The overall goal of IRG2 is to learn, through experiment, theory, and simulation, the syntactical rules for the design of "syntactomers” whose phase behaviors facilitate programming of their self-assembly into supramolecular nano- to mesoscalestructures. Syntactomers are macromolecules that consist of a collection of “letters” (monomers that can either be amino acids, nucleotides or synthetic components) are arranged within “words” (repeat units), which are in turn arranged by following a syntax —defined as the arrangement of words— into “phrases” (macromolecules). Although a limited number of the genetically encoded polymers studied thus far exhibit self-assembly, there currently is no research that systematically studies the effect of polymer syntax on hierarchical self-assembly and function. The prophigherorderhierarchicalosed research intends to do just that —program self-assembly over several hierarchical levels by controlling syntactomer syntax.

There are four main objectives:

• to explore the full syntax available by screening large libraries of possible peptide“words”,
• to add nucleotides and polymer segments to the types of letters and words considered,
• to develop a molecular level understanding of the relationship between the syntax of the syntactomers andtheir structure and hierarchical self-assembly, and
• to learn how to control the assembly into higher order hierarchical assemblies, enabling us to exploit their potential for applications.

To meet these objectives, IRG2 is organized into three themes of increasing syntactical and functional sophistication. First, a lexicon of simple homo-syntactomers will be synthesized and studied as to their predictable response to a number of environmental stimuli at technologically relevant environmental conditions. This knowledge will then be used to create more complex syntactomers, i.e., peptide phrases containing morethan one word or peptide-nucleotide hybrids that self-assemble into a variety of structures, spanning thenano- to meso-scale, Finally, the programmed self-assembly of these first order assemblies (micelles and vesicles) into higher order assemblies will be investigated in solution and on surfaces. The major intellectual impact of IRG2 will the development of a new paradigm in macromolecular design that moves away from the current concept of polymerizable letters to words, thereby endowing a greater level of structural and functional sophistication to synthetic macromolecules.

Researchers:

Synthesis & Characterization

Ashutosh Chilkoti, Duke University. Specializes in genetically encoded synthesis, in situ DNA polymers, and light scattering.

Stefan Zauscher, Duke University. Specializes in polymer brushes, in situ DNA polumerization, AFM, SPR and QCM.

Jan Genzer, North Carolina State University. Specializes in controlled polymerization, ellipsometry, NEXAFS, and Kerr effect.

Theory

Michael Rubinstein, University of North Carolina-Chapel Hill. Specializes in scaling theory of polymer self-assembly and computer simulation.

Simulation

Carol Hall, North Carolina State University. Specializes in computer simulations, self-assembly of soft matter, and protein aggregation.

Yara Yingling, North Carolina State University. Specializes in MD simulations of DNA & syntactomers, structure-function of biomolecules.

Processing

Gabriel Lopez, Duke University. Specializes in hybrid responsive colloids, surfaces and membranes.

Darlene Taylor, North Carolina Central University. Specializes in programmed thin film casting and polymer synthesis.