Self‐Assembled Peptide Nano‐Superstructure towards Enzyme Mimicking Hydrolysis

Abstract

The structural arrangement of amino acid residues in native enzymes underlies their remarkable catalytic properties,t hus providing an otable point of reference for designing potent yet simple biomimetic catalysts.H erein, we describe am inimalistic approach to construct ad ipeptide-based nanosuperstructure with enzyme-like activity.T he self-assembled biocatalyst comprises one peptide as as ingle building block, readily synthesized from histidine.Through coordination with zinc ion, the peptide self-assembly procedure allows the formation of supramolecular b-sheet ordered nanocrystals, which can be used as basic units to further construct higherorder superstructure.A sar esult, remarkable hydrolysis activity and enduring stability are demonstrated. Our work exemplifies the use of ab ioinspired supramolecular assembly approach to develop next-generation biocatalysts for biotechnological applications.

Artificial Metal–Peptide Assemblies: Bioinspired Assembly of Peptides and Metals through Space and across Length Scales

“…Indeed, the rational design of MPA-15 provides a successful example that can mimic the catalytic behavior of carbonic anhydrases. 106 An intriguing possibility is to immobilize privileged organometallic catalysts within the peptide-MOFs for achieving highly efficient catalytic activity.…”

“…The self-assembled metal−peptide structure (MPA-15) displays a 1D coordination polymer with helically arranged conformation stabilized by β-sheet-like hydrogen bonding between two adjacent cyclic dipeptides (Figure 10A,B). 106 Note that the Zn(II) was coordinated with two nitrogen atoms from the imidazole groups, which is reminiscent of Zn(II)-containing metalloenzyme of carbonic anhydrase. Impressively, the 3D packing framework of MPA-15 is quite stable (Figure 10C), as confirmed by Brunner− Emmet−Teller measurements and a powder X-ray diffraction pattern.…”

“…For example, inspired by the structure of carbonic anhydrase (CA) II, a cyclic dipeptide ligand (L-12) consisting of two histidine (His) residues has been proposed to serve as an active site by binding the cofactor Zn­(II). The self-assembled metal–peptide structure ( MPA-15 ) displays a 1D coordination polymer with helically arranged conformation stabilized by β-sheet-like hydrogen bonding between two adjacent cyclic dipeptides (Figure A,B) . Note that the Zn­(II) was coordinated with two nitrogen atoms from the imidazole groups, which is reminiscent of Zn­(II)-containing metalloenzyme of carbonic anhydrase.…”

“…Furthermore, the resulting nanopores with controlled size and side-chain group generally possess guest-adaptive feature that can facilitate chemical transformation, especially for asymmetric catalysis. Indeed, the rational design of MPA-15 provides a successful example that can mimic the catalytic behavior of carbonic anhydrases . An intriguing possibility is to immobilize privileged organometallic catalysts within the peptide-MOFs for achieving highly efficient catalytic activity.…”

Mitochondria-Targeted Self-Assembly of Peptide-Based Nanomaterials

“…Since the emergences of technologies for the peptide manufacture and screening, especially the solid-phase peptide synthesis proposed by Merrifield in 1963(Merrifield, 1963 and the phage display described by Smith in 1985(Smith, 1985, numerous peptide-based pharmaceuticals and functional materials have been developed (Figure 1A) (Hosoyama et al, 2019;Lopez-Silva and Schneider, 2021;Muttenthaler et al, 2021). Particularly, self-assembling peptides have attracted increasing interest due to their improved stability and biological performance (Guyon et al, 2018;Levin et al, 2020), and have been applied in a wide range of fields including the tissue engineering (Gelain et al, 2020;Zhang et al, 2021), drug delivery (Moitra et al, 2014;Abbas et al, 2017;Yang J. et al, 2020;Kumar et al, 2020;, catalysis (Rufo et al, 2014;Wang M. et al, 2020;Liu Q. et al, 2021;Chen et al, 2021), semi-conducting device (Tao et al, 2017), and energy materials (Hu et al, 2018;Lee et al, 2018;Nguyen et al, 2021). With the molecular basis to form secondary structures including the α-helix and β-sheet, the self-assembling peptides can assemble into well-defined nanostructures like nanofibrils driven by non-covalent interactions, such as the hydrophobic interaction, electrostatic interaction, π-π stacking, hydrogen bond, etc (Hendricks et al, 2017;Hu et al, 2020;Zheng et al, 2021).…”