Communications
bis(aminomethyl)anthracene derivative is negatively influenced
by the first protonated amine, as a result of the repulsion existing
between its ammonium group and the second incoming proton.
In this way, larger macrocycles like those presented here would
protonate the second amine (and hence lead to restoration of the
fluorescence) at a lower concentration of protons (higher pKa)
than the smaller macrocycles, as the former macrocycles would
accommodate the second positive charge more easily than the
latter. However, other contributions should not be disregarded,
in particular solvation effects in protonated species. A more
extensive study of a larger family of peptidomimetic molecules is
in progress.
Keywords: biosensors · fluorescent probes · macrocycles ·
peptidomimetics · protonation
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[1] T. Hirano, K. Kikuchi, Y. Urano, T. Higuchi, T. Nagano, Angew.
Chem. 2000, 112, 1094 – 1096; Angew. Chem. Int. Ed. 2000, 39,
1052 – 1054.
[2] Z. H. Lin, M. Wu , M. Schaferling, O. S. Wolfbeis, Angew. Chem.
2004, 116, 1767 – 1770; Angew. Chem. Int. Ed. 2004, 43, 1735 –
1738.
[3] N. Umezawa, K. Tanaka, Y. Urano, K. Kikuchi, T. Higuchi, T.
Nagano, Angew. Chem. 1999, 111, 3076 – 3079; Angew. Chem.
Int. Ed. 1999, 38, 2899 – 2901.
[4] H. Kojima, Y. Urano, K. Kikuchi, T. Higuchi, Y. Hirata, T.
Nagano, Angew. Chem. 1999, 111, 3419 – 3422; Angew. Chem.
Int. Ed. 1999, 38, 3209 – 3212.
[19] For a recent and comprehensive study of the effect of variations
of the chemical structure on the photophysical properties of pH
probes useful in vivo, see: C. J. Fahrni, L. Yang, D. G. VanDerv-
eer, J. Am. Chem. Soc. 2003, 125, 3799 – 3812.
[5] a) P. D. Beer, P. A. Gale, Angew. Chem. 2001, 113, 502 – 532;
Angew. Chem. Int. Ed. 2001, 40, 486 – 516; b) R. Martínez-
Mµæez, F. Sancenón, Chem. Rev. 2003, 103, 4419 – 4476.
[6] a) A. P. de Silva, H. Q. N. Gunaratne, T. Gunnlaugsson, A. J. M.
Huxley, C. P. McCoy, J. T. Rademacher, T. E. Rice, Chem. Rev.
1997, 97, 1515 – 1566; b) A. W. Czarnik, Acc. Chem. Res. 1994,
27, 302 – 308; c) Fluorescent Chemosensors for Ion and Molecule
Recognition, ACS Symp. Ser. 1993, 538.
[7] a) H. Izumi, T. Torigoe, H. Ishiguchi, H. Uramoto, Y. Yoshida,
M. Tanabe, T. Ise, T. Murakami, T. Yoshida, M. Nomoto, K.
Kohno, Cancer Treat. Rev. 2003, 29, 541 – 549; b) M. Chesler,
Physiol. Rev. 2003, 83, 1183 – 1221; c) M. M. Wu, J. Llopis, S.
Adams, J. M. McCaffery, M. S. Kulomaa, T. E. Machen, H.-P. H.
Moore, R. Y. Tsien, Chem. Biol. 2000, 7, 197 – 209; d) A. M.
Paradiso, R. Y. Tsien, T. E. Machen, Nature 1987, 325, 447 – 450.
[8] a) R. P. Haugland,
Handbook of Fluorescent Probes and
Research Products, 9th ed., Molecular Probes, Eugene, OR,
2002; b) Z. J. Diwu, C.-S. Chen, C. Zhang, D. H. Klaubert, R. P.
Haugland, Chem. Biol. 1999, 6, 411 – 418; c) J. Liu, Z. J. Diwu,
W.-Y. Leung, Bioorg. Med. Chem. Lett. 2001, 11, 2903 – 2905;
d) H.-J. Lin, P. Herman, J. S. Kang, J. R. Lakowicz, Anal.
Biochem. 2001, 294, 118 – 125; e) J. Liu, Z. Diwu, D. H. Klaubert,
Bioorg. Med. Chem. Lett. 1997, 7, 3069 – 3072.
[9] M. Schindler, S. Grabski, E. Hoff, S. M. Simon, Biochemistry
1996, 35, 2811 – 2817.
[10] J. M. Holopainen, J. Saarikoski, P. K. J. Kinnunen, I. Jarvela, Eur.
J. Biochem. 2001, 268, 5851 – 5856.
[11] Patent pending. Application number GB 0509245.7
[12] J. Becerril, M. Bolte, M. I. Burguete, F. Galindo, E. García-
Espaæa, S. V. Luis, J. F. Miravet, J. Am. Chem. Soc. 2003, 125,
6677 – 6686.
[13] a) F. Galindo, M. I. Burguete, S. V. Luis, Chem. Phys. 2004, 302,
287 – 294; b) F. Galindo, J. Becerril, M. I. Burguete, S. V. Luis, L.
Vigara, Tetrahedron Lett. 2004, 45, 1659 – 1662; c) B. Escuder, J.
Becerril, M. I. Burguete, F. Galindo, R. Gavara, J. F. Miravet,
S. V. Luis, G. Peris, Chem. Eur. J. 2004, 10, 3879 – 3890.
[14] J. S. Nowick, S. Insaf, J. Am. Chem. Soc. 1997, 119, 10903 –
10908.
[15] a) A. P. de Silva, R. A. D. D. Rupasinghe, J. Chem. Soc. Chem.
Commun. 1985, 1669 – 1670; b) R. A. Bissell, E. Calle, A. P.
de Silva, S. A. de Silva, H. Q. N. Gunaratne, J.-L. Habib-Jiwan,
S. L. A. Peiris, R. A. D. D. Rupasinghe, T. K. S. D. Samara-
singhe, K. R. A. S. Sandanayake, J.-P. Soumillion, J. Chem. Soc.
Perkin Trans. 2 1992, 1559 – 1564.
[16] LysoSensor and LysoTracker probes are available from Molec-
ular Probes, Eugene, OR, USA.
[17] D. Rehm, A. Weller, Isr. J. Chem. 1970, 8, 259 – 271.
[18] Such
a different protonation behavior must occur for a
combination of reasons. To partially explain the phenomenon,
the observation made years ago for related systems (ref. [15b]) is
relevant: The protonation of the second amine in a 9,10-
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Angew. Chem. Int. Ed. 2005, 44, 6504 –6508