Biocatalytic Pathway Selection in Transient Tripeptide Nanostructures

Abstract

Structural adaption in living systems is achieved by competing catalytic pathways that drive assembly and disassembly of molecular components under the influence of chemical fuels. We report on a simple mimic of such a system that displays transient, sequence-dependent formation of supramolecular nanostructures based on biocatalytic formation and hydrolysis of self-assembling tripeptides. The systems are catalyzed by α-chymotrypsin and driven by hydrolysis of dipeptide aspartyl-phenylalanine-methyl ester (the sweetener aspartame, DF-OMe). We observed switch-like pathway selection, with the kinetics and consequent lifetime of transient nanostructures controlled by the peptide sequence. In direct competition, kinetic (rather than thermodynamic) component selection is observed.

Bio-inspired metal ions regulate the structure evolution of self-assembled peptide-based nanoparticles

“…CD spectrum results confirmed that there were no intermolecular H-bonds initially with random coil structure (negative bands at 195 nm, Figure 2c). 36,37 The BKR still showed particulate morphologies, (30.3  2.5 nm, Figure 3) with β-sheet like H-bond formation, which were characterized by CD (Figure 2c) and IR spectra (1631 cm -1 absorption, Figure S4) in 4 d. 38 The RGD can bind hard metal ions Ca 2+ and Mg 2+ with high stability and 2:1 molar ratio. 31 (Figure 2c).…”

Biocatalytic Feedback‐Driven Temporal Programming of Self‐Regulating Peptide Hydrogels

“…[9] Despite intense development, it has remained achallenge to advance their properties from classical, passive responsiveness to create systems that show autonomous dynamics and self-regulation. [11] Routes toward single transient states in closed systems include kinetically controlled transformations of peptide nanofibril precursors [12] or dissipative structure formation. [10] More recent oscillators target rational design by defined chemical or enzymatic reaction networks.…”

Tandem Molecular Self‐Assembly in Liver Cancer Cells

“…[2] General approaches usually utilize chemical triggers,external energy,and solvent evaporation to trigger the self-assembly process,while biology takes advantage of biocatalysts to generate building blocks in am ore controllable and efficient way.I nspired by nature,c atalytic self-assembly has been widely explored to construct dynamic, [3] dissipative, [4] and reversible [5] nanostructures. [11] Although kinetic control has shown pronounced influence on the outcome of single-step self-assembly, [12] multistep self-assembly could lead to more sophisticated and functional materials.Using two reactions to control supramolecular selfassembly has recently attracted research interest. [10] However,r esearch efforts mainly focus on using as ingle-step reaction catalyzed by an enzyme or on using asmall molecule to trigger the self-assembly process.…”

“…These nanostructures not only offer ap latform for understanding the hierarchical self-assembly processes occurring in biological systems but also show promising applications in sensing, [6] drug delivery, [7] cell fate control, [8] immune response manipulation, [9] and regenerative medicine. [11] Although kinetic control has shown pronounced influence on the outcome of single-step self-assembly, [12] multistep self-assembly could lead to more sophisticated and functional materials. [11] Although kinetic control has shown pronounced influence on the outcome of single-step self-assembly, [12] multistep self-assembly could lead to more sophisticated and functional materials.…”