₃), 1.26-2.49 (20H,m, laurate-CH₂),3.87 (3H,s,C_6^- OCH₃),5.38(2H,s,C_3^-COCH_2^-),7.05(1H,s,C_5^-H),7.27 (1H,s,C_7^-H),7.33(1H,s,C_8^-H),8.59(1H,s, C_4^-H). MS m/z:416(M⁺).
21). A. Takadate, T. Masuda, C. Murata, T. Tanaka, H. Miyahara and S. Goya, Chem. Lett., 1993, 811.

Right : 1). T. Hinohara, K. Amano and K. Matsui, Nippon Kagaku Kaishi, 1976, 247.
2). I. Abe, J. Koga and N. Kuroki, Nippon Kagaku Kaishi, 1974, 1744.
3). A. Takadate, T. Tahara, H. Fujino and S. Goya, Chem. Pharm. Bull., 30, 4120 (1982).
4). A. Takadate, M. Irikura, T. Suehiro, H. Fujino and S. Goya, Chem. Pharm. Bull., 33, 1164 (1985).
5). A. Takadate, I. Yagashiro, M. Irikura, H. Fujino and S. Goya, Chem. Pharm. Bull., 37, 373 (1989).
6). A. Takadate, T. Masuda, C. Tajima, C. Murata, M. Irikura and S. Goya, Anal. Sci., 8, 663 (1992).
7). A. Takadate, T. Masuda, C. Murata, C. Haratake, A. Isobe, M. Irikura and S. Goya, Anal. Sci., 8, 695 (1992).
8). S. Goya, A. Takadate, H. Fujino, M. Otagiri and K. Uekama, Chem. Pharm. Bull., 30, 1363 (1982); A. Takadate, M. Irikura, Y. Ohkubo, S. Goya and M. Otagiri, Chem. Pharm. Bull., 35, 2104 (1987); M. Irikura, A. Takadate, S. Goya and M. Otagiri, Chem. Pharm. Bull., 39, 724 (1991).
9). T. Masuda, C. Murata, A. Takadate, T. Tanaka, M. Irikura and S. Goya, Abstract of papers, The 55th Symposium on Analytical Chemistry, Toyama, 1994,p. 251.
10). H. Gunther, J. Prestien and P. Joseph-Nathan, Org. Magn. Resonance, 7, 339 (1975).
11). A. H. Jackson and J. A. Martin, J. Chem. Soc. (C), 1966, 2222.
12). R. Adams(ed.), "Organic Reaction", Vol. VII, John Willey and Sons, Inc., New York, 1953, pp. 1-58.
13). E. C. Horning and M. G. Horning, J. Am. Chem. Soc., 69, 968 (1947).
14). R. Baker and J. L. Castro, J. Chem. Soc. Perkin Trans.1, 1990, 47; R. S. Mali, V. J. Yadav and R. N. Zaware, Indian J. Chem., 21B, 759 (1982); R. A. Glennon, S. M. Liebowitz, D. Leming-boot and J. A. Rosecrans, J. Med. Chem., 23, 990 (1980); F. S. H. Head and A. Robertson, J. Chem. Soc., 1930, 2434; W. Baker, J. F. W. McOmie and D. Miles, J. Chem. Soc., 1953, 820.
15). C. A. Parker and W. T. Rees, Analyst [London], 85, 587 (1960).
16). K. Yagi, Z. Yoshida and T. Tabata, "Keikou (Fluo-rescence, in Japanese)", 4th ed., pp. 27-42, Nankoudou, Tokyo, 1964.
17). T. H. Lowry and K. S. Richardson, "Mechanism and Theory in Organic Chemistry", 2nd ed., pp. 130-134, Harper & Row, Publishers, New York, 1981.
18). C. Hamada, M. Iwasaki, S. Goya, K. Zaitsu and Y. Ohkura, The 100th Annual Meeting of Pharmaceutical Society of Japan, Tokyo, April 1980, p. 567; C. Hamada, M. Iwasaki, N. Kuroda and Y. Ohkura, J. Chromatogr. Biomed. Appl., 341, 426 (1985).
19). Mp 147-148°C. NMR (CDCl₃)δ:3.88 (3H,s, C_6^- OCH₃),4.77(2H,s,C_3^-COCH_2^-),7.07(1H,s,C_5^-H), 7.28 (1H,d,C_7^-H), 7.34 (1H,d,C_8^-H),8.59 (1H,s,C_4^-H). MS m/z:296(M⁺),298(M⁺+2).
20). Mp 96-97°C. NMR (CDCl₃)δ:0.88 (3H,t,laurate-CH₃), 1.26-2.49 (20H,m, laurate-CH₂),3.87 (3H,s,C_6^- OCH₃),5.38(2H,s,C_3^-COCH_2^-),7.05(1H,s,C_5^-H),7.27 (1H,s,C_7^-H),7.33(1H,s,C_8^-H),8.59(1H,s, C_4^-H). MS m/z:416(M⁺).
21). A. Takadate, T. Masuda, C. Murata, T. Tanaka, H. Miyahara and S. Goya, Chem. Lett., 1993, 811.}}

Date of correction: July 04, 2006 Reason for correction: - Correction: PDF FILE Details: -

Abstract

The fluorescence characteristics of various methoxycoumarin fluorophores for the development of fluorescence reagents were examined in relation to their structures. The fluorescence emission mechanisms were also considered from the viewpoint of the intramolecular charge-transfer (CT) between methoxyl substituents and the coumarin ring. The arrangement of 6-methoxyl and 3-acetyl group pairs on the coumarin ring significantly contributed to the fluorescence enhancement through the intramolecular CT. We found that the structural features of methoxycoumarins required for intense fluorescence are to hold both diether bonds at the 6- and 7-positions and an electron-withdrawing group at the 3-position, as shown in 3-acetyl-6, 7-dimethoxycoumarin with 0.52 in quantum yield.

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