3 years ago

Donut-Shaped Nanoparticles Templated by Cyclic Bottlebrush Polymers

Donut-Shaped Nanoparticles Templated by Cyclic Bottlebrush Polymers
Zhengping Liu, Lifen Xiao, Lin Qu, Ying Wu, Ke Zhang, Wen Zhu
Cyclic bottlebrush polymers were synthesized and used as single molecular templates to prepare donut-shaped hybrid nanoparticles with organo-silica cross-linked and gold nanocluster coordinated internal structures. “Grafting-onto” strategy was adopted to prepare cyclic bottlebrush polymers by combining ring-expansion metathesis polymerization (REMP), reversible addition–fragmentation chain transfer (RAFT) polymerization, and triazolinedione (TAD)-diene click reaction. In this approach, cyclic poly(norbornene imide) backbones with diene side groups (C-PNB-diene) were synthesized based on REMP technique. TAD-terminated diblock copolymer side chains were produced from RAFT polymerization including TAD-terminated poly(3-(triethoxysilyl)propyl methacrylate)-block-poly(oligo(ethylene glycol) methacrylate) (TAD-PTEPM-b-POEGMA) and TAD-terminated poly(glycidyl methacrylate)-block-poly(oligo(ethylene glycol) methacrylate) (TAD-PGMA-b-POEGMA). The cyclic bottlebrush polymers 1 and 2 were then prepared by virtue of TAD-diene click reaction to graft TAD-PTEPM-b-POEGMA and TAD-PGMA-b-POEGMA side chains onto C-PNB-diene backbones, respectively. Furthermore, the donut-shaped hybrid nanoparticles with organo-silica cross-linked internal structures were obtained by in situ cross-linking PTEPM domains of the cyclic bottlebrush polymer 1 templates. For the formation of donut-shaped hybrid nanoparticles coordinating gold nanoclusters inside, the cyclic bottlebrush polymer 2 templates were first postmodified to introduce the functional pyridine groups inside the PGMA domains, which were then used as location to coordinate the gold nanoclusters.

Publisher URL: http://dx.doi.org/10.1021/acs.macromol.7b01512

DOI: 10.1021/acs.macromol.7b01512

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