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EPR Study of Spin Labeled Brush Polymers in Organic Solvents

Xia, Yan and Li, Yongjun and Burts, Alan O. and Ottaviani, M. Francesca and Tirrell, David A. and Johnson, Jeremiah A. and Turro, Nicholas J. and Grubbs, Robert H. (2011) EPR Study of Spin Labeled Brush Polymers in Organic Solvents. Journal of the American Chemical Society, 133 (49). pp. 19953-19959. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20120214-082513251

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Abstract

Spin-labeled polylactide brush polymers were synthesized via ring-opening metathesis polymerization (ROMP), and nitroxide radicals were incorporated at three different locations of brush polymers: the end and the middle of the backbone, and the end of the side chains (periphery). Electron paramagnetic resonance (EPR) was used to quantitatively probe the macromolecular structure of brush polymers in dilute solutions. The peripheral spin-labels showed significantly higher mobility than the backbone labels, and in dimethylsulfoxide (DMSO), the backbone end labels were shown to be more mobile than the middle labels. Reduction of the nitroxide labels by a polymeric reductant revealed location-dependent reactivity of the nitroxide labels: peripheral nitroxides were much more reactive than the backbone nitroxides. In contrast, almost no difference was observed when a small molecule reductant was used. These results reveal that the dense side chains of brush polymers significantly reduce the interaction of the backbone region with external macromolecules, but allow free diffusion of small molecules.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja2085349DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja2085349PublisherArticle
ORCID:
AuthorORCID
Tirrell, David A.0000-0003-3175-4596
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2011 American Chemical Society. Publication Date (Web): October 24, 2011. Received: September 9, 2011. We gratefully thank Dr. Xuegong Lei for help with initial EPR experiments. This work was supported by the Department of Energy (DE-FG02-05ER46218) and by the NSF Center for the Science and Engineering of Materials at the California Institute of Technology.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-FG02-05ER46218
NSFUNSPECIFIED
Issue or Number:49
Record Number:CaltechAUTHORS:20120214-082513251
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20120214-082513251
Official Citation:EPR Study of Spin Labeled Brush Polymers in Organic Solvents Yan Xia, Yongjun Li, Alan O. Burts, M. Francesca Ottaviani, David A. Tirrell, Jeremiah A. Johnson, Nicholas J. Turro, and Robert H. Grubbs Journal of the American Chemical Society 2011 133 (49), 19953-19959
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:29267
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:14 Feb 2012 17:18
Last Modified:03 Oct 2019 03:39

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