Conversion of supramolecular clusters to macromolecular objects

Science

Volumn 283, Issue 5401, 1999, Pages 523-526

  Zubarev, Eugene R ^a   Pralle, Martin U ^a   Li, Leiming ^a   Stupp, Samuel I ^a,b  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

^b Northwestern University   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

NANOPARTICLE;

ANISOTROPY; ARTICLE; CLUSTER ANALYSIS; COVALENT BOND; CROSS LINKING; DEVICE; ELECTRON MICROSCOPY; MACROMOLECULE; PRIORITY JOURNAL; RADIATION SCATTERING;

EID: 0033593624     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.283.5401.523     Document Type: Article

References (35)

1. S. I. Stupp et al., J. Am. Chem. Soc. 117, 5212 (1995).
2. M. Muthukumar, C. K. Ober, E. L. Thomas, Science 277, 1225 (1997).
3. D. A. Tomalia and H. D. Durst, Top. Curr. Chem. 165, 193 (1993); J. M. J. Fréchet, Science 263, 1710 (1994); G. R. Newkome, C. N. Moorefield, G. R. Baker, A. L. Johnson, R. J. Behera, Angew. Chem. Int. Ed. Engl. 30, 1176 (1991); J. S. Moore, J. Zhang, Z. Wu, D. Venkataraman, S. Lee, Makromol. Chem. Macromol. Symp. 77, 295 (1994).
4. D. A. Tomalia and H. D. Durst, Top. Curr. Chem. 165, 193 (1993); J. M. J. Fréchet, Science 263, 1710 (1994); G. R. Newkome, C. N. Moorefield, G. R. Baker, A. L. Johnson, R. J. Behera, Angew. Chem. Int. Ed. Engl. 30, 1176 (1991); J. S. Moore, J. Zhang, Z. Wu, D. Venkataraman, S. Lee, Makromol. Chem. Macromol. Symp. 77, 295 (1994).
5. D. A. Tomalia and H. D. Durst, Top. Curr. Chem. 165, 193 (1993); J. M. J. Fréchet, Science 263, 1710 (1994); G. R. Newkome, C. N. Moorefield, G. R. Baker, A. L. Johnson, R. J. Behera, Angew. Chem. Int. Ed. Engl. 30, 1176 (1991); J. S. Moore, J. Zhang, Z. Wu, D. Venkataraman, S. Lee, Makromol. Chem. Macromol. Symp. 77, 295 (1994).
6. D. A. Tomalia and H. D. Durst, Top. Curr. Chem. 165, 193 (1993); J. M. J. Fréchet, Science 263, 1710 (1994); G. R. Newkome, C. N. Moorefield, G. R. Baker, A. L. Johnson, R. J. Behera, Angew. Chem. Int. Ed. Engl. 30, 1176 (1991); J. S. Moore, J. Zhang, Z. Wu, D. Venkataraman, S. Lee, Makromol. Chem. Macromol. Symp. 77, 295 (1994).
7. S. I. Stupp, S. Son, H. C. Lin, L. S. Li, Science 259, 59 (1993).
8. S. I. Stupp et al., ibid. 276, 384 (1997).
9. J.-M. Lehn, Supramolecular Chemistry (VCH, New York, 1995); Pure Appl. Chem. 66, 1961 (1994); S. C. Zimmerman, F. Zeng, D. E. C. Reichert, S. V. Kolotuchin, Science 271, 1095 (1996); J. C. M. van Hest, D. A. P. Delnoye, M. W. P. L. Baars, M. H. P. van Genderen, E. W. Meijer, ibid. 268, 1592 (1995); T. W. Bell, ibid. 271, 1077 (1996); V. Percec, G. Johansson, G. Ungar, J. Zhou, J. Am. Chem. Soc. 118, 9855 (1996); V. Percec, G. Johansson, J. Heck, G. Ungar, S. V. Batty, J. Chem. Soc. Perkin Trans. I 1, 1411 (1993); G. R. Newkome, X. Lin, C. Yaxiong, G. H. Escamilla, J. Org. Chem. 58, 3123 (1993).
