Fluorophobic effect promotes partitioning of organics into macroporous organic polymers: A method for achieving high local concentrations

Journal of the American Chemical Society

Volumn 125, Issue 30, 2003, Pages 9048-9054

  Leeder, Shannon M ^a   Gagné, Michel R ^a  

^a University of North Carolina at Chapel Hill   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

MACROPOROUS MATERIALS;

CONCENTRATION (PROCESS); CROSSLINKING; MONOMERS; ORGANIC SOLVENTS; POROUS MATERIALS;

FLUORINE CONTAINING POLYMERS;

ANTHRACENE DERIVATIVE; CYCLOHEXANE DERIVATIVE; HEXANE; METHANOL; MONOMER; ORGANIC COMPOUND; PERFLUORO COMPOUND; PERFLUOROMETHYLCYCLOHEXANE; POLYMER; SOLVENT; TOLUENE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL STRUCTURE; MEASUREMENT; PARTITION COEFFICIENT; POLYMERIZATION; SYNTHESIS; TEMPERATURE SENSITIVITY; ULTRAVIOLET SPECTROSCOPY;

EID: 0042805250     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0353558     Document Type: Article

References (62)

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39. For recent references on the effect of cross-link density on surface area see: (a) Sellergren, B. Makromol. Chem. 1989, 190, 2703. For poly-(divinylbenzene) polymers (c) Law, R. V.; Sherrington, D. C.; Snape, C. E. Macromolecules 1997, 30, 2868. (d) Xie, S.; Svec, F.; Fréchet, J. M. J. Chem. Mater. 1998, 10, 4072-4078. For multifunctional methacrylate polymers (e) Rohr, T.; Knaus, S.; Gruber, H.; Sherrington, D. C. Macromolecules 2002, 35, 97, (f) Steinke, J. H. G.; Dunkin, I. R.; Sherrington, D. C. Macromolecules 1996, 29, 5826.
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41. In the absence of substrate, this mixture misces at 89 °C, 104 °C if the mixture is 0.25 M in methyl trans-cinnamate.
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46. Several more sophisticated approaches to modeling analyte uptake have been used to separate diffusion into macro-, micro-, and bulk polymer diffusion phases. See, for example: (a) Hradil, J.; Svec, F.; Podlesnyuk, V. V.; Marutovskij, R. M.; Friedman, L. E.; Klimenko, N. A. Ind. Eng. Chem. Res. 1991, 30, 1926-931. (b) Wang, C.; Xu, M.; Shi, Z.; Fan, Y.; Ji, C. Chinese J. React. Polym. 2000, 9, 81-89.
47. Several more sophisticated approaches to modeling analyte uptake have been used to separate diffusion into macro-, micro-, and bulk polymer diffusion phases. See, for example: (a) Hradil, J.; Svec, F.; Podlesnyuk, V. V.; Marutovskij, R. M.; Friedman, L. E.; Klimenko, N. A. Ind. Eng. Chem. Res. 1991, 30, 1926-931. (b) Wang, C.; Xu, M.; Shi, Z.; Fan, Y.; Ji, C. Chinese J. React. Polym. 2000, 9, 81-89.
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50. Functional group like amines have been observed to enhance the partitioning of phenols from aqueous solutions into EDMA-type materials, see for example footnotes 11b and 12.
51. A reviewer correctly pointed out that monomer reactivity ratio differences might not necessarily lead to interior surface functionalizations that are identical to the feed ratios. For several recent examples of derivatizing the interior surface of a porous monolithic polymer through a functional comonomer, see: Viklund, C.; Nordström, A.; Irgum, K.; Svec, F.; Fréchet, J. M. J. Macromolecules 2001, 34, 4361-4369, and footnote 18d.
52. Wende, M.; Meier, R.; Gladysz, J. A. J. Am. Chem. Soc. 2001, 123, 11 490-11 491.
53. This effect is also the basis of thermomorphic catalysts, which are soluble at high temperatures and then phase separate upon cooling For fluoro-based methodologies, see: (a) Rocaboy, C.; Gladysz, J. A. New J. Chem. 2003, 27, 39-49. (b) Rocaboy, C.; Gladysz, J. A. Org. Lett. 2002, 4, 1993-1996. For examples of this approach in nonfluorous systems, see: (c) Bergbreiter, D. E. Chem. Rev. 2002, 102, 3345-3384. (d) Bergbreiter, D. E.; Osburn, P. L.; Frels, J. D. J. Am. Chem. Soc. 2001, 123, 11 105-11 106. (e) Bergbreiter, D. E.; Osburn, P. L.; Wilson, A.; Sink, E. M. J. Am. Chem. Soc. 2000, 122, 9058-9064. (f) Bergbreiter, D. E.; Liu, Y.-S.; Osborn, P. L. J. Am. Chem. Soc. 1998, 120, 4250-4251.
