Fuzzy Nanoassemblies: Toward Layered Polymeric Multicomposites Gero Decher, et al. Science 277, 1232 (1997); DOI: 10.1126/science.277.5330.1232 This copy is for your personal, non-commercial use only. If you wish to distribute this article to others, you can order high-quality copies for your colleagues, clients, or customers by clicking here. Permission to republish or repurpose articles or portions of articles can be obtained by following the guidelines here. The following resources related to this article are available online at www.sciencemag.org (this information is current as of February 24, 2010 ): Updated information and services, including high-resolution figures, can be found in the online version of this article at: http://www.sciencemag.org/cgi/content/full/277/5330/1232 This article has been cited by 30 articles hosted by HighWire Press; see: http://www.sciencemag.org/cgi/content/full/277/5330/1232#otherarticles This article appears in the following subject collections: Materials Science http://www.sciencemag.org/cgi/collection/mat_sci on February 24, 2010 www.sciencemag.org Downloaded from Science (print ISSN 0036-8075; online ISSN 1095-9203) is published weekly, except the last week in December, by the American Association for the Advancement of Science, 1200 New York Avenue NW, Washington, DC 20005. Copyright 1997 by the American Association for the Advancement of Science; all rights reserved. The title Science is a registered trademark of AAAS. Physics (Cornell Univ. Press, Ithaca, NY, 1979); F. W. 27. J. T. Chen, E. L. Thomas, C. K. Ober, G.-P. Mao, 32. We have benefited from interactions with many stu- Wiegel, Conformational Phase Transitions in a Mac- ibid. 273, 343 (1996); J. T. Chen et al., Macromole- dents and co-workers and would like to thank former romolecule: Exactly Solvable Models in Phase Tran- cules 28, 1688 (1995). members of our research groups. In particular, sitions and Critical Phenomena, C. Domb and J. L. 28. G.-P. Mao et al., Macromolecules 30, 2556 (1997). C.K.O. thanks G.-P. Mao and J.-G. Wang and E.L.T. Lebowitz, Eds. (Academic Press, New York, 1983), 29. A. Omenat, R. A. M. Hikmet, J. Lub, P. Van der Sluis, thanks J. T. Chen. Funding from NSF (DMR-970527) vol. 7. ibid. 29, 6730 (1996); W. Y. Zheng and P. T. Ham- (to M.M., C.K.O., and E.L.T.) and both NSF (DMR- 4. F. S. Bates and G. H. Fredrickson, Annu. Rev. Phys. mond, Macromol. Rapid Commun. 17, 813 (1996). 9201845) and the Air Force Office of Sponsored Chem. 41, 525 (1990). 30. M. Brehmer, R. Zentel, G. Mao, C. K. Ober, Macro- Research (MURI PC 218975) (to C.K.O. and E.L.T.) 5. For a discussion of several of the processes leading mol. Symp. 117, 245 (1997). is gratefully acknowledged. C.K.O. thanks the Office to self-organization, see special issue on the 1996 31. J.-G. Wang, G.-P. Mao, C. K. Ober, E. J. Kramer, of Naval Research for support of the fluoropolymer NATO Workshop on Tandem Molecular Interactions, Macromolecules 30, 1906 (1997). work. in R. Zentel, G. Galli, C. K. Ober, Eds., Macromol. Symp. 117 (1997). 6. E. Dessipri, D. A. Tirrell, E. D. T. Atkins, Macromole- cules 29, 3545 (1996). 7. M. Muthukumar, J. Chem. Phys. 103, 4723 (1995); Comput. Mater. Sci. 4, 370 (1995). Fuzzy Nanoassemblies: 8. For the specific example of diblock copolymers, the topological connectivity of various monomers in ev- ery chain appears as a density-density correlation Toward Layered Polymeric at a distance r being proportional to 1/r so that a5 2 (the Fourier transform of 1/r is 1/k 2 in three di- mensions). The long-range interaction can origi- Multicomposites nate from such entropic correlations or electrostat- ic interactions (as in the case of surfactant and polyelectrolyte solutions) or chemical reactions (as Gero Decher in the case of simultaneous occurrence of mac- rophase separation and chemical reactions or hy- drogen bonding). Multilayer films of organic compounds on solid surfaces have been studied for more than 9. The scheme requires consideration of shape and 60 years because they allow fabrication of multicomposite molecular assemblies of packing at the atomic and molecular level as well as tailored architecture. However, both the Langmuir-Blodgett technique and chemisorp- at higher levels of scale leading to the three dimen- sional structure of the overall aggregate. Bringing the tion from solution can be used only with certain classes of molecules. An alternative set of components together into the requisite array in approach—fabrication of multilayers by consecutive adsorption of polyanions and poly- a single process step (for example, by cooling the cations—is far more general and has been extended to other materials such as proteins mixture) is extremely difficult, particularly when the basic units have conformational diversity under the or colloids. Because polymers are typically flexible molecules, the resulting superlattice conditions of the assembly process. Indeed, this sit- architectures are somewhat fuzzy structures, but the absence of crystallinity in these on February 24, 2010 uation is a critical issue, for if the system or parents of films is expected to be beneficial for many potential applications. the system adopt wrong shapes and packings, then the desired structures may not even form. 10. A. H. Simmons, C. A. Michal, L. W. Jelinski, Science 271, 84 (1996). 