Abstract
Based on our recent results, the present paper overviews noncovalent formation of high-axial-ratio nanostructures (HARNs), such as fibers, rods, tubes and ropes, through molecular self-assembly of bola-form amphiphilic (bolaamphiphilic) monomers. A variety of bolaamphiphiles, in which sugars, peptides, or nucleobases as headgroups are connected to both ends of a hydrocarbon spacer, were newly designed and synthesized. Their self-assembling behavior was examined in aqueous solutions in terms of bottom-up fabrication of organic nanostructures. The morphologies proved to strongly depend on the headgroup structure, spacer chain lengths and even-odd carbon numbers of used oligo(methylene) spacers. Typical examples of self-assembled morphologies include nanofibers from 1-glucosamide- or thymidine-appended bolaamphiphiles, vesicle-encapsulated microtubes from glycylglycine-appended bolaamphiphiles, double-helical ropes from thymine-appended bolaamphiphiles. These self-assembled HARNs are constructed hierarchically in a manner similar to biological structures. On the basis of several solid-state analyses, molecular packing and orientation within the HARNs are discussed and compared with the single crystal structures in terms of hydrogen-bond networks. Furthermore, pH-dependent reversible polymer formation was achieved using the combination of glucuronamide- and aromatic boronic acid-appended bola-form derivatives. Polymerization of bola-form 1-glucosamide derivatives with a 1,4-butadiyne group was performed in self-assembled nanometer-sized fibers, giving a single polydiacetylene chain of 64-mer that can be seen in TEM.
Similar content being viewed by others
Article PDF
References
E. Baer, A. Hiltner, and H. D. Keith, Science, 235, 1015 (1987).
D. A. Tomalia, A. M. Naylor, and A. Goddard, Angew. Chem., Int. Ed. Eng., 29, 138 (1990).
C. J. Hawker and J. M. J. Frechet, J. Am. Chem. Soc., 112, 7638 (1990).
T. M. Miller, Chem. Mater., 2, 346 (1990).
A. W. Bosman, H. M. Janssen, and E. W. Meijer, Chem. Rev., 99, 1665 (1999).
J.-P. Majoral and A.-M. Caminade, Chem. Rev., 99, 845 (1999).
S. C. Schülter, Adv. Mater., 3, 282 (1991).
H. Oike, H. Imaizumi, T. Mouri, Y. Yoshioka, A. Uchibori, and Y. Tezuka, J. Am. Chem. Soc., 122, 9592 (2000).
F. Wang, R. D. Rauh, and T. L. Rose, J. Am. Chem. Soc., 119, 11106 (1997).
J. Roovers, L.-L. Zhou, P. M. Toporowski, M.v.d. Zwan, H. Iatrou, and N. Hadjichristidis, Macromolecules, 26, 4324 (1993).
R. B. Grubbs, C. J. Hawker, J. Dao, and J. M. J. Frechet, Angew. Chem., Int. Ed. Eng., 36, 270 (1997).
R. Taylor and D. R. Walton, Nature, 363, 685 (1993).
I. Amato, Science, 254, 30 (1991).
D. B. Amabilino, I. W. Parsons, and J. F. Stoddart, TRIP, 2, 146 (1994).
C. Hamers, F. M. Raymo, and J. F. Stoddart, Eur. J. Org. Chem., 2109 (1998).
T. Ichi, J. Watanabe, T. Ooya, and N. Yui, Biomacromolecules, 2, 204 (2001).
H. Okumura, M. Okada, Y. Kawaguchi, and A. Harada, Macromolecules, 33, 4297 (2000).
Y. Okumura and K. Ito, Adv. Mater., 13, 485 (2001).
N. Yamaguchi and H. W. Gibson, Angew. Chem., Int. Ed. Eng., 38, 143 (1999).
C. Hamers, O. Kocian, F. M. Raymo, and J. F. Stoddart, Adv. Mater., 10, 1366 (1998).
J.-L. Weidmann, J.-M. Kern, J.-P. Sauvage, D. Muscat, S. Mullins, W. Köhler, C. Rosenauer, H.J. Räder, K. Martin, and Y. Geerts, Chem. Eur. J., 5, 1841 (1999).
