Synthesis, physicochemical characterization, and self-assembly of linear, dibranched, and miktoarm semifluorinated triphilic polymers

• Published in: Journal of polymer science. Part A, Polymer chemistry Polymer chemistry, 2014-12, Vol.52 (23), p.3324-3336
• Main Authors: Tucker, William B., McCoy, Aaron M., Fix, Samantha M., Stagg, Melissa F., Murphy, Matt M., Mecozzi, Sandro
• Format: Article
• Language: English
• Subjects: Agglomeration; Aggregates; Applied sciences; Architecture; Biological and medical sciences; Chemical modifications; Chemical reactions and properties; Encapsulation; Exact sciences and technology; Fluorocarbons; fluorous; General pharmacology; Medical sciences; Micelles; Organic polymers; Pharmaceutical technology. Pharmaceutical industry; Pharmacology. Drug treatments; Physicochemistry of polymers; Polymers; Self assembly; surfactants
• ISSN: 0887-624X; 1099-0518
• DOI: 10.1002/pola.27394

ABSTRACT Linear, dibranched, and miktoarm amphiphiles containing both hydrophobic and fluorophilic moieties were synthesized and characterized in an attempt to elucidate the relationship between semifluorinated amphiphile structure and aggregate behavior in aqueous solution. For the linear and dibranched amphiphiles, there was an exponential decrease in critical aggregation concentration (CMC) and a logarithmic increase in core microviscosity with increasing length of the fluorocarbon segments; while the miktoarm architecture produced no notable trend in microviscosity or CMC. Furthermore, the linear and dibranched surfactants showed enhanced kinetic stability, dissociating more slowly in the presence of human serum than did either the dibranched or miktoarm amphiphiles. Finally, encapsulation studies with the hydrophobic drug paclitaxel (PTX) showed that the ability to solubilize and retain PTX increased with the presence and with the increasing size of the fluorocarbon moiety for both the linear and dibranched amphiphiles, while no such trend was observed for the miktoarm amphiphiles. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 3324–3336 Three classes of semifluorinated amphiphiles were synthesized and their aggregation behavior was characterized. It was found that critical micelle concentration, microviscosity and aggregate stability were related to amphiphile architecture and the size of the fluorocarbon segment. Furthermore, it has been shown that a hydrophobic molecule—paclitaxel—can be encapsulated within the semifluorinated micelles derived from these polymers, thus demonstrating the potential to encapsulate hydrophobic species within a lipophilic shell without necessitating a lipophilic core.