Recognition-mediated unfolding of a self-assembled polymeric globule

Macromolecules

Volumn 32, Issue 15, 1999, Pages 4956-4960

  Deans, Robert ^a   Ilhan, Faysal ^a   Rotello, Vincent M ^a  

^a UNIVERSITY OF MASSACHUSETTS   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

COPOLYMERS; GEL PERMEATION CHROMATOGRAPHY; HYDROGEN BONDS; MICELLES; MOLECULAR STRUCTURE; NUCLEAR MAGNETIC RESONANCE; NUMERICAL METHODS; SOLVENTS; STOICHIOMETRY; SUBSTITUTION REACTIONS; SYNTHESIS (CHEMICAL); THERMODYNAMICS;

COMPETITIVE INTERMOLECULAR HOST GUEST INTERACTIONS; DIAMINOTRIAZINE FUNCTIONALIZED POLYSTYRENE; NONPOLAR SOLVENTS; POLYMERIC GLOBULE;

POLYSTYRENES;

EID: 0033154102     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma990735s     Document Type: Article

References (43)

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19. Folding of our polymer system is not strictly a micellar process, since self-assembly arises from specific interactions, rather than solvophobic forces. For examples of micellar block copolymers formed via solvophobic self-assembly, see: Wilhelm, M.; Zhao, C.; Wang, Y.; Xu, R.; Winnik, M.; Mura, J.; Riess, G.; Croucher, M. Macromolecules 1991, 24, 1033. Zhang, L.; Eisenberg, A. Science 1995, 268, 1728. Wooley, K. Chem. Eur. J. 1997, 3, 1397.
20. Folding of our polymer system is not strictly a micellar process, since self-assembly arises from specific interactions, rather than solvophobic forces. For examples of micellar block copolymers formed via solvophobic self-assembly, see: Wilhelm, M.; Zhao, C.; Wang, Y.; Xu, R.; Winnik, M.; Mura, J.; Riess, G.; Croucher, M. Macromolecules 1991, 24, 1033. Zhang, L.; Eisenberg, A. Science 1995, 268, 1728. Wooley, K. Chem. Eur. J. 1997, 3, 1397.
21. Folding of our polymer system is not strictly a micellar process, since self-assembly arises from specific interactions, rather than solvophobic forces. For examples of micellar block copolymers formed via solvophobic self-assembly, see: Wilhelm, M.; Zhao, C.; Wang, Y.; Xu, R.; Winnik, M.; Mura, J.; Riess, G.; Croucher, M. Macromolecules 1991, 24, 1033. Zhang, L.; Eisenberg, A. Science 1995, 268, 1728. Wooley, K. Chem. Eur. J. 1997, 3, 1397.
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26. Higher triazine densities in copolymer 1 resulted in poor solubility, indicative of aggregation. This can be attributed to insufficient chain length between diaminotriazines to allow efficient micellar packing.
27. 3) of 20 ps (300 K) followed by the final 20 ps (300 K) simulation shown in Figure 1. For a description of the solvation method used see: Still, W.; Tempczyk, A.; Hawley, R.; Hendrickson, T. J. Am. Chem. Soc. 1990, 112, 6127-6129.
28. 3) of 20 ps (300 K) followed by the final 20 ps (300 K) simulation shown in Figure 1. For a description of the solvation method used see: Still, W.; Tempczyk, A.; Hawley, R.; Hendrickson, T. J. Am. Chem. Soc. 1990, 112, 6127-6129.
29. -1 lower than in dilute solution: Silverstein, R.; Webster, F. Spectrometric Identification of Organic Compounds, 6th ed.; Wiley: New York 1998; p 102. These values are consistent with those observed in polymer 1 relative to monomer 4.