For example, M. Kimura, M. Sano, T. Muto, K. Hanabusa, H. Shirai, and N. Kobayashi, Macromolecules, 32, 7951 (1999).
S. Kelch and M. Rehahn, Macromolecules, 30, 6185 (1997).
J. M. Lehn, Angew. Chem. Int. Ed. Eng., 29, 1304 (1990).
T. Kato and J. M. J. Frechet, J. Am. Chem. Soc., 111, 8533 (1989).
R. P. Sijbesma, F. H. Beijer, L. Brunsveld, B. J. B. Folmer, J. H. K. K. Hirschberg, R. F. M. Large, J. K. L. Lowe, and E. W. Meijer, Science, 278, 1601 (1997).
T. Shimizu, “Polymer Objects: Towards New Polymer Architectures”, in “Macromolecular Science and Engineering”, 2nd ed., Y. Tanabe, Ed., Springer-Verlag GmbH & Co. KG, Berlin, 1999, p 53.
T. Shimizu, Macromol. Rapid Commun., 23, 311 (2002).
T. Kunitake, Y. Okahata, M. Shimomura, S. Yasunami, and K. Takarabe, J. Am. Chem. Soc., 103, 5401 (1981).
T. Kunitake, Angew. Chem., Int. Ed. Eng., 31, 709 (1992).
S. I. Stupp, S. Son, H. C. Lin, and L. S. Li, Science, 259, 59 (1993).
L. H. Radzilowski, B. O. Carragher, and S. I. Stupp, Macromolecules, 30, 2110 (1997).
V. Percec, C.-H. Ahn, G. Ungar, D. J. P. Yeardley, M. Moller, and S. S. Sheiko, Nature, 391, 161 (1998).
A. Kumar and G. M. Whiteside, Appl. Phys. Lett., 63, 2002 (1993).
S. R. J. Oliver, T. D. Clark, N. Bowden, and G. M. Whitesides, J. Am. Chem. Soc., 123, 8119 (2001).
S. C. Zimmerman, F. Zeng, D. E. C. Reichert, and S. V. Kolotuchin, Science, 271, 1095 (1996).
G. M. Whitesides, J. P. Mathias, and C. T. Seto, Science, 254, 1312 (1991).
G. A. Jeffrey and W. Sänger, Ed., “Hydrogen Bonding in Biological Structures”, Springer-Verlag, Gmbh & Co. KG, Berlin, 1991.
J.-M. Lehn, Makromol. Chem., Macromol. Symp., 69, 1 (1993).
J. M. Whiteside, E. E. Simanek, J. P. Mathias, C. T. Seto, D. N. Chin, M. Mammen, and D. N. Gordon, Acc. Chem. Res., 28, 37 (1995).
P. Terech, in “Specialist Surfactants”, 2nd ed., I. D. Robb, Ed., Blackie Academic & Professional, 1997, pp 208–268.
K. Hanabusa, R. Tanaka, M. Suzuki, M. Kimura, and H. Shirai, Adv. Mater., 9, 1095 (1997).
K. Yoza, N. Amanokura, Y. Ono, T. Akao, H. Shinmori, M. Takeuchi, S. Shinkai, and D. N. Reinhoudt, Chem. Eur. J., 5, 2722 (1999).
T. Kato, H. Kihara, T. Uryu, A. Fujishima, and J. M. J. Frechet, Macromolecules, 29, 8734 (1996).
T. Kato and J. M. J. Frechet, in “Polymeric Materials Encyclopedia”, 2nd ed., J. C. Salamone, Ed., CRC Press, Boca Raton, FL, 1996, p 8158.
M. C. Etter, Acc. Chem. Res., 23, 120 (1990).
J. C. MacDonald and G. M. Whietesides, Chem. Rev., 94, 2383 (1994).
J.-H. Fuhrhop and W. Helfrich, Chem. Rev., 93, 1565 (1993).
J.-H. Fuhrhop and J. Köning, Ed., “Membranes and Molecular Assemblies: The Synkinetic Approach”, The Royal Society of Chemistry, Cambridge, 1994.
