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Published October 23, 2012 | Supplemental Material + Published
Journal Article Open

Using EPR To Compare PEG-branch-nitroxide "Bivalent-Brush Polymers" and Traditional PEG Bottle–Brush Polymers: Branching Makes a Difference

Abstract

Attachment of poly(ethylene glycol) (PEG) to polymeric nanostructures is a general strategy for sterically shielding and imparting water solubility to hydrophobic payloads. In this report, we describe direct graft-through polymerization of branched, multifunctional macromonomers that possess a PEG domain and a hydrophobic nitroxide domain. Electron paramagnetic resonance (EPR) spectroscopy was used to characterize microenvironments within these novel nanostructures. Comparisons were made to nitroxide-labeled, traditional bottle-brush random and block copolymers. Our results demonstrate that bivalent bottle-brush polymers have greater microstructural homogeneity compared to random copolymers of similar composition. Furthermore, we found that compared to a traditional brush polymer, the branched-brush, "pseudo-alternating" microstructure provided more rotational freedom to core-bound nitroxides, and greater steric shielding from external reagents. The results will impact further development of multivalent bottle-brush materials as nanoscaffolds for biological applications.

Additional Information

© 2012 American Chemical Society. Published In Issue October 23, 2012; Article ASAP: October 04, 2012; Received: September 06, 2012.

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Published - ma301874d.pdf

Supplemental Material - ma301874d_si_001.pdf

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August 19, 2023
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