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31. The polymer 1 used in this experiment was obtained from the same batch of cyano polymer 3 used as a nonfolding control. As such, polymer 1 would be expected (in the absence of intramolecular self-assembly) to possess an essentially identical radius of gyration as polymer 3 .
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35. 3 can be attributed to the small radius and hence lower extinction coefficient of the folded polymer. The intramolecular aggregation of triazine units causes a depression in the extinction coefficient of the folded polymer. For limitations to the applicability of Beer's law see: Principles of Instrumental Analysis, 2nd ed; Skoog, D. A., West, D. M., Eds.; Saunders: Philadelphia, 1980; pp 153-157.
36. a's used in this paper for polymer 1 refer to the association constant per triazine moiety.
37. As with its enzymatic prototypes, unfolding of polymer 1 is expected to be cooperative. The use of polymer in excess as guest minimizes this effect, as videnced by the excellent fits to (1:1) binding isotherms for 1·5 complexation.
38. For other examples of host-guest recognition based on diaminopyridine-imide interactions see: Ge, Y.; Lilienthal, R.; Smith, D. J. Am. Chem. Soc. 1996, 118, 3976. Muehldorf, A. V.; Van Engen, D.; Warner, J. C.; Hamilton, A. D. J. Am. Chem. Soc. 1988, 110, 6561-6562. Park, T.; Schroeder, J.; Rebek, J. J. Am. Chem. Soc. 1991, 113, 5125-5127. For examples of polymeric host-guest recognition using this system see: (a) Asanuma, H.; Ban, T.; Gotoh, S.; Hishiya, T.; Komiyama, M. Macromolecules 1998, 31, 371-377.
39. For other examples of host-guest recognition based on diaminopyridine-imide interactions see: Ge, Y.; Lilienthal, R.; Smith, D. J. Am. Chem. Soc. 1996, 118, 3976. Muehldorf, A. V.; Van Engen, D.; Warner, J. C.; Hamilton, A. D. J. Am. Chem. Soc. 1988, 110, 6561-6562. Park, T.; Schroeder, J.; Rebek, J. J. Am. Chem. Soc. 1991, 113, 5125-5127. For examples of polymeric host-guest recognition using this system see: (a) Asanuma, H.; Ban, T.; Gotoh, S.; Hishiya, T.; Komiyama, M. Macromolecules 1998, 31, 371-377.
40. For other examples of host-guest recognition based on diaminopyridine-imide interactions see: Ge, Y.; Lilienthal, R.; Smith, D. J. Am. Chem. Soc. 1996, 118, 3976. Muehldorf, A. V.; Van Engen, D.; Warner, J. C.; Hamilton, A. D. J. Am. Chem. Soc. 1988, 110, 6561-6562. Park, T.; Schroeder, J.; Rebek, J. J. Am. Chem. Soc. 1991, 113, 5125-5127. For examples of polymeric host-guest recognition using this system see: (a) Asanuma, H.; Ban, T.; Gotoh, S.; Hishiya, T.; Komiyama, M. Macromolecules 1998, 31, 371-377.
41. For other examples of host-guest recognition based on diaminopyridine-imide interactions see: Ge, Y.; Lilienthal, R.; Smith, D. J. Am. Chem. Soc. 1996, 118, 3976. Muehldorf, A. V.; Van Engen, D.; Warner, J. C.; Hamilton, A. D. J. Am. Chem. Soc. 1988, 110, 6561-6562. Park, T.; Schroeder, J.; Rebek, J. J. Am. Chem. Soc. 1991, 113, 5125-5127. For examples of polymeric host-guest recognition using this system see: (a) Asanuma, H.; Ban, T.; Gotoh, S.; Hishiya, T.; Komiyama, M. Macromolecules 1998, 31, 371-377.
42. (b) Lange, R.; Meijer, E. Macromolecules 1995, 28, 782.
43. For the synthesis of monomer 4 see: Deans, R.; Rotello, V. M. J. Org. Chem. 1997, 62, 4528-4529. This monomer does not aggregate in the concentration range used for these studies.