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Education and Outreach:

Controlled Macromolecular Heterogeneity by ATRP Krzysztof Matyjaszewski, Carnegie-Mellon University, DMR 0969301.

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Education and Outreach:

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  1. Controlled Macromolecular Heterogeneity by ATRPKrzysztof Matyjaszewski, Carnegie-Mellon University, DMR 0969301 The main activity of DMR-09-69301 project is focused on synthesis, characterization and potential applications of polymers with controlled heterogeneities. Three major elements of molecular heterogeneity: chain uniformity (dispersity), composition (gradients) and chain topology (branching / crosslinking) are explored and their effect on nanostructured morphology and macroscopic properties studied. The cover in the first issue of ACS MacroLetters shows how atom transfer radical polymerization (ATRP) methods were developed in water-based media, to grow polymers from proteins under biologically relevant conditions. Several reaction parameters (ligand structure, halide species, initiation mode) were optimized in water and PBS buffer to yield well-defined polymers grown from bovine serum albumin (BSA), functionalized with cleavable ATRP initiators (I). The CuCl complex with ligand 2,2′-bipyridyne (bpy) provides the best conditions for the polymerization of oligo(ethylene oxide) methacrylate (OEOMA) in water at 30 °C under normal ATRP conditions (I/CuCl/CuCl2/bpy = 1/1/9/22). Activators generated by electron transfer (AGET) ATRP gave well-controlled polymerization of OEOMA at 30 °C with the ligand tris(2-pyridylmethyl) amine (TPMA), (I/CuBr2/TPMA = 1/10/11). The AGET ATRP reactions required slow feeding of a very small amount of ascorbic acid into the aqueous reaction medium/buffer. The reaction conditions developed were used to create a smart, thermoresponsive, protein−polymer hybrid.

  2. Controlled Macromolecular Heterogeneity by ATRPKrzysztof Matyjaszewski, Carnegie-Mellon University, DMR 0969301 Education and Outreach: -6 graduate students (Cho, Li, Dong, Yoon, Ye and Nese), 6 postdocs (Tonge, Magenau, Wu, Zhu, Amamoto and Konkolewicz) contributed to this project. -2 books were published by ACS in April 20012 with papers presented at the 2011 ACS Denver meeting, where 182 papers were presented. -10 Volume (270 Chapters, 7550 pages) “Polymer Science: A Comprehensive Reference” was co-edited & published by Elsevier in June 2012.

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