Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 132, Issue 47, Pages 16741-16744Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja1078305
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Funding
- National Science Foundation [DMR-0906898, DMR-0821313, CHE-0517909]
- Lubrizol Corporation
- Direct For Mathematical & Physical Scien
- Division Of Materials Research [906898, 0821313] Funding Source: National Science Foundation
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A novel giant surfactant possessing a well-defined hydrophilic head and a hydrophobic polymeric tail, polystyrene-(carboxylic acid-functionalized polyhedral oligomeric silsesquioxane) conjugate (PS-APOSS), has been designed and synthesized via living anionic polymerization, hydrosilylation, and thiol-ene click chemistry. PS-APOSS forms micelles in selective solvents, and the micellar morphology can be tuned from vesicles to wormlike cylinders and further to spheres by increasing the degree of ionization of the carboxylic acid. The effect of APOSS-APOSS interactions was proven to be essential in the morphological transformation of the micelles. The PS tails in these micellar cores were found to be highly stretched in comparison with those in traditional amphiphilic block copolymers, and this can be explained in terms of minimization of free energy. This novel class of giant surfactants expands the scope of macromolecular amphiphiles and provides a platform for the study of the basic physical principles of their self-assembly behavior.
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