10930 J. Phys. Chem. B, Vol. 102, No. 52, 1998
Kotchevar et al.
1990, 112, 5851. (c) Nagawa, Y.; Regen, S. L. J. Am. Chem. Soc. 1992,
114, 1668. (d) Naka, K.; Sadownik, A.; Regen, S. L. J. Am. Chem. Soc.
1993, 115, 2278.
(8) Scrimin, P.; Tecilla, P.; Moss, R. A.; Bracken, K. J. Am. Chem.
Soc. 1998, 120, 1179.
(9) (a) Ohsumi, Y.; Kitamoto, K.; Anraku, Y. J. Bacteriol. 1998, 170,
2676. (b) Zhang, D.; Yasuda, T.; Yu, Y.; Okada, S. Acad. Med. Okayama.
1994, 48, 131.
(10) (a) Gutteridge, J. M. C.; Quinlan, G. J.; Clark, I.; Halliwell, B.
Biochim. Biophys. Acta 1985, 835, 441. (b) Quinlan, G. J.; Halliwell, B.;
Moorhouse, C. P.; Gutteridge, J. M. C. Biochim. Biophys. Acta 1988, 962,
196. (c) Deleers, M.; Servais, J.-P.; Wulfert, E. Biochim. Biophys. Acta
1985, 813, 195.
(11) (a) Verstraeten, S. J.; Oteiza, P. I. Arch. Biochem. Biophys. 1995,
322, 284. (b) Verstraeten, S. V.; Nogueira, L. V.; Schreier, S.; Oteiza, P. I.
Arch. Biochem. Biophys. 1997, 338, 121.
(12) (a) Ozawa, T.; Hanaki, A. Chem. Phar. Bull. 1989, 37, 1407. (b)
Carmichael, A. J. FEBS Lett. 1990, 261, 165. (c) Younes, M.; Strubelt, O.
Toxicology 1991, 66, 63. (d) Sakurai, H.; Nakai, M.; Miki, T.; Tsuchiya,
K.; Takada, J.; Matsushita, R. Biochem. Biophys. Res. Commun. 1995, 189,
1090. (e) Shi, X.; Wang, P.; Jiang, H.;Mao, Y.; Ahmed, N.; Dalal, N. Ann.
Clin. Lab. Sci. 1996, 26, 39.
(13) (a) D’Cruz, O. J.; Ghosh, P.; Uckun, F. M. Biol. Reprod. 1998,
58, 1515. (b) D’Cruz, O. J.; Ghosh, P.; Uckun, F. M. Mol. Hum. Reprod.
1998, 4, 683. (c) Ghosh, P.; Uckun, F. M. Manuscript in preparation.
(14) (a) Kroemer, G. Cell Death Diff. 1997, 4, 443. (b) Zamzani, N.;
Marchetti, P.; Castedo, M.; Zanin, C.; Vayssiere, J.-L.; Petit, P. X.; Kroemer,
G. J. Exp. Med. 1995, 181, 1661.
model studies. We found that two of these compounds (1 and
2) cause the liposomes to become permeable, and this effect is
not related to the extent of peroxidation of the lipids by the
vanadium-chelated complexes or to a tendency to cause ag-
gregation or fusion or alter the membrane packing order. We
believe that in order to observe such properties, these two
compounds must have a unique structural requirement, particu-
larly the hydrophobicity, planarity, and rigidity of the coordi-
nated ancillary ligands, which could alter the membrane by
intercalation. Although these results do not explain the cause
of the sperm immobilization and apoptosis by vanadocene
complexes, we can concur with the findings of D’Cruz et al.13a,b
that these complexes certainly do not cause disruption of
membranes, as evidenced from the above physicochemical
studies of the model liposomal membranes.
Supporting Information Available: Figures depicting the
vanadocene-chelated complex concentration-dependent liposo-
mal aggregation, fusion, and fluorescence polarization experi-
ments with different liposomes (PC and PG) (3 pages). See any
current masthead page for ordering and Internet access instruc-
tions.
(15) Hyde, J. S. ReV. Sci. Instrum. 1972, 43, 629.
(16) (a) Doyle, G.; Tobias, R. S. Inorg. Chem. 1968, 7, 2479. (b) Casey,
A. T.; Thackeray, J. R. Aust. J. Chem. 1974, 27, 757.
References and Notes
(17) Betageri, G. V.; Jenkins, S. A.; Parsons, D. L. Liposome Drug
DeliVery Systems; Technomic: Lancaster, PA. 1993; pp 13-14.
(18) Control experiments demonstrated that the small amount of
methanol added did not affect the permeability of the liposome.
(19) Bramhall, J.; Hofmann, J.; DeGuzman, R.; Montestruque, S.; Schell,
R. Biochemistry 1987, 26, 6330.
(20) Gutteridge, J. M. C. Anal. Biochem. 1975, 69, 518.
(21) Jahnig, F. Proc. Natl. Acad. Sci. U.S.A. 1979, 76, 6361.
