Complex macromolecular architectures by reversible addition fragmentation chain transfer chemistry: Theory and practice

Leonie Barner, Thomas P. Davis, Martina H. Stenzel, Christopher Barner-Kowollik

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317 Citations (Scopus)


Reversible addition-fragmentation chain transfer (RAFT) chemistry can be effectively employed to construct macromolecular architectures of varying topologies. The present article explores the principle design routes to star, block, and comb polymers in the context of theoretical design criteria for the so-called Z- and R-group approaches. The specific advantages and disadvantages of each approach are underpinned by selected examples generated in the CAMD laboratories. In particular, we demonstrate how the modeling of full molecular weight distributions can be employed to guide the synthetic effort. We further explore the theory and practice of generating amphiphilic block copolymer structures and their self-assembly. In addition, the article foreshadows how modern synthetic techniques that combine RAFT chemistry with highly orthogonal click chemistry can be employed as a powerful tool that furthers the enhancement of macromolecular design possibilities to generate block (star) copolymers of monomers with extremely disparate reactivities. Finally, the ability of RAFT chemistry to modify the surface of well-defined nano- and microspheres as devices in biomedical application is detailed.

Original languageEnglish
Pages (from-to)539-559
Number of pages21
JournalMacromolecular Rapid Communications
Issue number5
Publication statusPublished - 1 Mar 2007
Externally publishedYes


  • Block copolymers
  • Comb polymers
  • Complex macromolecular architectures
  • Grafting from microspheres
  • Living free radical polymerization
  • Mechanism and kinetics
  • Reversible addition-fragmentation chain transfer (RAFT)
  • Star polymers

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