Sequence Defined Polymers And Their Structural Evaluation
Abstract
The objective of this proposal is to employ a novel fluorous solid-phase extraction technique to create sequence-defined and architecturally diverse polymers and investigate the relationships between primary sequence and intrinsic macroscopic properties. If successful, this effort will render a methodology capable of the highest level of control over polymer properties and may ultimately render synthetic materials with functional properties comparable to those found in natural systems. The proposed effort seeks to create sequence-defined polymers through the design of novel N-allyl acrylamide monomers that can undergo efficient orthogonal reactions with thiol-based co-monomers and the use of a fluorous solid-phase extraction technique to mediate solution phase reactions and purifications. Preliminary studies have shown that this coupling technique can be performed quickly (10-15 minutes), devoid of any protecting groups, and open to air at room temperature and pressure. This effort will specifically focus on synthesizing a panel of compositionally diverse N-allylacrylamide and dithiol monomers bearing sterically bulky substituents to render a library of structurally rigid polymers capable of intra- and inter- molecular interactions in solution. Polymer primary structure will be analyzed via mass spectroscopy and 1D and 2D NMR. Rotating frame nuclear Overhauser effect spectroscopy (ROESY) and electron spin resonance (ESR) will be employed to assess rigidity. This library will be designed to contain a variety of structures for exploring the effect of composition and sequence on secondary structure, folding, and self-assembly. Secondary and/or higher order structures will be evaluated with a range of spectroscopic tools including size exclusion chromatography, deuterium exchange mass spectrometry (DX-MS), ROESY, ESR, circular dichroism (CD) and X-ray crystallography. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) will be used to determine the presence of higher order aggregates and nanostructures. Results from these spectroscopic studies will be correlated with primary sequence and polymer architecture in order to gain preliminary sequence-structure understanding. Further exploration around specific sequences or sequence patterns that show promising macromolecular properties will be conducted in order to arrive at definitive sequence-structure correlations.
Document Details
- Document Type
- DoD Grant Award
- Publication Date
- Jan 12, 2017
- Source ID
- W911NF1510179
Entities
People
- Christopher A Alabi
Organizations
- Army Contracting Command
- Cornell University
- United States Army