Typical Stochastic Paths in the Transient Assembly of Fibrous Materials.

Abstract

When chemically fueled, molecular self-assembly can sustain dynamic aggregates of polymeric fibers-hydrogels-with tunable properties. If the fuel supply is finite, the hydrogel is transient, as competing reactions switch molecular subunits between active and inactive states, drive fiber growth and collapse, and dissipate energy. Because the process is away from equilibrium, the structure and mechanical properties can reflect the history of preparation. As a result, the formation of these active materials is not readily susceptible to a statistical treatment in which the configuration and properties of the molecular building blocks specify the resulting material structure. Here, we illustrate a stochastic-thermodynamic and information-theoretic framework for this purpose and apply it to these self-annihilating materials. Among the possible paths, the framework variationally identifies those that are typical-loosely, the minimum number with the majority of the probability. We derive these paths from computer simulations of experimentally-informed stochastic chemical kinetics and a physical kinetics model for the growth of an active hydrogel. The model reproduces features observed by confocal microscopy, including the fiber length, lifetime, and abundance as well as the observation of fast fiber growth and stochastic fiber collapse. The typical mesoscopic paths we extract are less than 0.23% of those possible, but they accurately reproduce material properties such as mean fiber length.