10. J.-M. Lehn, Supramolecular Chemistry (VCH, New York, 1995); Pure Appl. Chem. 66, 1961 (1994); S. C. Zimmerman, F. Zeng, D. E. C. Reichert, S. V. Kolotuchin, Science 271, 1095 (1996); J. C. M. van Hest, D. A. P. Delnoye, M. W. P. L. Baars, M. H. P. van Genderen, E. W. Meijer, ibid. 268, 1592 (1995); T. W. Bell, ibid. 271, 1077 (1996); V. Percec, G. Johansson, G. Ungar, J. Zhou, J. Am. Chem. Soc. 118, 9855 (1996); V. Percec, G. Johansson, J. Heck, G. Ungar, S. V. Batty, J. Chem. Soc. Perkin Trans. I 1, 1411 (1993); G. R. Newkome, X. Lin, C. Yaxiong, G. H. Escamilla, J. Org. Chem. 58, 3123 (1993).
11. J.-M. Lehn, Supramolecular Chemistry (VCH, New York, 1995); Pure Appl. Chem. 66, 1961 (1994); S. C. Zimmerman, F. Zeng, D. E. C. Reichert, S. V. Kolotuchin, Science 271, 1095 (1996); J. C. M. van Hest, D. A. P. Delnoye, M. W. P. L. Baars, M. H. P. van Genderen, E. W. Meijer, ibid. 268, 1592 (1995); T. W. Bell, ibid. 271, 1077 (1996); V. Percec, G. Johansson, G. Ungar, J. Zhou, J. Am. Chem. Soc. 118, 9855 (1996); V. Percec, G. Johansson, J. Heck, G. Ungar, S. V. Batty, J. Chem. Soc. Perkin Trans. I 1, 1411 (1993); G. R. Newkome, X. Lin, C. Yaxiong, G. H. Escamilla, J. Org. Chem. 58, 3123 (1993).
12. J.-M. Lehn, Supramolecular Chemistry (VCH, New York, 1995); Pure Appl. Chem. 66, 1961 (1994); S. C. Zimmerman, F. Zeng, D. E. C. Reichert, S. V. Kolotuchin, Science 271, 1095 (1996); J. C. M. van Hest, D. A. P. Delnoye, M. W. P. L. Baars, M. H. P. van Genderen, E. W. Meijer, ibid. 268, 1592 (1995); T. W. Bell, ibid. 271, 1077 (1996); V. Percec, G. Johansson, G. Ungar, J. Zhou, J. Am. Chem. Soc. 118, 9855 (1996); V. Percec, G. Johansson, J. Heck, G. Ungar, S. V. Batty, J. Chem. Soc. Perkin Trans. I 1, 1411 (1993); G. R. Newkome, X. Lin, C. Yaxiong, G. H. Escamilla, J. Org. Chem. 58, 3123 (1993).
13. J.-M. Lehn, Supramolecular Chemistry (VCH, New York, 1995); Pure Appl. Chem. 66, 1961 (1994); S. C. Zimmerman, F. Zeng, D. E. C. Reichert, S. V. Kolotuchin, Science 271, 1095 (1996); J. C. M. van Hest, D. A. P. Delnoye, M. W. P. L. Baars, M. H. P. van Genderen, E. W. Meijer, ibid. 268, 1592 (1995); T. W. Bell, ibid. 271, 1077 (1996); V. Percec, G. Johansson, G. Ungar, J. Zhou, J. Am. Chem. Soc. 118, 9855 (1996); V. Percec, G. Johansson, J. Heck, G. Ungar, S. V. Batty, J. Chem. Soc. Perkin Trans. I 1, 1411 (1993); G. R. Newkome, X. Lin, C. Yaxiong, G. H. Escamilla, J. Org. Chem. 58, 3123 (1993).
14. J.-M. Lehn, Supramolecular Chemistry (VCH, New York, 1995); Pure Appl. Chem. 66, 1961 (1994); S. C. Zimmerman, F. Zeng, D. E. C. Reichert, S. V. Kolotuchin, Science 271, 1095 (1996); J. C. M. van Hest, D. A. P. Delnoye, M. W. P. L. Baars, M. H. P. van Genderen, E. W. Meijer, ibid. 268, 1592 (1995); T. W. Bell, ibid. 271, 1077 (1996); V. Percec, G. Johansson, G. Ungar, J. Zhou, J. Am. Chem. Soc. 118, 9855 (1996); V. Percec, G. Johansson, J. Heck, G. Ungar, S. V. Batty, J. Chem. Soc. Perkin Trans. I 1, 1411 (1993); G. R. Newkome, X. Lin, C. Yaxiong, G. H. Escamilla, J. Org. Chem. 58, 3123 (1993).
