Solvent programmable polymers based on restricted rotation

Journal of the American Chemical Society

Volumn 131, Issue 34, 2009, Pages 12062-12063

  Zhang, Yagang ^a   Lavin, Judith M ^a   Shimizu, Ken D ^a  

^a UNIVERSITY OF SOUTH CAROLINA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL EQUATIONS; CROSS-LINKED POLYMERS; DIFFERENT SOLVENTS; ELEVATED TEMPERATURE; NON-POLAR SOLVENTS; POLAR SOLVENTS; PROGRAMMABILITY; RECOGNITION PROPERTIES; RESTRICTED ROTATIONS; SOLVENT POLARITY; SWITCHING PROCESS;

CARBOXYLIC ACIDS; CROSSLINKING; GELATION; HEATING; ORGANIC ACIDS; POLYMERS; ROTATION; SOLVENTS; SURFACE PLASMON RESONANCE; TOLUENE;

ORGANIC SOLVENTS;

ACETONITRILE; CARBON; HYDROGEN; MONOMER; NITROGEN; ORGANIC SOLVENT; POLYMER; SOLVENT; WATER;

ARTICLE; CHEMICAL BINDING; CHEMICAL BOND; CHEMICAL REACTION; CONFORMATION; COOLING; HEAT SENSITIVITY; HEATING; HYDROGEN BOND; KINETICS; MOLECULAR RECOGNITION; POLARIZATION; ROOM TEMPERATURE; ROTATION; SOLUBILITY; STIMULATION;

ACETATES; ADENINE; POLYMERS; ROTATION; SOLVENTS; TEMPERATURE;

EID: 69349104686     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja904234w     Document Type: Article

References (29)

1. (a) Bohidar, H. B.; Dubin, P.; Osade, Y. Polymer Gels: Fundamentals and Applications (ACS Symposium Series); American Chemical Society: 2002.
2. (b) Galaev, I.; Mattiasson, B. Smart Polymers: Applications in Biotechnology and Biomedicine, 2nd ed.; CRC: 2007.
3. (c) Kumar, A.; Srivastava, A.; Galaev, I. Y.; Mattiasson, B. Prog. Polym. Sci. 2007, 32, 1205-1237.
4. (d) Ha, C. S.; Gardella, J. A. Chem. Rev. 2005, 105, 4205-4232.
5. (e) Lee, K. Y.; Mooney, D. J. Chem. Rev. 2001, 101, 1869-1879.
6. (f) Alarcon, C. D. H.; Pennadam, S.; Alexander, C. Chem. Soc. Rev. 2005, 34, 276-285.
7. (a) Alexander, C.; Shakesheff, K. M. Adv. Mater. 2006, 18, 3321-3328.
8. (b) Kost, J.; Langer, R. Adv. Drug Delivery Rev. 2001, 46, 125-148.
9. (c) Mano, J. F. Adv. Eng. Mater. 2008, 10, 515-527.
10. (d) Kulkarni, R. V.; Biswanath, S. J. Appl. Biomater. Biomech. 2007, 5, 125-139.
11. (e) Rzaev, Z. M. O.; Dincer, S.; Piskin, E. Prog. Polym. Sci. 2007, 32, 534-595.
12. (f) Ahn, S. K.; Kasi, R. M.; Kim, S. C.; Sharma, N.; Zhou, Y. X. Soft Matter 2008, 4, 1151-1157.
13. (g) Miyata, T.; Uragami, T.; Nakamae, K. Adv. Drug Delivery Rev. 2002, 54, 79-98.
14. (a) Wilson, M. D.; Whitesides, G. M. J. Am. Chem. Soc. 1988, 110, 8718-8719.
15. (b) Welch, C. J. J. Chromatogr., A 1995, 689, 189-193.
16. (a) Lavin, J. M.; Shimizu, K. D. Chem. Commun. 2007, 228-230.
17. (b) Degenhardt, C. F.; Lavin, J. M.; Smith, M. D.; Shimizu, K. D. Org. Lett. 2005, 7, 4079-4081.
18. (c) Chong, Y. S.; Smith, M. D.; Shimizu, K. D. J. Am. Chem. Soc. 2001, 123, 7463-7464.
19. (d) Kishikawa, K.; Yoshizaki, K.; Kohmoto, S.; Yamamoto, M.; Yamaguchi, K.; Yamada, K. J. Chem. Soc., Perkin Trans. 1 1997, 1233-1239.
20. (e) Curran, D. P.; Geib, S.; DeMello, N. Tetrahedron 1999, 55, 5681-5704.
21. (f) Verma, S. M.; Singh, N. B. Aust. J. Chem. 1976, 29, 295-300.
22. Buchmeiser, M. R. Chem. Rev. 2000, 100, 1565-1604.
23. The rotational barrier of 1 could not be measured because the bicyclic bridge sterically biases the atropisomer to form only a single isomer. After polymerization, this steric bias is removed as the bicyclic ring is broken in the ROMP. Thus, the fused ring system of compound 4 is a more appropriate model for the C-N rotational barrier in the ROMP product.
24. For a binding study, 60 mg of polymer were shaken with 0.1 mM EA9A in CH3CN (2.5 mL). The concentration of EA9A in the supernatant was measured by UV-vis (257 nm) and compared with the original stock solution.
25. (a) Lancelot, G. J. Am. Chem. Soc. 1977, 99, 7037.
26. (b) Shea, K. J.; Spivak, D. A.; Sellergren, B. J. Am. Chem. Soc. 1993, 115, 3368-3369.
27. Reichardt, C. Solvents and Solvent Effects in Organic Chemistry, 2nd ed.; VCH: Weinheim, 1988.
28. A number of studies have established that barriers of atropisomers in polymer matrices and films are very similar to those measured in solution, and in some cases, the rotational barriers in polymer matrices can be lower. See: Park, J. W.; Green, M. M.; Morawetz, H. Macromolecules 2001, 34, 5719-5722, and references therein.
29. Using the Eyring equation, a barrier of 27.1 kcal/mol equates to a half-life of 56 days at 25°C.