CNMS

Office of Basic Energy Sciences
Office of Science


Macromolecular Complex Systems

The overall goal of this program is to develop a fundamental understanding of how the chemical composition and the molecular and supramolecular architecture of stimuli-responsive polymers impacts their physical and chemical properties. Stimuli-responsive polymers are those that undergo a dramatic physical or chemical change in response to a small change in their environment. These polymers are currently of tremendous interest because they can mimic the properties of biopolymers found in living organisms, and they can lead to new (biocompatible) materials whose properties can be precisely controlled by external stimuli. However, there currently is a lack of understanding of how the chemical composition and molecular architecture of stimuli-responsive polymers affect their properties.

To address these issues, the specific aims of this program are:

  1. to synthesize well-defined synthetic polypeptides and study their properties as a function of chemical composition, architecture, and environment, in order to gain insights into biological systems and the design of biomimetic materials;
  2. to synthesize and study the thermal response and properties of novel PEGylated acrylate-, ethacrylate-, and thiophene-containing polymers and copolymers in order to learn how structure affects properties; and
  3. to design, synthesize and characterize stimuli-responsive nanoporous polymer membranes as biomimetic membranes.

In order to predict and control the self-assembly and response of these macromolecules, it is necessary to tailor the materials using rigorous synthetic techniques to control their chemical nature, molecular weight, macromolecular architecture, and positioning of monomer units, as well as build in specific interactions.

We will utilize our expertise in the controlled synthesis of well-defined polymer and copolymer architectures by anionic and controlled radical polymerization techniques to design and synthesize well-defined stimuli-responsive polymers based on biocompatible materials, i.e., amino acids and oligo(ethylene glycols). We will rigorously characterize these polymers by spectroscopic, chromatographic, thermal and mechanical, and scattering (light, X-rays and neutron) techniques and study their self-assembly in solution, at interfaces, and in the bulk. The response of these polymers to external stimuli, such as temperature, pH, solvent polarity and ionic strength, will be studied in solution and on surfaces in order to determine structure-property relationships, thereby engendering the opportunity to rationally design and tune the properties of the next-generation materials. We will explore new synthetic techniques to control the sequence of amino acids in large polypeptide chains from the anionic polymerization of amino acid N-carboxyanhydrides in order to control primary and secondary structure and function. Surface polymerization techniques will be developed to grow well-defined polypeptide brushes from model surfaces to study their interfacial properties and the impact of short peptide chains that engenders a specific binding functionality will be probed. Thermally responsive water-soluble polymers and copolymers based on oligo(ethylene glycol) substituted acrylates, methacrylates, and thiophenes will be studied in solution and on surfaces as a function of molecular weight and chemical composition to determine how structure affects aggregation and their thermal response. Finally, we will utilize the knowledge gained to synthesize nanoporous membranes containing heat or pH responsive polymers and investigate the controlled permeation of liquids through the pores.

This comprehensive program will provide a better understanding of the structure-property relationships of stimuli-responsive polymers, thereby significantly advancing the goal of developing novel materials that mimic the properties and functions of biopolymers.

Capabilities for User Research in Macromolecular Complex Systems

Updated Friday, 17-Nov-2006 14:04:34 EST - 1,008