Pre-Organization and Induced-Fit in Chemo-Mechanical Peptide Materials
Abstract
We propose to develop a class of supramolecular materials that change their properties in response to specific chemical stimuli via induced fit supramolecular recognition and consequent non-linear amplification resulting in mechanical deformation or chemical reaction within their macroscopic structures. The proposed materials will be composed of designed short peptides that self-assemble to form porous supramolecular crystal lattices that are composed of periodic stiff/ordered and reconfigurable/disordered domains. The stiff domains surround binding pores that contain hydrogen bond donor and acceptor sites integrated to form proton relay networks, whereas the soft domains are rich in aromatic groups which easily reconfigure through aromatic slippage. We propose that these materials can be actuated by reversible chemical bonding events at the pore interface connecting to stiff domains, and ultimately, they will be investigated to perform selective recognition of analytes leading to their mechanical actuation. We will also study changes in intrinsic fluorescence emission of these aromatic peptides in order to report on these binding events. Finally, by incorporating nucleophilic sites alongside binding moieties we aim to obtain chemical stimuli-driven enzyme-like catalysis focusing on amide and ester hydrolysis and condensation reactions. Demonstration of these approaches using an integrated experimental and computational approach will provide breakthroughs in relation to dynamically regulating the properties materials and functional soft condensed matter in response to chemical reactions. We will use the following technical approaches: (i) Develop integrated experimental and computational methods to search and map the conformational space of modular short peptide composed of aromatic sections and polar residues. We will establish predictive correlations between peptide conformation and morphology in self-assembled state. (ii) Explore hydrogen-bond induced actuation of peptide crystals with variable aromatic and polar domains using multiscale characterization. (iii) Demonstrate selective chemical binding induced actuation of peptide crystals and consequent non-linear modulation of mechanical properties. (iv) Explore introduction of nucleophiles in order to demonstrate catalyzed chemical reactions through induced fit, with a focus on enabling ester and amide hydrolysis and condensation reactions. The anticipated outcomes include new insights for design of adaptive functions for supramolecular crystals, including induced-fit reconfiguration, ligand-induced actuation, and conformation reporting. Furthermore, we seek to demonstrate the ability to catalyze condensation reactions in overall bulk aqueous media. The research activities and outcomes are anticipated to be of relevance to technologies of ARO Chemical Science program, including molecular sensing modalities, reconfigurable systems and materials, which may, in the long term, be relevant to maintaining or enhancing warfighter resilience and performance.
Document Details
- Document Type
- DoD Grant Award
- Publication Date
- Jun 25, 2021
- Source ID
- W911NF2110172
Entities
People
- Rein V Ulijn
Organizations
- Army Contracting Command
- Research Foundation of The City University of New York
- United States Army