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Electrochemically Mediated Atom Transfer Radical Polymerization

Magenau, Andrew J. D. and Strandwitz, Nicholas C. and Gennaro, Armando and Matyjaszewski, Krzysztof (2011) Electrochemically Mediated Atom Transfer Radical Polymerization. Science, 332 (6025). pp. 81-84. ISSN 0036-8075.

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Atom transfer radical polymerization is a versatile technique for exerting precise control over polymer molecular weights, molecular weight distributions, and complex architectures. Here, we show that an externally applied electrochemical potential can reversibly activate the copper catalyst for this process by a one-electron reduction of an initially added air-stable cupric species (Cu^(II)/Ligand). Modulation of polymerization kinetics is thereby tunable in real time by varying the magnitude of applied potential. Application of multistep intermittent potentials successfully triggers initiation of polymerization and subsequently toggles the polymerization between dormant and active states in a living manner. Catalyst concentrations down to 50 parts per million are demonstrated to maintain polymerization control manifested in linear first-order kinetics, a linear increase in polymer molecular weight with monomer conversion, and narrow polymer molecular weight distributions over a range of applied potentials.

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Additional Information:© 2011 American Association for the Advancement of Science. Received 30 December 2010; accepted 2 March 2011. We acknowledge the U.S. National Science Foundation (grants DMR 09-69301 and CHE 10-26060) and the members of the CRP Consortium at Carnegie Mellon University for financial support. N.C.S. acknowledges the U.S. National Science Foundation for an American Competitiveness in Chemistry postdoctoral fellowship (CHE-1042006). A.J.D.M. and K.M. filed a U.S. provisional patent application (61/459,724) related to this work.
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Carnegie Mellon UniversityUNSPECIFIED
Issue or Number:6025
Record Number:CaltechAUTHORS:20110420-081252582
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Official Citation:Electrochemically Mediated Atom Transfer Radical Polymerization Andrew J. D. Magenau, Nicholas C. Strandwitz, Armando Gennaro, and Krzysztof Matyjaszewski Science 1 April 2011: 332 (6025), 81-84. [DOI:10.1126/science.1202357]
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:23388
Deposited By: Tony Diaz
Deposited On:20 Apr 2011 16:19
Last Modified:03 Oct 2019 02:46

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