Polymerization along macromolecular templates (i.e., template polymerization) occurs when the parent polymer templates and growing daughter chains associate through electrostatic, hydrophobic and/or hydrogen bonding interactions. Such polymerization has been used to create materials across different lengthscales, ranging from nanoparticles to macroscopic gels. To illustrate some applications of this technique, here we present three examples of template polymerization use in our lab: (1) photodirected assembly of custom-shaped polyelectrolyte complexes (PECs); (2) use of these PECs as shape-directing templates for other soft materials; and (3) assembly of PEC nanoparticles with highly tunable size. Custom-shaped 3-D PECs with either microscale or macroscopic dimensions are prepared through photolithographic directed assembly, via photopolymerization of an anionic monomer in the presence of a polycation, which generates PECs whose shapes reflect the photoirradiation pattern. Besides their own stimulus-responsive properties (e.g., ability to change shape or dissolve on demand with changes in pH or ionic strength), these custom-shaped PECs can be used as sacrificial, structure-directing templates for other materials. To this end, we have recently shown how these PECs can direct the shape of thermoreversible gels. Such custom-shaped gel formation was achieved by adding agarose to the anionic monomer/polycation/photoinitiator precursor solutions. Upon photopatterning of these gelled mixtures, which causes photolithographically generated PECs to form inside agarose gels, the hydrogels surrounding the PECs are melted (through heating) and washed away. Dissolving the PEC templates in concentrated salt solutions then generates custom-shaped agarose gels whose shapes and sizes match those of their parent PEC templates. Lastly, we show how thermal template polymerization can, when performed at low polymer concentrations, be used to prepare colloidal PEC particles with narrow size distributions and highly tunable average sizes. Systematic analysis of compositional effects on this process reveals formation of particles ranging from ~20 nm (which, to our knowledge, is significantly smaller than the template polymerization-derived PECs reported to date) to micron-scale dimensions. Collectively, these findings indicate template polymerization to be an accessible and versatile tool for directing soft materials structure.<br/>

Soft materials synthesis from template-polymerized polyelectrolyte complexes

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.