Well-defined core-shell brush block copolymers were prepared by tandem ring-opening metathesis polymerization (ROMP) and living radical polymerization (LRP), and used as unimolecular templates for the synthesis of polymer-based nanoparticles. Several bifunctional compounds, containing a norbornene functionality and an alkoxyamine, haloester, or trithiocarbonate functionality, were synthesized. ROMP of these compounds gave well-defined polyfunctional macroinitiators or macro-chain transfer agents for LRP. Sequential LRP of different monomers using these macroinitiators or macro-chain transfer agents yielded core-shell brush block copolymers with controlled macromolecular architectures. The entire synthetic procedure of core-shell brush block copolymers could be simplified by one-pot sequential ROMP and LRP based on their excellent compatibility. Shell-crosslinked nanoparticles were prepared by selectively crosslinking the shell domains of core-shell brush block copolymers, and nanocages were further obtained by degradation of the core domains of these nanoparticles. Core-crosslinked nanoparticles with controlled shape and size were also synthesized by selectively crosslinking the core domains of core-shell brush block copolymers.

References: 1). Cheng, C.; Qi, K.; Germack, D. G.; Khoshdel, E.; Wooley, K. L. Adv. Mater. 2007, 19, accepted. 2). Cheng, C.; Khoshdel, E.; Wooley, K. L. Macromolecules 2007, 40, 2289-2292. 3). Cheng, C.; Khoshdel, E.; Wooley, K. L. Nano Letters 2006, 6, 1741-1746. 4). Cheng, C.; Qi, K.; Khoshdel, E.; Wooley, K. L. J. Am. Chem. Soc. 2006, 128, 6808-6809. 5). Cheng, C.; Khoshdel, E.; Wooley, K. L. Macromolecules 2005, 38, 9455-9465.

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