N. Kimizuka, T. Kawasaki, and T. Kunitake, J. Am. Chem. Soc., 115, 4387 (1993).
N. Kimizuka, T. Kawasaki, K. Hirata, and T. Kunitake, J. Am. Chem. Soc., 120, 4094 (1998).
M. R. Ghadiri, J. R. Granja, R. A. Milligan, D. E. McRee, and N. Khazanovich, Nature, 366, 324 (1993).
J.-H. Fuhrhop, H.-H. David, J. Mathieu, U. Liman, H.-J. Winter, and E. Boekema, J. Am. Chem. Soc., 108, 1785 (1986).
L. Leisoeroviz and M. Tuval, Acta Crystallogr., Sec. B., 34, 1230 (1978).
F. D. Lewis, J.-S. Yang, and C. L. Stern, J. Am. Chem. Soc., 118, 12029 (1996).
M. Masuda and T. Shimizu, J. Carbohydr. Chem., 17, 405 (1998).
I. Nakazawa, M. Masuda, Y. Okada, T. Hanada, K. Yase, M. Asai, and T. Shimizu, Langmuir, 15, 4757 (1999).
I. Nakazawa, S. Suda, M. Masuda, M. Asai, and T. Shimizu, Chem. Commun., 881 (2000).
T. Shimizu and M. Masuda, Mol. Cryst. Liq. Cryst., 295, 197 (1997).
T. Shimizu and M. Masuda, J. Am. Chem. Soc., 119, 2812 (1997).
T. Shimizu, M. Mori, H. Minamikawa, and M. Hato, J. Chem. Soc., Chem. Commun., 183 (1990).
T. Shimizu and M. Hato, Biochim. Biophys. Acta, 1147, 50 (1993).
N. Nakashima, S. Asakuma, and T. Kunitake, J. Am. Chem. Soc., 107, 509 (1985).
J.-H. Funrhop, P. Schnieder, E. Boekema, and W. Helfrich, J. Am. Chem. Soc., 110, 2861 (1988).
T. Shimizu, M. Shibakami, and M. Masuda, Chem. Lett., 267 (1997).
M. Masuda and T. Shimizu, Carbohydr. Res., 326, 56 (2000).
S. Amelinckx, Acta Crystallogr., 8, 530 (1955).
S. Amelinckx, Acta Crystallogr., 9, 16 (1956).
S. Amelinckx, Acta Crystallogr., 9, 217 (1956).
J. Schneider, C. Messerschmidt, A. Schulz, M. Gnade, B. Schade, P. Luger, P. Bombicz, V. Hubert, and J.-H. Fuhrhop, Langmuir, 16, 8575 (2000).
N. Yamada and M. Kawasaki, J. Chem. Soc., Chem. Commun., 568 (1990).
N. Yamada, K. Okuyama, T. Serizawa, M. Kawasaki, and S. Oshima, J. Chem. Soc., Perkin Trans., 2, 2707 (1996).
M. Masuda and T. Shimizu, Chem. Commun., 1057 (1996).
M. Masuda and T. Shimizu, Carbohydr. Res., 302, 139 (1997).
Y. Kinoshita, Makromol. Chem., 33, 21 (1959).
E. Benedetti, M. R. Ciajolo, and P. Coradini, Eur. Polym. J., 10, 1201 (1974).
Cambridge Structural Database Center, 1996, Cambridge Structural Database System Version 5.1.2., Cambridge Structural Data Center, 12 Union Road, Cambridge CB2 1EW, England.
G. A. Jeffrey and L. M. Wingert, Liq. Cryst., 12, 179 (1992).
M. Masuda, V. Vill, and T. Shimizu, J. Am. Chem. Soc., 122, 12327 (2000).
I. Nakazawa, S. Suda, M. Masuda, M. Asai, and T. Shimizu, Chem. Commun., 881 (2000).
Y. Nagai, K. Kobayashi, H. Toi, and Y. Aoyama, Bull. Chem. Soc. Jpn., 66, 2965 (1993).
T. J. James, K. R. A. S. Sandanayake, and S. Shinkai, Angew. Chem. Int. Ed. Engl., 35, 1910 (1996).
J.C. Norild and H. Eggert, J. Am. Chem. Soc., 117, 1479 (1995).
