Multivalent display of chemical signals on self‐assembled peptide scaffolds

Abstract

Self-assembled peptide materials have emerged as promising bioinspired tools for applications that include regenerative medicine, drug delivery, antimicrobial and vaccine development, optics, and catalysis. Peptide self-assembly mediated by noncovalent hydrogen bonding, coulombic, hydrophobic, and aromatic interactions gives rise to a variety of supramolecular structures that reflect on the nature of the constituent peptides. The emergent properties of these supramolecular peptide materials often depend on the multivalent presentation of functional appendages on the self-assembled scaffold. For example, the multivalent display of cell-signaling motifs on self-assembled peptide nanofibrils provides materials that are excellent extracellular matrix mimetics for tissue engineering applications. This review includes a discussion of chemical strategies that address the challenge of appending functional signal motifs in a multivalent display on self-assembled peptide and protein materials. In addition, recent examples of supramolecular peptide materials that rely on the multivalent display of chemical signals for the desired applications are presented. Collectively, this discussion illustrates the potential of self-assembled peptides as sustainable materials to address challenges in contemporary materials science and provides principles for the design of next-generation agents for a variety of applications.

Peptidomimetic-Based Asymmetric Catalysts

“…Recently, an emerging topic regarded self-assembled short peptides acting as organocatalysts. Their efficiencies are comparable to those found in enzymes [23,24], and their supramolecular state can accelerate the organocatalysis activity [25][26][27].…”

A Dual‐Metal‐Catalyzed Sequential Cascade Reaction in an Engineered Protein Cage**

“…They include further surface functionalization, for example, for targeted delivery of the nanoreactors. [52] Along these lines, we are confident that the prospects of encapsulin engineering are ideally suited for achieving future applications, such as targeted prodrug activation.…”

Mismatched covalent and noncovalent templating leads to large coiled coil-templated macrocycles

“…[9][10][11] Higher order supramolecular assemblies of peptides that are driven by covalent linkage, metal templation, and noncovalent assembly, which result in the formation of complex 1-, 2-and 3D assemblies with interesting materials properties, have also been investigated. 6,8,[12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] The coupling of dynamic combinatorial chemistry (DCC) 27 with noncovalent peptide assembly is complementary to de novo design as it allows for the discovery of new, oen unexpected assemblies and properties. DCC utilizes building blocks that can reversibly react with one another via covalent bond formation to produce a dynamic combinatorial library (DCL) whose speciation is controlled by thermodynamic stability.…”

“…9–11 Higher order supramolecular assemblies of peptides that are driven by covalent linkage, metal templation, and noncovalent assembly, which result in the formation of complex 1-, 2- and 3D assemblies with interesting materials properties, have also been investigated. 6,8,12–26…”