TY - JOUR
T1 - Synthesis and Self-Assembly of Amphiphilic Star/Linear-Dendritic Polymers
T2 - Effect of Core versus Peripheral Branching on Reverse Micelle Aggregation
AU - Kosakowska, Karolina A.
AU - Casey, Brittany K.
AU - Albert, Julie N.L.
AU - Wang, Yang
AU - Ashbaugh, Henry S.
AU - Grayson, Scott M.
N1 - Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/8/13
Y1 - 2018/8/13
N2 - A series of branched polymers, consisting of a poly(ethylene glycol) (PEG) core and lipophilic peripheral dendrons, were synthesized and their self-assembly into reverse micelles studied toward the ultimate goal of carrier-mediated transdermal drug delivery. More specifically, this investigation systematically explores the structure-property contributions arising from location and extent of branching by varying the number of branch points at the core and the generation of dendrons at the polar/nonpolar interface. For branching at the core, PEGs were selected with one, two or four arms, with one terminal functionality per arm. For peripheral branching, end groups were modified with polyester dendrons (of dendritic generations 0, 1, and 2) for each of the three cores. Finally, lauric acid (LA) was used to esterify the periphery, yielding a library of branched, amphiphilic polymers. Characterization of these materials via MALDI-TOF MS, GPC and NMR confirmed their exceptionally well-defined structure. Furthermore, atomic force microscopy (AFM) and dynamic light scattering (DLS) confirmed these polymers' abilities to make discrete aggregates. As expected, increased multiplicity of branching resulted in more compact aggregates; however, the location of branching (core vs periphery) did not seem as important in defining aggregate size as the extent of branching. Finally, computational modeling of the branched amphiphile series was explored to elucidate the macromolecular interactions governing self-assembly in these systems.
AB - A series of branched polymers, consisting of a poly(ethylene glycol) (PEG) core and lipophilic peripheral dendrons, were synthesized and their self-assembly into reverse micelles studied toward the ultimate goal of carrier-mediated transdermal drug delivery. More specifically, this investigation systematically explores the structure-property contributions arising from location and extent of branching by varying the number of branch points at the core and the generation of dendrons at the polar/nonpolar interface. For branching at the core, PEGs were selected with one, two or four arms, with one terminal functionality per arm. For peripheral branching, end groups were modified with polyester dendrons (of dendritic generations 0, 1, and 2) for each of the three cores. Finally, lauric acid (LA) was used to esterify the periphery, yielding a library of branched, amphiphilic polymers. Characterization of these materials via MALDI-TOF MS, GPC and NMR confirmed their exceptionally well-defined structure. Furthermore, atomic force microscopy (AFM) and dynamic light scattering (DLS) confirmed these polymers' abilities to make discrete aggregates. As expected, increased multiplicity of branching resulted in more compact aggregates; however, the location of branching (core vs periphery) did not seem as important in defining aggregate size as the extent of branching. Finally, computational modeling of the branched amphiphile series was explored to elucidate the macromolecular interactions governing self-assembly in these systems.
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U2 - 10.1021/acs.biomac.8b00679
DO - 10.1021/acs.biomac.8b00679
M3 - Article
C2 - 29986144
AN - SCOPUS:85049841616
SN - 1525-7797
VL - 19
SP - 3177
EP - 3189
JO - Biomacromolecules
JF - Biomacromolecules
IS - 8
ER -