Pathway-Dependent Catalytic Activity of Short-Peptide-Based Metallozyme: From Promiscuous Activity to Cascade Reaction

Nano Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 2, 2025

Many natural enzymes contain metal ions as cofactors in the active site for biological activity. However, pathway of introduction earliest protein folds emergence higher catalytic activity remains an intriguing open question. Herein, we demonstrate that pathway-dependent self-assembly short-peptide-based metallozymes results differences Short-peptide-based amyloids with solvent exposed arrays colocalized units are able to bind highly soluble Cu2+ oxidase-like and RNase-like (promiscuity). Further, metallozyme was exhibit hydrolase-oxidase cascade compared mixture enzymes, esterase, laccase. The collaboration between amyloid microphases suggests might have played a pivotal role early metabolic processes biopolymer evolution on prebiotic earth.

Language: Английский

ATP‐Regulated Formation of Transient Peptide Amphiphiles Superstructures

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

Abstract Self‐assembly of biotic systems serves as inspiration for the preparation synthetic supramolecular assemblies to mimic structural, temporal, and functional aspects living systems. Despite peptide amphiphiles (PAs) being widely studied in context biomimetic bioactive nanomaterials, very little is currently known about reversible spatiotemporal control their hierarchical self‐assemblies. Here, it shown that PA‐based nanofibers can transiently form superstructures, through binding with oppositely charged adenosine triphosphate (ATP), leading charge screening stabilization bundled nanofibers. Enzymatic hydrolysis ATP monophosphate phosphates causes disassembly superstructures recovery individual The lifetime be controlled by adjusting concentration either or enzyme. role formation PA has on chemical reactivity catalysis also evaluated. It observed superstructuration responsible downregulation activity, which then recovered gradual bundles. These results demonstrate potential self‐assembly modulate nanostructures.

Language: Английский

Imine-Based Transient Supramolecular Polymers

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 19, 2025

Systems that change properties upon exposure to chemical stimuli offer the interesting prospect of (partially) mimicking functions living systems. Over past decade, numerous supramolecular systems whose composition and are regulated by dissipation fuels have been reported. These typically based on transient transformation a "dormant" species into an active, self-assembling monomer. The process is powered fuel consumption terminates depletion, restoring initial dormant state. Previously reported out-of-equilibrium polymerizations relied activation adding or removing small structural units enable polymerization. Here, we present approach combines reversibility dynamic covalent chemistry trigger "recycling" components combinatorial library (DCL). Treatment equilibrated DCL aliphatic imines aromatic amines with activated carboxylic acid (ACA) generates dissipative protonated amines. acidic conditions creation polymer held together interactions between crown ether moieties embedded in scaffold imines. Thus, reshuffles connectivity enables temporary purely (polymeric) system polymer. We demonstrate strategy using two different feedstocks consisting diimine macrocycle involving calix[4]arene distribution imine (cyclo)oligomers derived from isophthalaldehyde skeleton.

Language: Английский