15. J.-M. Lehn, Supramolecular Chemistry (VCH, New York, 1995); Pure Appl. Chem. 66, 1961 (1994); S. C. Zimmerman, F. Zeng, D. E. C. Reichert, S. V. Kolotuchin, Science 271, 1095 (1996); J. C. M. van Hest, D. A. P. Delnoye, M. W. P. L. Baars, M. H. P. van Genderen, E. W. Meijer, ibid. 268, 1592 (1995); T. W. Bell, ibid. 271, 1077 (1996); V. Percec, G. Johansson, G. Ungar, J. Zhou, J. Am. Chem. Soc. 118, 9855 (1996); V. Percec, G. Johansson, J. Heck, G. Ungar, S. V. Batty, J. Chem. Soc. Perkin Trans. I 1, 1411 (1993); G. R. Newkome, X. Lin, C. Yaxiong, G. H. Escamilla, J. Org. Chem. 58, 3123 (1993).
16. J.-M. Lehn, Supramolecular Chemistry (VCH, New York, 1995); Pure Appl. Chem. 66, 1961 (1994); S. C. Zimmerman, F. Zeng, D. E. C. Reichert, S. V. Kolotuchin, Science 271, 1095 (1996); J. C. M. van Hest, D. A. P. Delnoye, M. W. P. L. Baars, M. H. P. van Genderen, E. W. Meijer, ibid. 268, 1592 (1995); T. W. Bell, ibid. 271, 1077 (1996); V. Percec, G. Johansson, G. Ungar, J. Zhou, J. Am. Chem. Soc. 118, 9855 (1996); V. Percec, G. Johansson, J. Heck, G. Ungar, S. V. Batty, J. Chem. Soc. Perkin Trans. I 1, 1411 (1993); G. R. Newkome, X. Lin, C. Yaxiong, G. H. Escamilla, J. Org. Chem. 58, 3123 (1993).
17. E. R. Zubarev, L. Li, S. I. Stupp, in preparation.
18. D. Doskocilova, J. Straka, B. Schneider, Polymer 34, 437 (1993).
19. I. C. McNeill, L. Ackerman, S. N. Gupta, J. Polym. Sci. Polym. Chem. Ed. 16, 2169 (1978).
20. N. Grassie and A. Heaney, Polym. Lett. 12, 89 (1974).
21. M. A. Golub and M. Sung, ibid. 11, 129 (1973).
22. 13C NMR and suggested that cross-linking involves the reaction of a pendant vinyl group (1,2 units) with the methylene group in 1,4-cis-butadiene units (8). However, little is known about the actual mechanism of this reaction. Grassie and Heaney found that introducing typical free radical inhibitors does not affect the rate at which vinyl groups disappear (10). Therefore, it is thought that cross-linking proceeds through a molecular mechanism and does not involve radical formation. A probable mechanism for cross-linking, which involves an activated intermediate complex between the pendant vinyl group (1,2 unit) and the methylene group of a 1,4-cis unit, has been suggested. A hydrogen transfer reaction then results in the simultaneous formation of the covalent bond between two carbon atoms.
23. B. E. Smart, in Organofluorine Chemistry: Principles and Commercial Applications, R. E. Banks, B. E. Smart, J. C. Tatlow, Eds. (Plenum, New York, 1994), pp. 57-69; D. F. Eaton and B. E. Smart, J. Am. Chem. Soc. 112, 2821 (1990).
24. B. E. Smart, in Organofluorine Chemistry: Principles and Commercial Applications, R. E. Banks, B. E. Smart, J. C. Tatlow, Eds. (Plenum, New York, 1994), pp. 57-69; D. F. Eaton and B. E. Smart, J. Am. Chem. Soc. 112, 2821 (1990).
25. An investigation of the annealed samples by NMR and GPC studies indicated that the cross-linking reaction starts at temperatures higher than 230°C. Annealing of precursor 1 at 220°C for 24 hours revealed no cross-linking of butadiene units, and the formation of molecular objects was not observed.