54. This effect is also the basis of thermomorphic catalysts, which are soluble at high temperatures and then phase separate upon cooling For fluoro-based methodologies, see: (a) Rocaboy, C.; Gladysz, J. A. New J. Chem. 2003, 27, 39-49. (b) Rocaboy, C.; Gladysz, J. A. Org. Lett. 2002, 4, 1993-1996. For examples of this approach in nonfluorous systems, see: (c) Bergbreiter, D. E. Chem. Rev. 2002, 102, 3345-3384. (d) Bergbreiter, D. E.; Osburn, P. L.; Frels, J. D. J. Am. Chem. Soc. 2001, 123, 11 105-11 106. (e) Bergbreiter, D. E.; Osburn, P. L.; Wilson, A.; Sink, E. M. J. Am. Chem. Soc. 2000, 122, 9058-9064. (f) Bergbreiter, D. E.; Liu, Y.-S.; Osborn, P. L. J. Am. Chem. Soc. 1998, 120, 4250-4251.
55. This effect is also the basis of thermomorphic catalysts, which are soluble at high temperatures and then phase separate upon cooling For fluoro-based methodologies, see: (a) Rocaboy, C.; Gladysz, J. A. New J. Chem. 2003, 27, 39-49. (b) Rocaboy, C.; Gladysz, J. A. Org. Lett. 2002, 4, 1993-1996. For examples of this approach in nonfluorous systems, see: (c) Bergbreiter, D. E. Chem. Rev. 2002, 102, 3345-3384. (d) Bergbreiter, D. E.; Osburn, P. L.; Frels, J. D. J. Am. Chem. Soc. 2001, 123, 11 105-11 106. (e) Bergbreiter, D. E.; Osburn, P. L.; Wilson, A.; Sink, E. M. J. Am. Chem. Soc. 2000, 122, 9058-9064. (f) Bergbreiter, D. E.; Liu, Y.-S.; Osborn, P. L. J. Am. Chem. Soc. 1998, 120, 4250-4251.
56. This effect is also the basis of thermomorphic catalysts, which are soluble at high temperatures and then phase separate upon cooling For fluoro-based methodologies, see: (a) Rocaboy, C.; Gladysz, J. A. New J. Chem. 2003, 27, 39-49. (b) Rocaboy, C.; Gladysz, J. A. Org. Lett. 2002, 4, 1993-1996. For examples of this approach in nonfluorous systems, see: (c) Bergbreiter, D. E. Chem. Rev. 2002, 102, 3345-3384. (d) Bergbreiter, D. E.; Osburn, P. L.; Frels, J. D. J. Am. Chem. Soc. 2001, 123, 11 105-11 106. (e) Bergbreiter, D. E.; Osburn, P. L.; Wilson, A.; Sink, E. M. J. Am. Chem. Soc. 2000, 122, 9058-9064. (f) Bergbreiter, D. E.; Liu, Y.-S.; Osborn, P. L. J. Am. Chem. Soc. 1998, 120, 4250-4251.
57. This effect is also the basis of thermomorphic catalysts, which are soluble at high temperatures and then phase separate upon cooling For fluoro-based methodologies, see: (a) Rocaboy, C.; Gladysz, J. A. New J. Chem. 2003, 27, 39-49. (b) Rocaboy, C.; Gladysz, J. A. Org. Lett. 2002, 4, 1993-1996. For examples of this approach in nonfluorous systems, see: (c) Bergbreiter, D. E. Chem. Rev. 2002, 102, 3345-3384. (d) Bergbreiter, D. E.; Osburn, P. L.; Frels, J. D. J. Am. Chem. Soc. 2001, 123, 11 105-11 106. (e) Bergbreiter, D. E.; Osburn, P. L.; Wilson, A.; Sink, E. M. J. Am. Chem. Soc. 2000, 122, 9058-9064. (f) Bergbreiter, D. E.; Liu, Y.-S.; Osborn, P. L. J. Am. Chem. Soc. 1998, 120, 4250-4251.
58. This effect is also the basis of thermomorphic catalysts, which are soluble at high temperatures and then phase separate upon cooling For fluoro-based methodologies, see: (a) Rocaboy, C.; Gladysz, J. A. New J. Chem. 2003, 27, 39-49. (b) Rocaboy, C.; Gladysz, J. A. Org. Lett. 2002, 4, 1993-1996. For examples of this approach in nonfluorous systems, see: (c) Bergbreiter, D. E. Chem. Rev. 2002, 102, 3345-3384. (d) Bergbreiter, D. E.; Osburn, P. L.; Frels, J. D. J. Am. Chem. Soc. 2001, 123, 11 105-11 106. (e) Bergbreiter, D. E.; Osburn, P. L.; Wilson, A.; Sink, E. M. J. Am. Chem. Soc. 2000, 122, 9058-9064. (f) Bergbreiter, D. E.; Liu, Y.-S.; Osborn, P. L. J. Am. Chem. Soc. 1998, 120, 4250-4251.
59. At high concentrations of 1 (> 1.0 mM) the partitioning is insensitive to temperature (∼850/o for 26-46 °C, and ∼83% for 51-66 °C. Sorption thermodynamics have been analyzed by both Frendlich and Langmuir isotherm models, see for example footnote 11.
60. See, for example: (a) Peters, E. C.; Svec, F.; Fréchet, J. M. J. Adv. Mater. 1999, 11, 1169-1181.
61. (b) Svec, F.; Fréchet, J. M. J. Chem. Mater. 1995, 7, 707-715.
62. The filling of the pores with solvent is accompanied by a rapid displacement of the air (seconds) in the interior pores, which is accompanied by the liberation of small air bubbles.