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

在化学系大分子、超分子和纳米化学计划的支持下，宾夕法尼亚大学的罗伯特·希基和宾夕法尼亚大学的罗伯特·里格尔曼旨在提供关于缔合聚合物中的非共价相互作用如何驱动纳米级自组装的基本分子水平的见解。在这个项目中，研究小组将结合实验、理论和模拟来探索极化变化对溶液中聚合物链之间相互作用和纳米级自组装的影响。该项目包括从实验和计算的角度对本科生和研究生进行大分子、超分子和纳米科学方面的培训。此外，该团队将创建结合实验和理论/模拟的聚合物学习模块，以补充本科化学课程。这项研究将专注于使用一系列Lewis酸(LAS)和Lewis碱(LBS)，它们可以以单体或聚合物的形式结合在一起，在形成Lewis加合物时改变聚合物的极化。在整个项目过程中，宾夕法尼亚州立大学和宾夕法尼亚州立大学合作的研究团队将系统地：i)研究结合强度和产生的偶极矩对聚合物/分子/溶剂体系的非共价相互作用和相行为的影响；ii)确定和控制使用聚合LAS和聚合LBS形成Lewis加合物的熵和热焓；iii)探索LAS或LBS引发的嵌段共聚物的可逆自组装。宾夕法尼亚州立大学的Hickey小组将合成和表征聚合物，宾夕法尼亚大学的Riggleman小组将使用可极化场论模拟和解析聚合物场理论来研究平衡纳米级自组装。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

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.