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Hybrid Bonding Bottlebrush Polymers Grafted from a Supramolecular Polymer Backbone.
Clemons, Tristan D; Egner, Simon A; Grzybek, Joseph; Roan, Joshua J; Sai, Hiroaki; Yang, Yang; Syrgiannis, Zois; Sun, Hao; Palmer, Liam C; Gianneschi, Nathan C; Stupp, Samuel I.
Afiliación
  • Clemons TD; Simpson Querrey Institute for BioNanotechnology, Northwestern University, Chicago, Illinois 60611, United States.
  • Egner SA; Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.
  • Grzybek J; Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, United States.
  • Roan JJ; Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.
  • Sai H; Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, United States.
  • Yang Y; Simpson Querrey Institute for BioNanotechnology, Northwestern University, Chicago, Illinois 60611, United States.
  • Syrgiannis Z; Simpson Querrey Institute for BioNanotechnology, Northwestern University, Chicago, Illinois 60611, United States.
  • Sun H; Simpson Querrey Institute for BioNanotechnology, Northwestern University, Chicago, Illinois 60611, United States.
  • Palmer LC; Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.
  • Gianneschi NC; Simpson Querrey Institute for BioNanotechnology, Northwestern University, Chicago, Illinois 60611, United States.
  • Stupp SI; International Institute of Nanotechnology, Chemistry of Life Processes Institute, Northwestern University, Evanston, Illinois 60208, United States.
J Am Chem Soc ; 146(23): 16085-16096, 2024 Jun 12.
Article en En | MEDLINE | ID: mdl-38831660
ABSTRACT
Bottlebrush polymers, macromolecules consisting of dense polymer side chains grafted from a central polymer backbone, have unique properties resulting from this well-defined molecular architecture. With the advent of controlled radical polymerization techniques, access to these architectures has become more readily available. However, synthetic challenges remain, including the need for intermediate purification, the use of toxic solvents, and challenges with achieving long bottlebrush architectures due to backbone entanglements. Herein, we report hybrid bonding bottlebrush polymers (systems integrating covalent and noncovalent bonding of structural units) consisting of poly(sodium 4-styrenesulfonate) (p(NaSS)) brushes grafted from a peptide amphiphile (PA) supramolecular polymer backbone. This was achieved using photoinitiated electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization in water. The structure of the hybrid bonding bottlebrush architecture was characterized using cryogenic transmission electron microscopy, and its properties were probed using rheological measurements. We observed that hybrid bonding bottlebrush polymers were able to organize into block architectures containing domains with high brush grafting density and others with no observable brushes. This finding is possibly a result of dynamic behavior unique to supramolecular polymer backbones, enabling molecular exchange or translational diffusion of monomers along the length of the assemblies. The hybrid bottlebrush polymers exhibited higher solution viscosity at moderate shear, protected supramolecular polymer backbones from disassembly at high shear, and supported self-healing capabilities, depending on grafting densities. Our results demonstrate an opportunity for novel properties in easily synthesized bottlebrush polymer architectures built with supramolecular polymers that might be useful in biomedical applications or for aqueous lubrication.

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Am Chem Soc Año: 2024 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Am Chem Soc Año: 2024 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos