(%): 882 (10) [Mꢀ ꢀ H] (unreacted ATTA-Eu31 was not
found). Unfortunately we were unable to obtain the precise
yield and data of EP-ATTA-Eu31 including 1H NMR and
elemental analysis because of the interference of some inor-
ganic ions abounding in the product. The purification of the
endoperoxide is difficult, since the solid endoperoxide is not
very stable, which can be reduced by some organic solvents.
3
4
R. D. Scurlock, B. Wang, P. R. Ogilby, J. R. Sheats and R. L.
Clough, J. Am. Chem. Soc., 1995, 117, 10194.
(a) I. E. Kochevar, M. C. Lynch, S. Zhuang and C. R. Lambert,
Photochem. Photobiol., 2000, 72, 548; (b) K. R. Weishaupt, C. J.
Gomer and T. J. Dougherty, Cancer Res., 1976, 36, 2326.
(a) L. O. Klotz, K. Briviba and H. Sies, Methods Enzymol., 2000,
319, 130; (b) S. W. Ryster and R. M. Tyrrell, Free Radical Biol.
Med., 1998, 24, 1520; (c) S. Basu-Modak and R. M. Tyrrell,
Cancer Res., 1993, 53, 4505.
(a) C. Schweitzer and R. Schmidt, Chem. Rev., 2003, 103, 1685; (b)
G. R. Martinez, P. D. Mascio, M. G. Bonini, O. Augusto,
K. Briviba, H. Sies, P. Maurer, U. Rothlisberger, S. Herold and
¨
W. H. Koppenol, Proc. Natl. Acad. Sci. USA, 2000, 97, 10307.
(a) A. A. Krasnovsky Jr., Biol. Membr., 1998, 15, 530; (b) T.
Keszthelyi, D. Weldon, T. N. Andersen, T. D. Poulsen, K. V.
Mikkelsen and P. R. Ogilby, Photochem. Photobiol., 1999, 70, 531;
(c) L. K. Andersen, Z. Cao, P. R. Ogilby, L. Poulsen and I.
Zebger, J. Phys. Chem. A, 2002, 106, 8488.
(a) E. J. Corey and W. C. Taylor, J. Am. Chem. Soc., 1964, 86,
3881; (b) H. H. Wasserman, J. R. Scheffer and J. L. Cooper, J.
Am. Chem. Soc., 1972, 94, 4991; (c) N. J. Turro, M. F. Chow and
J. Rigaudy, J. Am. Chem. Soc., 1981, 103, 7218; (d) M. J.
Steinbeck, A. U. Khan and M. J. Karnovsky, J. Biol. Chem.,
1992, 267, 13425; (e) M. J. Steinbeck, A. U. Khan and M. J.
Karnovsky, J. Biol. Chem., 1993, 268, 15649.
5
6
7
Reactions of ATTA-Eu31 with reactive oxygen species
All reactions were carried out in 0.05 M carbonate buffer of pH
10.5 with the same ATTA-Eu31 concentration (100 nM).
Superoxide solution was prepared by adding KO2 to dry
dimethyl sulfoxide and stirring vigorously for 10 min.26 Hy-
droxyl radical was generated through the Fenton reaction of
ferrous ammonium sulfate and hydrogen peroxide.26 Singlet
oxygen was chemically generated from the MoO42ꢀ–H2O2
system in alkaline media.15
8
9
1
Detection of O2 in aqueous media
The reaction of ATTA-Eu31 with 1O2 generated from a
MoO42ꢀ–H2O2 system was performed in 0.1 M carbonate
buffer of pH 10.5. A series of H2O2 solutions were added to
the buffer solutions containing 10 mM of ATTA-Eu31 and
1 mM of Na2MoO4. After the reaction, the solutions were
diluted 10-fold (final probe concentration ¼ 1.0 mM) with 0.05
M borate buffer of pH 9.1, and the excitation and emission
spectra were measured with a time-resolved mode.
(a) N. Umezawa, K. Tanaka, Y. Urano, K. Kikuchi, T. Higuchi
and T. Nagano, Angew. Chem., Int. Ed., 1999, 38, 2899; (b) K.
Tanaka, T. Miura, N. Umezawa, Y. Urano, K. Kikuchi, T.
Higuchi and T. Nagano, J. Am. Chem. Soc., 2001, 123, 2530.
10 X. H. Li, G. X. Zhang, H. M. Ma, D. Q. Zhang, J. Li and D. B.
Zhu, J. Am. Chem. Soc., 2004, 126, 11543.
11 (a) E. Soini and T. Lovgren, CRC Crit. Rev. Anal. Chem., 1987,
¨
18, 105; (b) E. P. Diamandis and T. K. Christopoulos, Anal.
Chem., 1990, 62, 1149A; (c) I. Hemmila and V.-M. Mukkala, Crit.
