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Brush-First and ROMP-Out with Functional (Macro)monomers: Method Development, Structural Investigations, and Applications of an Expanded Brush-Arm Star Polymer Platform.


ABSTRACT: The efficient synthesis of complex functional polymeric nanomaterials is often challenging. Ru-initiated ring-opening metathesis polymerization (ROMP) of multivalent macromonomers followed by cross-linking to form brush-arm star (BASP) polymers enables access to well-defined nano-structures with diverse functionality. This "brush-first" method leaves active Ru in the BASP microgel core, which could potentially be used in a subsequent "ROMP-out" (RO) step to introduce further modifications to the BASP structure via the addition of (macro)monomers. Here, we study this RO approach in depth. The efficiency of RO is assessed for a variety of BASP compositions using a combination of inductively coupled plasma mass spectrometry and gel permeation chromatography. To demonstrate the modularity of the RO process, arylboronic acid-functionalized BASPs were prepared; uptake of these RO-BASPs into hypersialylated cancer cells was enhanced relative to non-functionalized BASPs as determined by flow cytometry and fluorescence microscopy. In addition, the self-assembly of miktoarm BASPs prepared via brush-first and RO with different macromonomers is demonstrated. The combination of brush-first ROMP with RO provides a simple, modular strategy for access to a wide array of functional nanomaterials.

SUBMITTER: Golder MR 

PROVIDER: S-EPMC6625813 | biostudies-literature | 2018 Dec

REPOSITORIES: biostudies-literature

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Brush-First and ROMP-Out with Functional (Macro)monomers: Method Development, Structural Investigations, and Applications of an Expanded Brush-Arm Star Polymer Platform.

Golder Matthew R MR   Nguyen Hung V-T HV   Oldenhuis Nathan J NJ   Grundler Julian J   Park Ellane J EJ   Johnson Jeremiah A JA  

Macromolecules 20181129 23


The efficient synthesis of complex functional polymeric nanomaterials is often challenging. Ru-initiated ring-opening metathesis polymerization (ROMP) of multivalent macromonomers followed by cross-linking to form brush-arm star (BASP) polymers enables access to well-defined nano-structures with diverse functionality. This "brush-first" method leaves active Ru in the BASP microgel core, which could potentially be used in a subsequent "ROMP-out" (RO) step to introduce further modifications to the  ...[more]

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