INTELLECTUAL MERIT: In their native environments, proteins accomplish tasks on the nanoscale that manifest in the form of chemical and mechanical work. The proposed research aims to transplant the exquisite functionality of proteins to bulk self-organized materials through the synthesis and characterization of novel biohybrid macromolecules. An unprecedented level of structural control over material structure and properties will be achieved by integrating properly folded protein domains into bulk soft materials. To reach this goal, highly branched synthetic amphiphiles called dendrons will be attached to the surface of peptides that mimic helical bundles found in natural proteins to investigate the molecular features required to produce bulk materials in which functional proteins are embedded. Three specific aims will be pursued to establish the feasibility of this biohybrid approach to bulk soft materials: (1) understand the requirements for site-isolation and self-organization of helix bundles in a nanostructured array by characterizing libraries of dendronized template-assembled synthetic protein (TASP) helical bundles, (2) determine the extent to which peptide amino acid sequence encodes dendronized helix bundle structure by characterizing dendronized peptides that self-assemble into bundles of two to four helices by virtue of differences in the amino acid sequence, and (3) establish strategies for co-assembling nanostructured arrays of dendronized helix bundles by characterizing blends of dendronized TASPs or dendronized helix bundle-forming peptides with amphiphilic dendrons. Altogether these aims will elucidate rules for understanding and anticipating the interplay between folding, assembly, and self-organization of helix bundles in liquid crystalline mesophases and, hence, enable a new platform for the design of nanostructured biohybrid materials. The education component of this proposal integrates the proposed research within the broader context of soft materials. Soft materials topics are being developed in the chemistry curriculum at Stony Brook University, and an outreach program is developing learning modules for high school students that emphasize soft materials.
BROADER IMPACTS: Given that current self-organizing materials have emerged as crucial elements in applications to nanofabrication and biotechnology, the proposed research has the potential to positively impact diverse areas of science and technology. Tuning material properties with the precision and accuracy traditionally associated only with molecular biology will empower detailed understanding and optimization of functional nanomaterials based on dendronized helix bundles. Students at the high school, undergraduate, and graduate levels involved with this cross-disciplinary research program will gain exposure to a unique cross-section of chemical synthesis and biophysical and polymer characterization techniques. An integrated education and training plan is proposed in conjunction with the research plan. Soft materials offer visual and tactile experiences that can engage audiences outside the research program. Hands-on demonstrations relating everyday experiences to materials chemistry and nanoscience provide a hook upon which educational modules are being developed. A collaboration with an area high school has been established to implement these modules in a classroom setting. The educational components pursue three related goals: (1) outreach to high school students through educational modules and research opportunities, (2) integration of soft materials into the chemistry curriculum, and (3) cross-disciplinary training of diverse graduate and undergraduate students in soft biomaterials research.