¨
The photosensitization reaction was carried out in 0.05 M
Tris-HCl buffer of pH 7.4. The buffer solution containing 200
mM TMPyP and 10 mM of ATTA-Eu31 were irradiated from a
distance of 2 cm by a 100 W tungsten lamp. After the reaction,
the solution was diluted 100-fold (final probe concentration ¼
100 nM) with the buffer, and the time-resolved luminescence
measurement was carried out on a Perkin Elmer Victor 1420
Multilabel Counter.
Rev. Clin. Laboratory Sci., 2001, 38, 441; (d) J. Yuan, G. Wang,
K. Majima and K. Matsumoto, Anal. Chem., 2001, 73, 1869.
12 B. Song, G. Wang and J. Yuan, Chem. Commun., 2005, 3553–
3555.
13 M. Latva, H. Takallo, V. M. Mukkala, C. Matachescu, J. C. R.
Ubis and J. Kankare, J. Lumin., 1997, 75, 149.
14 (a) G. Albano, V. Balzani, E. C. Constable, M. Maestri and D. R.
Smith, Inorg. Chim. Acta, 1998, 277, 225; (b) G. J. Wilson, A.
Launikonis, W. H. F. Sasse and A. W. H. Mau, J. Phys. Chem. A,
1997, 101, 4860.
1
The experiments of real-time monitoring of O2 generation
in an HRP-catalyzed oxidation system of IAA were carried out
in 0.05 M sodium acetate buffer of pH 4.0. To a series of IAA
solutions (2.0 ml) containing 10 mM ATTA-Eu1 were added
10 ml of 50 mM HRP (the molar concentration of HRP was
calculated by using the molecular weight, MHRP ¼ 40 000)
under constant stirring. The reaction kinetic curves were
recorded simultaneously after the addition of HRP on a Perkin
Elmer LS 50B luminescence spectrometer with a time-resolved
mode.
15 (a) J. M. Aubry and B. Cazin, Inorg. Chem., 1988, 27, 2013; (b) J.
M. Aubry, B. Cazin and F. Duprat, J. Org. Chem., 1989, 54, 726.
16 M. H. V. Werts, J. W. Verhoeven and J. W. Hofstraat, J. Chem.
Soc., Perkin Trans. 2, 2000, 433.
17 A. Beeby, I. M. Clarkson, R. S. Dickins, S. Faulkner, D. Parker,
L. Royle, A. S. de Sousa, J. A. G. Williams and M. Woods,
J. Chem. Soc., Perkin Trans. 2, 1999, 493.
18 O. S. Wolfbeis, A. Durkpo, M. Wu and Z. Lin, Angew. Chem., Int.
Ed., 2002, 41, 4495.
¨
19 J. R. Harbour and S. L. Issler, J. Am. Chem. Soc., 1982, 104, 903.
20 A. Villanueva, L. Caggiari, G. Jori and C. Milanesi, J. Photochem.
Photobiol. B: Biol., 1994, 23, 49.
21 R. H. Kenten, Biochem. J., 1955, 59, 110.
22 (a) M. P. De Mello, S. M. De Toledo, M. Haun, G. Cilento and N.
Duran, Biochem., 1980, 19, 5270; (b) J. R. Kanofsky, J. Biol.
Chem., 1988, 263, 14171.
23 M. H. V. Werts, R. T. F. Jukes and J. W. Verhoeven, Phys. Chem.
Chem. Phys., 2002, 4, 1542.
24 G. Ofelt, J. Chem. Phys., 1963, 38, 2171.
Acknowledgements
The authors thank for the partial support from The National
Natural Science Foundation of China (20175027) and Scien-
tific Research Innovation Foundation of the Chinese Academy
of Sciences.
25 (a) G. Albano, V. Balzani, E. C. Constable, M. Maestri and D. R.
Smith, Inorg. Chim. Acta, 1998, 277, 225; (b) G. J. Wilson, A.
Launikonis, W. H. F. Sasse and A. W. H. Mau, J. Phys. Chem. A,
1997, 101, 4860.
26 H. T. Zhao, S. Kalivendi, H. Zhang, J. Joseph, K. Nithipatikom,
J. Vasquez-Vivar and B. Kalyanaraman, Free Radical Biol. Med.,
2003, 34, 1359.
References
1
(a) C. Foote, in Free Radicals in Biology, ed. W. A. Pryor,
Academic Press, New York, 1976, vol. 2, pp. 85–133; (b) H. Sies
and C. F. Menck, Mutat. Res., 1992, 275, 367.
2
(a) M. E. Murphy and H. Sies, Methods Enzymol., 1990, 186, 595;
(b) J. R. Kanofsky, Chem. Biol. Interact., 1989, 70, 1.
1438
N e w J . C h e m . , 2 0 0 5 , 2 9 , 1 4 3 1 – 1 4 3 8