11. T. Gulik-Krzywicki, C. Fouquey, J.-M. Lehn, Proc. n the last two to three decades, materials structures, although it is also clear that struc Natl. Acad. Sci. U.S.A. 90, 163 (1993); M. Kotera, I - J.-M. Lehn, J.-P. Vigneron, Tetrahedron 51 (No. 7), science has developed into an interdiscipli- tures as complex as those found in the bio- 1953 (1995). nary field that encompasses organic, poly- logical world, such as the flagellar motor, 12. M. Mu¨ ller, F. Kremer, R. Stadler, E. W. Fischer, U. meric, and even biological components in cannot yet be fabricated. Seidel, Colloid Polym. Sci. 273, 38 (1995). 13. T. Kato, H. Kihara, U. Kumar, T. Uryu, J. M. J. Fre´- addition to the classic metals and inorgan- It is, however, possible to consecutively www.sciencemag.org chet, Angew. Chem. Int. Ed. Engl. 33, 1644 (1994); ics. Although carbon-based molecules offer deposit single molecular layers onto planar T. Kato, M. Nakano, T. Moteki, T. Uryu, S. Ujiie, an enormous structural diversity and tun- solid supports and to form multilayers in Macromolecules 28, 8875 (1995). 14. C. G. Bazuin, F. A. Brandys, T. M. Eve, M. Plante, ability in terms of potential properties or which nanoscale arrangements of organic Macromol. Symp. 84, 183 (1994); C. G. Bazuin and processability, they also typically suffer from molecules can be controlled at least in one A. Tork, Macromolecules 28, 8877 (1995); R. a lack of stability when exposed to heat, dimension (along the layer normal). This Tal’roze, S. Kuptsov, T. Sycheva, V. Bezborodov, N. Plate, ibid., p. 8689. oxidizing agents, electromagnetic radiation, approach also fulfills another prerequisite 15. J. Ruokalainen et al., Macromolecules 28, 7779 or (as in the case of complex biomolecules) for functional macroscopic devices: a fixed (1995); J. Ruokalainen, G. ten Brinke, O. Ikkala, M. dehydration. Multicomposites make it pos- relation between nanoscopic order and Downloaded from Torkkeli, R. Serimaa, ibid. 29, 3409 (1996). sible to combine two or more desirable prop macroscopic orientation. To fully exploit an 16. A. Pron, J. Lostra, J.-E. O¨ sterholm, P. J. Smith, - Polymer 34, 4235 (1993); T. Vikki et al., Macromol- erties, as in the classic reinforced plastics, or assembled structure, it is necessary to know ecules 29, 2945 (1996). to provide additional stability for otherwise the location or orientation (or both) of 17. Peter R. Ashton et al., Angew. Int. Ed. Engl. 36, 735 highly labile functional biomolecules or bio- every molecule, not only with respect to (1997). 18. C. Gong and H. Gibson, Macromolecules 29, 7029 molecular assemblies. Even higher device each other (as in ordered or phase-separated (1996); G. Wenz, Angew. Chem. Int. Ed. Engl. 33, functionality will arise from a combination bulk systems at the nanometer scale, such as 803 (1994). of physical and chemical processes (such as liquid crystals, copolymers, or zeolites), but 19. C. K. Ober and G. Wegner, Adv. Mater. 9, 17 (1997). 20. V. Percec and G. Johansson, Macromol. Symp. 95, electron or energy transfer) and chemical also with respect to a macroscopic coordi- 173 (1995). transformations found in nature (such as nate. Only materials that have such struc- 21. J. M. Park, B. B. Muhoberac, P. L. Dubin, J. Xia, photochemical energy conversion). Such tural hierarchy (1) allow molecular proper- Macromolecules 25, 290 (1992). 22. E. L. Thomas, D. M. Anderson, C. J. Henkee, D. devices require control of molecular orien- ties to be fully exploited in macroscopic Hoffman, Nature 334, 598 (1988). tation and organization on the nanoscale, as devices, as, for example, in organic 23. J. M. Seddon, Biochim. Biophys. Acta 1031,1 their function strongly depends on the local waveguides for second-order nonlinear op- (1990); T. Hashimoto, M. Takenaka, T. Izumitani, J. chemical environment. It is therefore highly tics or in biosensors. Chem. Phys. 97, 697 (1992); J. Lauger, R. Lay, W. Gronski, ibid. 101, 7181 (1994). desirable to develop methods for the con- In simple multilayer systems, this de- 24. J.-P. Billot, A. Douy, B. Gallot, Makromol. Chem. trolled assembly of multicomponent nano- mand is reduced to the sequence of layers 178, 1641 (1977). and to the orientation of molecules with 25. J. Adams and W. Gronski, Makromol. Chem. Rapid Universite´ Louis Pasteur and CNRS, Institut Charles Sad- Commun.