Autonomous Growth of a Spatially Localized Supramolecular Hydrogel with Autocatalytic Ability

Abstract

Autocatalysis and self‐assembly are key processes in developmental biology and are involved in the emergence of life. In the last decade both of these features were extensively investigated by chemists with the final goal to design synthetic living systems. Herein, we describe the autonomous growth of a self‐assembled soft material, that is, a supramolecular hydrogel, able to sustain its own formation through an autocatalytic mechanism that is not based on any template effect and emerges from a peptide (hydrogelator) self‐assembly. A domino sequence of events starts from an enzymatically triggered peptide generation followed by self‐assembly into catalytic nanofibers that induce and amplify their production over time, resulting in a 3D hydrogel network. A cascade is initiated by traces (10−18 m) of a trigger enzyme, which can be localized allowing for a spatial resolution of this autocatalytic buildup of hydrogel growth, an essential condition on the route towards further cell‐mimic designs.

Reciprocal Coupling in Chemically Fueled Assembly: A Reaction Cycle Regulates Self-Assembly and Vice Versa

“…Both strategies of feedback of the assembly on their reaction cycle rely on phase separation, which up- or- downconcentrate reactants in the reaction cycle. − ,,, However, such mechanisms differ vastly from the feedback mechanism observed, for example, in microtubules, in which the assembly catalyzes the deactivation reaction. While catalytic activity by molecular assemblies has been explored extensively, − examples of molecular assemblies accelerating the kinetics of their building block activation or deactivation via catalysis are underexplored. In one recent example, Das and coworkers made use of histidine-based peptides to accelerate building block deactivation via catalysis in a chemically fueled assembly .…”

Biological functions of supramolecular assemblies of small molecules in the cellular environment

“…With the ability to design SASMs 121–123 and to determine the morphologies 124 and structures of SASMs, 125,126 it is time to explore the functions and applications of SASMs. While SASMs have exhibited a wide range of biological functions, the mechanistic study of SASMs remains insufficient.…”

Feedback and Communication in Active Hydrogel Spheres with pH Fronts: Facile Approaches to Grow Soft Hydrogel Structures

“…Building on this, CRNs were combined into materials to control physiochemical responses,[ 26 , 27 ] capsule permeability,[ 28 , 29 ] patterns, [30] communication,[ 31 , 32 , 33 , 34 ] gating, [35] chemotaxis, [36] diffusiophoresis,[ 37 , 38 ] and hydrogel formation. [ 39 , 40 , 41 , 42 , 43 , 44 ] Hence, feedback‐driven CRNs can offer a great control on a molecular scale, but their behavioral diversification demands for a proper sketch of the kinetics and network topology, and the step from molecular systems to materials continues to be a significant challenge.…”