Collaborative Research: Controlling Nanoscale Self-Assembly via Binding-Induced Polarization

With the support of the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Robert Hickey of Penn State University and Robert Riggleman of the University of Pennsylvania aim to provide fundamental molecular level insights into how non-covalent interactions in associating polymers drive nanoscale self-assembly. In this project, the research team will use a combination of experiment, theory, and simulation to explore the effects of changes in polarization on the interactions between polymer strands in solution and nanoscale self-assembly. The project involves the training of both undergraduate and graduate students in macromolecular, supramolecular, and nano-science from both the experimental and computational perspective. Furthermore, the team will create polymer learning modules that incorporate experiment and theory/simulation to supplement the undergraduate chemistry curriculum.This research will focus on using a family of Lewis acids (LAs) and Lewis bases (LBs) that can be incorporated in either monomeric or polymeric form to change polymer polarization upon formation of Lewis adducts. Over the course of this project, the collaborative Penn State/Penn research team will systematically: i) investigate the impact of the binding strength and resulting dipole moment on the non-covalent interactions and phase behavior of polymer/molecule/solvent systems, ii) determine and control the entropy and enthalpy of Lewis adduct formation using polymerized LAs and polymerized LBs, and iii) explore reversible self-assembly of block copolymers triggered by LAs or LBs. The Hickey group at Penn State will synthesize and characterize the polymers, and the Riggleman group at the University of Pennsylvania will use polarizable field-theoretic simulations and analytic polymer field theory to study equilibrium nanoscale self-assembly.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.