Porphyrins
2456±2461
brecht, A. Louati, M. Gross, Angew. Chem. 1995, 107, 2906; Angew.
Chem. Int. Ed. Engl. 1995, 34, 2725; c)P. J. Dandliker, F. Diederich, A.
Zingg, J. P. Gisselbrecht, M. Gross, A. Louati, E. M. Sanford, Helv.
Chim. Acta 1997, 80, 1773.
[
[
5] a)P. Bhyrappa, J. K. Young, J. S. Moore, K. S. Suslick, J. Am. Chem.
Soc. 1996, 118, 5708; b)P. Bhyrappa, G. Vaijayanthimala, K. S. Suslick,
J. Am. Chem. Soc. 1999, 121, 262.
6] a)Y. Tomoyose, D.-L. Jiang, R.-H. Jin, T. Aida, T. Yamashita, K.
Horie, E. Yashima, Y. Okamoto, Macromol. 1996, 29, 5236; b)N.
Tomioka, D. Takasu, T. Takahashi, T. Aida, Angew. Chem. 1998, 110,
1
611; Angew. Chem. Int. Ed. Engl. 1998, 37, 1531; c)M. Numata, A.
Ikeda, C. Fukuhara, S. Shinkai, Tetrahedron Lett. 1999, 40, 6945.
[
7] a)R. Sadamoto, N. Tomioka, T. Aida, J. Am. Chem. Soc. 1996, 118,
Figure 6. Uncorrected emission spectra of the acidified sample (pH ꢀ0.01)
3
978; b)K. W. Pollak, J. W. Leon, J. M. J. FreÂchet, M. Maskus, H. D.
3
of H
2
PorphGlu OH (N 3)( 3)resulted from excitation at different
Abruna, Chem. Mater. 1998, 10, 30.
wavelengths. The intensities of the spectra marked with ª Â 10º are
[8] D. L. Jiang, T. Aida, J. Am. Chem. Soc. 1998, 120, 10895.
9] K. W. Pollak, E. M. Sanford, J. M. J. Fr e chet, J. Mater. Chem. 1998, 8,
enlarged by a factor of 10.
[
5
19.
[
10] a)S. A. Vinogradov, D. F. Wilson, Adv. Exp. Med. Biol. 1997, 428, 657;
b)S. A. Vinogradov, L. W. Lo, D. F. Wilson, Chem. Eur. J. 1999, 5,
size are shown to alter the protonation constants of the
encapsulated porphyrin. An important result is that the value
of the first protonation constant of the three-layered den-
1
338.
[
11] F. Vögtle, M. Plevoets, M. Nieger, G. C. Azzellini, A. Credi, L.
3
drimer± porphyrin H PorphGlu OH, pK 6.98, is appropri-
De Cola, V. De Marchis, M. Venturi, V. Balzani, J. Am. Chem. Soc.
2
3
1
999, 121, 6290.
ate for broad pH sensing in biological systems. This combined
with almost unlimited water solubility, impermeability
[
[
12] M. Gouterman in The Porphyrins, Vol. III (Ed.: D. Dolphin),
Academic Press, New York, 1979, pp. 1 ± 165.
13] N. Datta-Gupta, T. J. Bardos, J. Heterocycl. Chem. 1966, 3, 495.
through the biological membranes, and the high quantum
3
efficiency of fluorescence make H PorphGlu OH a promising
[14] P. G. Seybold, M. Gouterman, J. Mol. Spectrosc. 1969, 31, 1.
[
[
2
15] M. Gouterman, J. Mol. Spectrosc. 1961, 6, 138.
16] P. Hanbright, in Porphyrins and Metalloporphyrins (Ed.: K. M.
Smith), Elsevier, Amsterdam, 1975, pp. 233 ± 278.
new pH indicator.
[
17] a)D. L. Akins, H.-R. Zhu, C. Guo, J. Phys. Chem. 1994, 98, 3612;
b)D. L. Akins, H. R. Zhu, C. Guo, J. Phys. Chem. 1996, 100, 5420;
c)D. L. Akins, S. Ozcelik, H. R. Zhu, C. Guo, J. Phys. Chem. 1996,
Acknowledgement
This work was supported by Grants CA-74062 and HL-60100 from
National Institutes of Health (NIH).
1
00, 14390.
[
18] a)R. F. Khairutdinov, N. Serpone, J. Phys. Chem. B 1999, 103, 761;
b)N. C. Maiti, S. Mazumdar, N. Periasamy, J. Phys. Chem. B 1998, 102,
1
528.
[
1] a)D. K. Smith, F. Diederich, Chem. Eur. J. 1998, 4, 1353; b)F. W.
Zeng, S. C. Zimmerman, Chem. Rev. 1997, 97, 1681; c)M. Fischer, F.
Vögtle, Angew. Chem. 1999, 111, 934; Angew. Chem. Int. Ed. Engl.
[19] a)R. F. Pasternak, P. R. Huber, P. Boyd, G. Engasser, L. Francesconi,
E. Gibbs, P. Fasella, G. Cerio Ventura, L. C. Hinds, J. Am. Chem. Soc.
1972, 94, 4511; b)D. C. Barber, R. A. Freitag-Beeston, D. G. Whitten,
J. Am. Chem. Soc. 1991, 95, 4074; c)J. M.Ribo, J. Crusats, J. A.
Farrera, M. L. Valero, J. Chem. Soc. Chem. Commun. 1994, 681.
1
999, 38, 885; d)G. R. Newkome, E. He, C. N. Moorefield, Chem. Rev.
999, 99, 1689.
1
[
[
2] D.-L. Jiang, T. Aida, Chem. Commun. 1996, 1523.
a
[20] The pK values for glutamic acid are 2.19 and 4.25 (A. L. Lehninger,
3] a)R.-H. Jin, T. Aida, S. Inoue, Chem. Commun. 1993, 1260; b)J. P.
Collman, L. Fu, A. Zingg, F. Diederich, Chem. Commun. 1997, 193;
c)D. L. Jiang, T. Aida, J. Macromol. Sci. Pure Appl. Chem. 1997, A34,
Biochemistry, 2nd ed., Worth Publishers, New York, 1977, p. 79).
[21] J. Sutter, P. Hambright, M. Krisnamurthu, P. B. Chock, Inorg. Chem.
1974, 13, 1974.
2
047.
[22] D. J. Quimby, F. R. Longo, J. Am. Chem. Soc. 1975, 97, 5111.
[
4] a)P. J. Dandliker, F. Diederich, M. Gross, C. B. Knobler, A. Louati,
E. M. Sanford, Angew. Chem. 1994, 106, 1821; Angew. Chem. Int. Ed.
Engl. 1994, 33, 1739; b)P. J. Dandliker, F. Diederich, J.-P. Gissel-
Received: October 21, 1999 [F2101]
Chem. Eur. J. 2000, 6, No. 13
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