Carnegie Mellon University Controlled Macromolecular Heterogeneity by ATRP Krzysztof Matyjaszewski, Carnegie-Mellon University, DMR The main activity is focused on synthesis, characterization and potential applications of polymers with controlled heterogeneities. Three major elements of molecular heterogeneity: chain uniformity, composition and chain topology are explored and their effect on nanostructured morphology and macroscopic properties studied. Materials prepared include bioconjugates with nucleic acids, inorganic hybrids and nanocarbons. n New covalent polymer-escort siRNA (short-interfering ribonucleic acids) constructs were prepared by click conjugation of polymers to the passenger strand of a siRNA duplex. The escorts confer both protection against nuclease, facilitate cellular internalization of the siRNA and were effective in knocking down reporter and endogenous genes. (S. Averick et al., J. Am. Chem. Soc. 2013;135: ) Binder-free films of nitrogen-enriched nanocarbons, prepared by the pyrolysis of polyacrylonitrile-block-poly(n-butyl acrylate) copolymer drop-casted on glassy carbon disk electrode, exhibited high electrocatalytic activity for the oxygen reduction reaction (ORR), matching that of Pt-based electrocatalysts. ORR performance critically depended on the presence of a nanoporous structure, i.e. nitrogen-terminated edges of nanographitic domains as catalytic sites.(M. Zhong et al., Chem. Sci. 2014;5: ) n An ATRP initiator was introduced into DNA using phosphoramidite chemistry to prepare well-defined copolymers both on the solid phase synthesis bead and in solution. (S. Averick et al., Angew. Chem., Int. Ed. 2014;53: )

Carnegie Mellon University Education and Outreach: -54 international chemical companies have been participating in Controlled Radical Polymerization Consortium at CMU. Current members include: Aculon, ATRP Solutions, DSM, Evonik, General Electric, Henkel, Kaneka, Kurary, Merck, ShineSun and PPG. 16 commercial licenses have been signed for ATRP technology and production of polymers by ATRP process has been commercialized in U.S., Japan and Europe. -Matyjaszewski will co-organize in August 10-14, 2014 the 7 th Controlled Radical Polymerization Meeting at ACS Meeting in San Francisco with 93 oral presentations and 92 posters. Proceedings from the ACS Symposium will be published as a volume within ACS Symposia series, as from 6 previous CRP Symposia. -Mingjiang Zhong was selected as a finalist for 2014 ACS Eastman Chemical Student Award in Applied Polymer Science, Saadyah Averick was selected a finalist for 2014 ACS DSM Science and Technology Award: Innovative Polymer Solutions for Biomedical Applications. KM received 2014 National Institute of Materials Science (Japan) Award and Distinguished Service Award from ACS Polymer Division. KM received Honorary Degree from Université P. & M. Curie, Sorbonne, Paris (France), and was elected as a Fellow of National Academy of Inventors. - Dissemination: 19 peer reviews papers were published with acknowledgement of DMR support in 2014 and 17 in Our website is visited >50,000 times each year. Controlled Macromolecular Heterogeneity by ATRP Krzysztof Matyjaszewski, Carnegie-Mellon University, DMR