Peptide-Based Supramolecular Systems Chemistry

Abstract

Peptide-based supramolecular systems chemistry seeks to mimic the ability of life forms to use conserved sets of building blocks and chemical reactions to achieve a bewildering array of functions. Building on the design principles for short peptide-based nanomaterials with properties, such as self-assembly, recognition, catalysis, and actuation, are increasingly available. Peptide-based supramolecular systems chemistry is starting to address the far greater challenge of systems-level design to access complex functions that emerge when multiple reactions and interactions are coordinated and integrated. We discuss key features relevant to systems-level design, including regulating supramolecular order and disorder, development of active and adaptive systems by considering kinetic and thermodynamic design aspects and combinatorial dynamic covalent and noncovalent interactions. Finally, we discuss how structural and dynamic design concepts, including preorganization and induced fit, are critical to the ability to develop adaptive materials with adaptive and tunable photonic, electronic, and catalytic properties. Finally, we highlight examples where multiple features are combined, resulting in chemical systems and materials that display adaptive properties that cannot be achieved without this level of integration.

Controlled aggregation properties of single amino acids modified with protecting groups

“…The self-assembly of aromatic amino acids and Fmoc-modified aromatic amino acids has already been reported to be caused by pi-pi stacking interactions. [55][56][57] Hence, similar to the hypothesis proposed by Gazit and coworkers, 58 Cbz-Phe-OH and Cbz-Trp-OH may assemble due to pi-pi stacking interactions. Herein too, the compositions of hydrophobic and hydrophilic residues present in amino acids play an important role as Cbz-Tyr-OH does not show any assembly.…”

Temporal stimulus patterns drive differentiation of a synthetic coacervate

“…A diphenylalanine sequence has been frequently used as a self-assembling moiety for supramolecular nanofibres and coacervates. [33][34][35][36][37][38] To avoid biased formation of nanofibres, we introduced a bulky tert-butyl group at the C-terminus. In addition, we attached a 4-phenylpyridinium group at the N-terminus to potentially induce cation-π interactions, which are often crucial for LLPS of biomacromolecules.…”

Peptide Self-Assembled Nanostructures: From Models to Therapeutic Peptides

“…and bionanotechnology (antifouling coating, biomineralization, bioinspired nano- and microdevices, etc.) [ 106 ].…”