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

Burts, Alan O. and Li, Yongjun and Zhukhovitskiy, Aleksandr V. and Patel, Paresma R. and Grubbs, Robert H. and Ottaviano, M. Francesca and Turro, Nicholas J. and Johnson, Jeremiah A. (2012) Using EPR To Compare PEG-branch-nitroxide “Bivalent-Brush Polymers” and Traditional PEG Bottle–Brush Polymers: Branching Makes a Difference. Macromolecules, 45 (20). pp. 8310-8318. ISSN 0024-9297. https://resolver.caltech.edu/CaltechAUTHORS:20121126-103324858

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ma301874dDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ma301874dPublisherArticle
ORCID:
AuthorORCID
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2012 American Chemical Society. Published In Issue October 23, 2012; Article ASAP: October 04, 2012; Received: September 06, 2012.
Issue or Number:20
Record Number:CaltechAUTHORS:20121126-103324858
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20121126-103324858
Official Citation:Using EPR To Compare PEG-branch-nitroxide “Bivalent-Brush Polymers” and Traditional PEG Bottle–Brush Polymers: Branching Makes a Difference Alan O. Burts, Yongjun Li, Aleksandr V. Zhukhovitskiy, Paresma R. Patel, Robert H. Grubbs, M. Francesca Ottaviani, Nicholas J. Turro, and Jeremiah A. Johnson Macromolecules 2012 45 (20), 8310-8318
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:35631
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:26 Nov 2012 21:12
Last Modified:03 Oct 2019 04:30

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