TOC of Polymer Stereocomplexation

Polymer Stereocomplexation as a Scalable Platform for Nanoparticle Assembly 

Allison Abdilla, Neil D. Dolinski, Puck de Roos, Jing Ming Ren, Erika van der Woude, Soyoung E. Seo, Manuel S. Zayas, Jimmy Lawrence, Javier Read de Alaniz, and Craig J. Hawker

J. Am. Chem. Soc. 2020, 142, 4, 1667-1672

Link to Article

Abstract: DNA-mediated assembly of inorganic particles has demonstrated to be a powerful approach for preparing nanomaterials with a range of interesting optical and electrical properties. Building on this inspiration, we describe a generalizable gram-scale method to assemble nanoparticles through the formation of poly(methyl methacrylate) (PMMA) triple-helices. In this work, alkene-terminated syndiotactic (st-) and isotactic (it-) PMMA polymers were prepared and subsequently functionalized to afford nanoparticle ligands. Nanoparticles with complementary st- and it-PMMA ligands could then be spontaneously assembled upon mixing at room temperature. This process was robust and fully reversible through multiple heating and cooling cycles. The versatility of PMMA stereocomplexation was highlighted by assembling hybrid structures composed of nanoparticles of different compositions (e.g., Au and quantum dots) and shapes (e.g., spheres and rods). These initial demonstrations of nanoparticle self-assembly from inexpensive PMMA-based materials present an attractive alternative to DNA-based nanomaterials.