5326
A. L. P. Nery et al. / Tetrahedron 56 (2000) 5317±5327
[IV](4.1^0.8)£1025
M
and [F]6.6£1025 to 6.2£
10. Schmidt, S. P.; Schuster, G. B. J. Am. Chem. Soc. 1980, 102,
306±314.
1022 M.
11. McCapra, F.; Beheshti, I.; Burford, A.; Hann, R. A.; Zaklika,
K. A. J. Chem. Soc., Chem. Commun. 1977, 944±946.
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3829.
Activation parameters for the initiated decomposition.
These experiments were performed as those for the uni-
molecular decomposition. The dioxetane was added to a
cuvette, containing 3 mL THF at the desired temperature,
followed by addition of 100 mL of TBAF (1.0 M solution in
THF) and the kinetic pro®les measured, using
[II](2.0^0.4)£1025 M, [IV](4.1^0.8)£1025 M, [F]
3.2£1022 M, at 0±258C.
13. Zakika, K. A.; Kissel, T.; Thayer, A. L.; Burns, P. A.; Schaap,
A. P. Photochem. Photobiol. 1979, 30, 35±44.
14. Schaap, A. P.; Gagnon, S. D. J. Am. Chem. Soc. 1982, 104,
3504±3506.
15. Nakamura, K.; Goto, T. Photochem. Photobiol. 1979, 30, 27±33.
È
16. White, E. H.; Worther, H.; Seliger, H. H.; McElroy, W. D.
J. Am. Chem. Soc. 1966, 88, 2015±2019.
Fluorescent quantum yields. The ¯uorescence quantum
yields of the cleavage products of II and IV were deter-
mined by deprotection of the corresponding silylated alde-
hydes 9b and 15 by TBAF ([TBAF]3.2£1022 M), in THF,
using ¯uorescein as standard (FFL0.91 in aqueous 0.1 M
NaOH).39 The ¯uorescence spectra of both solutions,
¯uorescein and the deprotected cleavage products, were
measured by exciting the samples at 430 nm under identical
experimental conditions.
17. Schaap, A. P.; Chen, T.-S.; Handley, R. S.; De Silva, R.; Giri,
B. P. Tetrahedron Lett. 1987, 28, 1155±1158.
18. Schaap, A. P.; Handley, R. S.; Giri, B. P. Tetrahedron Lett.
1987, 28, 935±938.
19. Schaap, A. P.; Sandison, M. D.; Handley, R. S. Tetrahedron
Lett. 1987, 28, 1159±1162.
20. Bronstein, I.; Voyta, J. C.; Lazzari, K. G.; Murphy, O.;
Edwards, B.; Kricka, L. J. Biotechniques 1992, 12, 748±753.
21. Nishizono, I.; Iida, S.; Suzuki, N.; Kawada, H.; Murakami, H.;
Ashihara, Y.; Okada, M. Clin. Chem. 1991, 37, 1639±1644.
22. Lim, T.; Komoda, Y.; Nakamura, N.; Matsunaga, T. Anal.
Chem. 1999, 71, 1298±1302.
Chemiluminescence and singlet quantum yields. In a
3 mL cuvette, containing anhydrous THF and the dioxetane,
100 mL of the ¯uoride solution (TBAF 1.0 M solution in
THF) were added at 258C. The kinetic pro®les for the
decomposition were measured and the integral of the curves
È
23. Beck, S.; Koster, H. Anal. Chem. 1990, 62, 2258±2270.
24. Adam, W.; Reinhardt, D.; Sahamoller, C. R. Analyst 1996,
121, 1527±1531.
calculated. The chemiluminescence quantum yield (FCHL
)
corresponds to the total light emission (area under the curve)
divided by the number of moles of dioxetane (n) using
[II](2.3^0.5)£1025 M and [IV](4.3^0.7)£1025 M.
After calculation of FCHL the singlet quantum yields (Fs)
were determined according to the following equation:
25. Matsumoto, M.; Watanabe, N.; Kobayashi, H.; Azami, M.;
Ikawa, H. Tetrahedron Lett. 1997, 38, 411±414.
26. Matsumoto, M.; Ishihara, T.; Watanabe, N.; Hiroshima, T.
Tetrahedron Lett. 1999, 40, 4571±4574.
27. Watanabe, N.; Suganuma, H.; Kobayashi, H.; Mutoh, H.;
Katao, Y.; Matsumoto, M. Tetrahedron 1999, 55, 4287±4298.
28. Watanabe, N.; Kobayashi, H.; Azami, M.; Matsumoto, M.
Tetrahedron 1999, 55, 6831±6840.
FsFCHL/FFL
.
Acknowledgements
29. Adam, W.; Reinhardt, D. Liebigs Ann. 1997, 1359±1364.
30. Imanishi, T.; Ueda, Y.; Tainaka, R.; Miyashita, K. Tetrahedron
Lett. 1997, 38, 841±844.
We thank FAPESP, FINEP, CAPES, CNPq and DAAD
foundations for ®nancial support. Furthermore, a donation
Â
of 60% hydrogen peroxide by Solvay Peroxidos do Brasil
Ltda Company is gratefully acknowledged.
31. Adam, W.; Bronstein, I.; Tro®mov, A. V.; Vasil'ev, R. F. J. Am
Chem. Soc. 1999, 121, 958±961.
È
32. Nery, A. L. P.; Ropke, S.; Catalani, L. H.; Baader, W. J.
Tetrahedron Lett. 1999, 40, 2443±2446.
33. Adam, W.; Baader, W. J. J. Am. Chem. Soc. 1985, 107, 410±
416.
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