Fig. 8 Transmission electron micrograph (negative stain, 2% uranyl acetate) of aggregates formed from bolaamphiphiles 4b: (A) Ñexible tubules
in neuron-like networks in aqueous medium at pH 2; (B) Ðbers rolled up into rings in aqueous medium at pH 6.3.
6
7
8
9
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cles (d D 30È60 nm), Ðbers rolled into rings (Fig. 8B) and thin
twisted Ðbers. So, if the presence of a glucosidic head group
seems to favor the formation of Ðbers, it does not induce
aggregation to give regular helices. This could be explained by
the predominance of aromatic ring stacking over the chiral
e†ect of the carbohydrate head. This hypothesis is supported
by the work of Nolte et al. concerning amphiphilic glucona-
mides bearing a pyridinium ring on C of the sugar.13b
6
Conclusion
The results presented here support the conclusions of our pre-
vious work concerning symmetrical amphiphiles: the impor-
tance of pH, the structure of the amphiphile, the positions of
the connecting links and the ability to form hydrogen-bonded
networks. Concerning this last point, the shape of the aggre-
gates given by O-alkylated compounds at low pH are related
to the existence in the amphiphile of several groups (amide,
carboxyl, hydroxyl and protonated imidazole) allowing hydro-
gen bonding between these molecules. Indeed, for amphiphiles
with only an imidazolium group, polar head hydration pre-
dominates, leading to vesicle formation. When another group
responsible for hydrogen bonds also exists in the molecules,
they become organized into Ñexible Ðbers (ribbons or tubules).
10 (a) T. Shimizu and M. Masuda, J. Am. Chem. Soc., 1997, 119,
2812; (b) M. Masuda and T. Shimizu, Chem. Commun., 1996,
1057; (c) T. Shimizu, M. Masuda and M. Shibakami, Chem. L ett.,
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11 J. H. Fuhrhop, C. Fritsch, B. Tesche and H. Schmiady, J. Am.
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R. J. M. Nolte, J. Org. Chem., 1999, 64, 412.
The addition of
] hydroxyl or imidazolium ] amide ] carboxyl) induces the
formation of rigid Ðbers (rods).
a third group (imidazolium ] amide
The importance of hydrogen bonding is also demonstrated
by the fact that the bolaamphiphile with an arbutin head
group gives Ðbers. This emphasizes the importance of the
hydrogen bonding. Indeed, all other N-alkylated urocanic
compounds give vesicles.
14 (a) N. Nakashima, S. Asakuma, J. M. Kim and T. Kunitake,
Chem. L ett., 1984, 1709; (b) N. Nakashima, S. Asakuma and T.
Kunitake, J. Am. Chem. Soc., 1985, 107, 509.
15 J. H. Fuhrhop and J. Koning, Membranes and Molecular
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17 S. Franceschi, V. Andreu, N. de Viguerie, M. Riviere and A.
Lattes, New J. Chem., 1998, 22, 225.
18 J. Sirieix, N. Lauth-de Viguerie, M. Riviere and A. Lattes, L ang-
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24 J. Sirieix, N. Lauth-de Viguerie, M. Riviere and A. Lattes, Het-
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25 N. Lauth-de Viguerie, N. Sergueeva, M. Damiot, H. Mawlawi,
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These results will allow the design of urocanic amphiphiles
in view of further applications of their aggregates.
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