26. 2. The 1064-nm fundamental was produced by a Q-switched yttrium-aluminum-garnet-Nd laser with a 20-ns pulse width operating at a 20-Hz repetition rate. The second harmonic at 532 nm was separated from the fundamental by a series of green pass filters and a monochromator. The light was collected in a photomultiplier tube, and the signal was sent to a digital data acquisition system and an oscilloscope. All data were corrected for the transmission of the fundamental and the absorption of the second harmonic. Maker fringes were observed from cast films of the uniform thickness when the incident angle of the p- and s-polarized laser beam was being changed continuously. This result suggests that the films possess ∞mm symmetry and polar order. The sinusoidal fringes that were obtained by plotting the square root of the second harmonic intensity (obtained by scanning an s-polarized laser beam with an incident angle of 40° across samples) against the thickness also indicated the polar nature of the material.
27. G. N. Tew, L. M. Li, S. I. Stupp, J. Am. Chem. Soc. 120, 5601 (1998).
28. 1H NMR spectra revealed the disappearance of 70% of the vinyl protons after annealing precursor 1 and after isolating the macromolecular product of narrow MW distribution. The disappearance of vinyl protons [δ4.8 to δ5.9 parts per million (ppm)] is accompanied by an increase of 20% in the number of aliphatic protons. These changes reflect the conversion of double to single bonds and are consistent with the expected values. The position of all the aromatic, aliphatic, and residual vinyl peaks were found to be the same after the transformation from precursor 1 to macromolecular objects. However, some broadening and suppression of aromatic resonances were observed (δ7.3 to δ8.5 ppm).
29. L. Song et al., Science 274, 1859 (1996); Y. Fang, S. Cheley, H. Baytey, J. Yang, Biochemistry 36, 9518 (1997); S. Cheley et al., Protein Eng. 10, 1433 (1997).
30. L. Song et al., Science 274, 1859 (1996); Y. Fang, S. Cheley, H. Baytey, J. Yang, Biochemistry 36, 9518 (1997); S. Cheley et al., Protein Eng. 10, 1433 (1997).
31. L. Song et al., Science 274, 1859 (1996); Y. Fang, S. Cheley, H. Baytey, J. Yang, Biochemistry 36, 9518 (1997); S. Cheley et al., Protein Eng. 10, 1433 (1997).
32. B. Walker and H. Bayley, J. Biol. Chem. 270, 23065 (1995); R. G. Panchal and H. Bayley, ibid., p. 23072; H. Bayley, Bioorg. Chem. 23, 340 (1995).
33. B. Walker and H. Bayley, J. Biol. Chem. 270, 23065 (1995); R. G. Panchal and H. Bayley, ibid., p. 23072; H. Bayley, Bioorg. Chem. 23, 340 (1995).
34. B. Walker and H. Bayley, J. Biol. Chem. 270, 23065 (1995); R. G. Panchal and H. Bayley, ibid., p. 23072; H. Bayley, Bioorg. Chem. 23, 340 (1995).
35. Supported by grants from the Office of Naval Research (N00014-96-1-0515), NSF (DMR 93-12601), the U.S. Department of Energy (DEF002-91 ER45439. which was obtained through the Materials Research Laboratory of the University of Illinois), and Master Builders Technologies. We acknowledge the use of facilities at the University of Illinois Center for Electron Microscopy and the Visualization Laboratory of the Beckman Institute for Advanced Science and Technology.