(22) Struck, D. K.; Hoekstra, D.; Pagano, R. E. Biochemistry 1981, 20,
4093.
(23) (a) Toney, J. H.; Brock, C. P.; Marks, T. J. J. Am. Chem. Soc.
1986, 108, 7263. (b) Casey, A. T.; Thackeray, J. R. Aust. J. Chem. 1972,
25, 2085.
(24) (a) Arkin, M. R.; Stemp, E. D. A.; Turro, C.; Barton, J. K. J. Am.
Chem. 1996, 118, 2267. (b) Davies, K.; Hassan, A. Langmuir 1993, 9, 3270.
(c) Ottaviani, M. F.; Ghatlia, N. D.; Turro, N. J. J. Phys. Chem. 1992, 96,
6073. (d) Kunjappu, J. T.; Somasundaran, P.; Turro, N. J. J. Phys. Chem.
1990, 94, 8464. (e) Snyder, S. W.; Buell, S. L.; Demas, J. N.; DeGraff, B.
A. J. Phys. Chem. 1989, 93, 5265.
(25) (a) Dupureur, C. M.; Barton, J. K. In ComprehensiVe Supramo-
lecular Chemistry; Lehn, J.-M., Ed.; Pergamon: Oxford, 1995; Vol. 5. (b)
Dupureur, C. M.; Barton, J. K. J. Am. Chem. Soc. 1994, 116, 10286. (c)
Hartshorn, R. M.; Barton, J. K. J. Am. Chem. Soc. 1992, 114, 5919.
(26) Konings, A. W. T. In Liposome Technology; Gregoriadis, G., Ed.;
CRC: Boca Raton, FL, 1992; Vol. 1, pp 139-161 and references therein.
(27) Sanyal, I.; Mahroof-Tahir, M.; Nasir, M. S.; Ghosh, P.; Cohen, B.
I.; Gultneh, Y.; Cruse, R. W.; Farooq, A.; Karlin, K. D.; Liu, S.; Zubieta,
J. Inorg. Chem. 1992, 31, 4322.
(1) (a) Gennis, R. B. Biomembranes, Molecular Structure and Function;
Springer-Verlag: New York, 1989; p 85. (b) Fendler, J. H. Membrane
Mimetic Chemistry; Wiley: New York, 1982; pp 3-4.
(2) (a) Langs, D. A. Science 1988, 241, 188. (b) O’Connell, A. M.;
Koeppe, R. E.; Andersen, O. S. Science 1990, 250, 1256. (c) Galvez, A.;
Maqueda, M.; Martinez-Bueno, M.; Valdivia, E. J. Bacteriol. 1991, 886.
(d) Matsuzaki, K.; Yoneyama, S.; Fujii, N.; Mijajima, K.; Yamada, K.;
Kirino, Y.; Anzai, K. Biochemistry 1997, 36, 9799.
(3) (a) Hartsel, S. C.; Perkins, W. R.; McGarvey, G. J.; Cafiso, D. S.
Biochemistry 1988, 27, 2656. (b) Fuhrhop, J.-H.; Liman, U.; Koesling, V.
J. Am. Chem. Soc. 1988, 110, 6840. (c) Lindloy, L. F.; Walker, G. W.;
Everett, G. W. J. Am. Chem. Soc. 1990, 112, 3659. (d) Bolard, J.; Legrand,
P.; Heitz, F.; Cybulska, B. Biochemistry 1991, 30, 5707. (e) Tsukube, H.;
Takagi, K.; Higashiyama, T.; Iwaachido, T.; Hayama, N. Inorg. Chem. 1994,
33, 2984.
(4) (a) Fyles, T. M.; James, T. D.; Kaye, K. C. J. Am. Chem. Soc.
1993, 115, 12315. (b) Carmichael, V. E.; Dutton, P. J.; Fyles, T. M.; James,
T. D.; Swan, J. A.; Zojaji, M. J. Am. Chem. Soc. 1989, 111, 767. (c) Voyer,
N.; Robitaille, M. J. Am. Chem. Soc. 1995, 117, 6599. (d) Kragten, U. F.;
Roks, F. M.; Nolte, R. J. M. J. Chem. Soc., Chem. Commun. 1985, 1275.
(e) Neevel, J. G.; Nolte, R. J. M. Tetrahedron Lett. 1984, 21, 2263. (f)
Pregel, M. J.; Jullien, L.; Canceill, J.; Lacombe, L.; Lehn, J.-M. J. Chem.
Soc., Perkin Trans. 2 1995, 417.
(5) Fuhrhop, J.-H.; Liman, U. J. Am. Chem. Soc. 1984, 106, 4643.
(6) Hunt, G. R. A. FEBS Lett. 1980, 119, 132.
(7) (a) Jayasuriya, N.; Bosak, S.; Regen, S. L. J. Am. Chem. Soc. 1990,
112, 5844. (b) Jayasuriya, N.; Bosak, S.; Regen, S. L. J. Am. Chem. Soc.