M. Mikami and S. Shinkai, J. Chem. Soc., Chem. Commun., 153 (1995).
M. Mikami and S. Shinkai, Chem. Lett., 603 (1995).
M. Masuda, T. Hanada, K. Yase, and T. Shimizu, Macromolecules, 31, 9403 (1998).
M. Masuda, T. Hanada, Y. Okada, K. Yase, and T. Shimizu, Macromolecules, 33, 9233 (2000).
H. Bader and H. Ringsdorf, J. Polym. Sci., Polym. Chem. Ed., 20, 1623 (1982).
F. Saremi, E. Maassen, B. Tieke, G. Jordan, and W. Rammensee, Langmuir, 11, 1068 (1995).
F. Saremi and B. Tieke, Adv. Mater., 7, 378 (1995).
J. H. Fendler, Acc. Chem. Res., 17, 3 (1984).
H. Ringsdorf, B. Schlarb, and J. Venzmer, Angew. Chem., Int. Ed. Eng., 27, 113 (1988).
B. Tieke and G. Wegner, in “Topics in Surface Chemistry”, 2nd ed., E. Kay, P. S. Bagus, Ed., Plenum Publishing Corporation, New York, N.Y., 1978.
D. F. O’Brien, T. H. Whitesides, and R. T. Kingbiel, J. Polym. Sci., Polym Lett. Ed., 19, 95 (1981).
D. A. Frankel and D. F. O’Brien, J. Am. Chem. Soc., 113, 7436 (1991).
D. A. Frankel and D. F. O’Brien, J. Am. Chem. Soc., 116, 10057 (1994).
T. Kim, K. Chan, and R. M. Crooks, J. Am. Chem. Soc., 119, 189 (1997).
V. Enkelman, Adv. Polym. Sci., 63, 91 (1984).
G. N. Patel, R. R. Chance, and J. D. Witt, J. Polym. Sci., Polym. Lett. Ed., 16, 607 (1978).
K. C. Lim and A. J. Heeger, J. Chem. Phys., 82, 522 (1985).
H. Nakanishi, N. Sumi, Y. Aso, and T. Otsubo, J. Org. Chem., 63, 8632 (1998).
S. Hung and J. M. Tour, J. Am. Chem. Soc., 121, 4908 (1999).
N. Aratani, A. Osuka, Y. H. Kim, D. H. Jeong, and D. Kim, Angew. Chem., Int. Ed. Eng., 39, 1458 (2000).
M. Kogiso, S. Ohnishi, K. Yase, M. Masuda, and T. Shimizu, Langmuir, 14, 4978 (1998).
T. Shimizu, M. Kogiso, and M. Masuda, Nature, 383, 487 (1996).
F. H. C. Crick and A. Rich, Nature, 176, 780 (1955).
D. R. Homes, C. W. Bunn, and D. J. Smith, J. Polym. Sci., 17, 159 (1955).
J. Bella, J. Puiggali, and J. A. Subirana, Polymer, 35, 1291 (1994).
E. Navarro, V. Tereshko, J. A. Subirana, and J. Puiggali, Biopolymers, 36, 711 (1995).
M. E. Feinstein and H. L. Rosano, J. Phys. Chem., 73, 601 (1969).
T. Imae, Y. Takahashi, and H. Muramatsu, J. Am. Chem. Soc., 114, 3414 (1992).
W. R. Hargreaves and D. W. Deamer, Biochemistry, 17, 3759 (1978).
T. Shimizu, M. Kogiso, and M. Masuda, J. Am. Chem. Soc., 119, 6209 (1997).
M. Kogiso, M. Masuda, and T. Shimizu, Supramol. Chem., 9, 183 (1998).
T. Shimizu, S. Ohnishi, and M. Kogiso, Angew. Chem., Int. Ed. Eng., 37, 3260 (1998).
Y. Murakami, Y. Aoyama, A. Nakano, T. Tada, and K. Fukuya, J. Am. Chem. Soc., 103, 3951 (1981).
T. Kunitake and N. Yamada, J. Chem. Soc., Chem. Commun., 655 (1986).
P. Berndt, G. B. Fields, and M. Tirrell, J. Am. Chem. Soc., 117, 9515 (1995).
Y. Murakami, A. Nakano, and H. Ikeda, J. Org. Chem., 47, 2137 (1982).
T. Shimizu, M. Mori, H. Minamikawa, and M. Hato, Chem. Lett., 1341 (1989).
K. Yamada, H. Ihara, T. Ide, T. Fukumoto, and C. Hirayama, Chem. Lett., 1713 (1984).
Y. Takahashi, A. Ueno, and H. Mihara, Chem. Eur. J., 4, 2475 (1998).
N. Yamada, K. Ariga, M. Naito, K. Matsubara, and E. Koyama, J. Am. Chem. Soc., 120, 12192 (1998).
M. Kogiso, Y. Okada, T. Hanada, K. Yase, and T. Shimizu, Biochim. Biophys. Acta, 1475, 346 (2000).
M. Kogiso, Y. Okada, M. Masuda, K. Yase, and T. Shimizu, Polym. Prepr. Jpn., 48, 1261 (1999).
J.-M. Lehn, M. Mascal, A. Decian, and J. Fischer, J. Chem. Soc., Chem. Commun., 479 (1990).
F. M. Menger and S. J. Lee, J. Am. Chem. Soc., 116, 5987 (1994).
D. Philp and J. F. Stoddart, Angew. Chem., Int. Ed. Eng., 35, 1154 (1996).
J. J. Storhoff and C. A. Mirkin, Chem. Rev., 99, 1849 (1999).
T. Kato, M. Nakano, T. Moteki, T. Uryu, and S. Ujiie, Macromolecules, 28, 8875 (1995).
T. Gulik-Krzywicki, C. Fouuey, and J.-M. Lehn, Proc. Natl. Acad. Sci. U.S.A., 90, 163 (1993).
D. Sasaki, K. Kurihara, and T. Kunitake, J. Am. Chem. Soc., 114, 10994 (1992).
T. Boland and B. D. Ratner, Langmuir, 10, 3845 (1994).
M. Shimomura, F. Nakamura, K. Ijiro, H. Taketsuna, M. Tanaka, H. Nakamura, and K. Hasebe, J. Am. Chem. Soc., 119, 2341 (1997).
W. Sänger, Ed., “Principles of Nucleic Acid Structure”, Springer-Verlag GmbH & Co. KG, Berlin, 1984.
J. S. Nowick and J. S. Chen, J. Am. Chem. Soc., 114, 1107 (1992).
V. M. Rotello, E. A. Viani, G. Deslongchamps, B. A. Murray, and J. Rebek, Jr., J. Am. Chem. Soc., 115, 797 (1993).
T. Shimizu, R. Iwaura, M. Masuda, T. Hanada, and K. Yase, J. Am. Chem. Soc., 123, 5947 (2001).
P. O. Ts’O and S. I. Chan, J. Am. Chem. Soc., 86, 4176 (1964).
M. P. Schwizer, S. I. Chan, and P. O. Ts’O, J. Am. Chem. Soc., 87, 5241 (1965).
H. Yanagawa, Y. Ogawa, H. Furuta, and K. Tsuno, J. Am. Chem. Soc., 111, 4567 (1989).
N. A. J. M. Somerdijk, P. J. J. A. Buynsters, H. Akdemir, D. G. Geurts, A. M. A. Pistorius, M. C. Feiters, R. J. M. Nolte, and B. Zwaneburg, Chem. Eur. J., 4, 127 (1998).
S. Svenson, B. Kirste, and J.-H. Fuhrhop, J. Am. Chem. Soc., 116, 11969 (1994).
T. Shimizu, Trans. Meter. Res. Soc. Jpn., 24, 431 (1999).
T. Tachibana and H. Kambara, J. Am. Chem. Soc., 87, 3015 (1965).
N. Yamada, T. Sasaki, H. Murata, and T. Kunitake, Chem. Lett., 205 (1989).
S. Wang, Nature, 200, 879 (1963).
D. L. Wulff and G. Fränkel, Biochim. Biophys. Acta, 51, 332 (1961).
M. J. Moghaddam, S. Hozumi, Y. Inaki, and K. Takemoto, J. Polym. Sci., Polym. Chem. Ed., 26, 3297 (1988).
G. Chen and A. S. Hoffman, Nature, 373, 49 (1995).
R. Yoshida, K. Uchida, Y. Kaneko, K. Sakai, A. Kikuchi, Y. Sakurai, and T. Okano, Nature, 374, 240 (1995).
C. Wang, R. J. Stewart, and J. Kopecek, Nature, 397, 417 (1999).
K. Lee and D. J. Mooney, Chem. Rev., 101, 1869 (2001).
J.-H. Fuhrhop and C. J. Böttcher, J. Am. Chem. Soc., 112, 1768 (1990).
G. R. Newkome, G. R. Baker, S. Arai, M. J. Saunders, P. S. Russo, K. J. Theriot, C. N. Moorefield, L. E. Rogers, J. E. Miller, T. R. Lieux, M. E. Murray, B. Phillips, and L. Pascal, J. Am. Chem. Soc., 112, 8458 (1990).
M. Jokic, J. Makarevic, and M. Zinic, J. Chem. Soc., Chem. Commun., 1723 (1995).
R. Oda, I. Huc, and S. J. Candau, Angew. Chem., Int. Ed., 37, 2689 (1998).
M. Kogiso, S. Ohnishi, K. Yase, M. Masuda, and T. Shimizu, Langmuir, 14, 4978 (1998).
S. Bhattacharya and S. N. G. Acharya, Chem. Mater., 11, 3504 (1999).
L. A. Estroff and A. D. Hamilton, Angew. Chem., Int. Ed. Eng., 39, 3447 (2000).
F. M. Menger and K. L. Caran, J. Am. Chem. Soc., 122, 11679 (2000).
C. Marmillon, F. Gauffre, T. Gulik-Krzywicki, C. Loup, A.-M. Caminade, and E. Rump, Angew. Chem., Int. Ed., 40, 2626 (2001).
J. H. Jung, S. Shinkai, and T. Shimizu, Chem. Eur. J., 8, 2684 (2002).
H. Yanagawa, Y. Ogawa, H. Furuta, and K. Tsuno, J. Am. Chem. Soc., 111, 4567 (1989).
F. Pincet, E. Perez, G. Bryant, L. Lebeau, and C. Mioskowski, Phys. Rev. Lett., 73, 2780 (1994).
S. Bonaccio, D. Capitani, A. L. Segre, P. Walde, and P. L. Luisi, Langmuir, 13, 1952 (1997).
D. Berti, P. Barbaro, I. Bucci, and P. Baglioni, J. Phys. Chem. B, 103, 4916 (1999).
S. L. Forman, J. C. Fettinger, S. Pieraccini, G. Gottarelli, and J. T. Davis, J. Am. Chem. Soc., 122, 4060 (2000).
R. Iwaura, K. Yoshida, M. Masuda, K. Yase, and T. Shimizu, Chem. Mater., 14, 3047 (2002).
K. Hanabusa, M. Yamada, M. Kimura, and H. Shirai, Angew. Chem. Int. Ed. Eng., 35, 1949 (1996).
E. Snip, S. Shinkai, and D. N. Reinhoudt, Tetrahedron Lett., 42, 2153 (2001).
M. C. Feiters and R. J. M. Nolte, Ed., “Advances in Supramolecular Chemistry”, JAI Press Inc., New York, N.Y., 2000, vol.6, pp 55–157.
G. John, M. Masuda, Y. Okada, K. Yase, and T. Shimizu, Adv. Mater., 13, 715 (2001).
J. H. Jung, H. Kobayashi, M. Masuda, T. Shimizu, and S. Shinkai, J. Am. Chem. Soc., 123, 8785 (2001).
G. John, J. H. Jung, H. Minamikawa, K. Yoshida, and T. Shimizu, Chem. Eur. J., 8, 5494 (2002).
J. H. Jung, G. John, K. Yoshida, and T. Shimizu, J. Am. Chem. Soc., 124, 10674 (2002).
J. H. Jung, S. Shinkai, and T. Shimizu, Nano Letters, 2, 17 (2002).
J. H. Jung, K. Yoshida, and T. Shimizu, Langmuir, 18, 8724 (2002).
H. Frusawa, A. Fukagawa, K. Ito, G. John, and T. Shimizu, Angew. Chem. Int. Ed. Eng., in press.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Shimizu, T. Bottom-Up Synthesis and Morphological Control of High-Axial-Ratio Nanostructures through Molecular Self-Assembly. Polym J 35, 1–22 (2003). https://doi.org/10.1295/polymj.35.1
Issue Date:
DOI: https://doi.org/10.1295/polymj.35.1