Feedback-Induced Temporal Control of “Breathing” Polymersomes To Create Self-Adaptive Nanoreactors

Abstract

Here we present the development of self-regulated “breathing” polymersome nanoreactors that show temporally programmable biocatalysis induced by a chemical fuel. pH-sensitive polymersomes loaded with horseradish peroxidase (HRP) and urease were developed. Addition of an acidic urea solution (“fuel”) endowed the polymersomes with a transient size increase and permeability enhancement, driving a temporal “ON” state of the HRP enzymatic catalysis; subsequent depletion of fuel led to shrinking of the polymersomes, resulting in the catalytic “OFF” state. Moreover, the nonequilibrium nanoreactors could be reinitiated several cycles as long as fuel was supplied. This feedback-induced temporal control of catalytic activity in polymersome nanoreactors provides a platform for functional nonequilibrium systems as well as for artificial organelles with precisely controlled adaptivity.

Substrate‐Induced Self‐Assembly of Cooperative Catalysts

“…This has sparked strong interest in the design of chemical‐fuel driven out‐of‐equilibrium systems, in particular related to self‐assembly . The majority of reported examples rely on the covalent modification of building blocks, which changes their propensity to form assemblies . However, driven self‐assembly processes in Nature, that is, fuel‐driven processes that lead to a population of a high‐energy state, rely exquisitely on the use of noncovalent interactions for building block activation .…”

Adaptive Polymersome Nanoreactors

“…More recently, van Hest et al. demonstrated the construction of a self‐regulated and time programmed polymersome nanoreactor . This system was based on an earlier developed “breathing” microgel system.…”

“…Compared to a simple one-step enzymatic reaction, the out-of-equilibrium enzymatic network in this work was able to control the energy consumption while keeping the constant More recently, van Hest et al demonstrated the construction of a self-regulated and time programmed polymersome nanoreactor. [39] This system was based on an earlier developed "breathing" microgel system. Herein, pH sensitive diethylamine moieties incorporated in a crosslinked polymer network were protonated upon addition of acid, which resulted in an increase in polarity and subsequent swelling of the gel.…”

Polymerization‐Induced Self‐Assembly for Artificial Biology: Opportunities and Challenges

“…Of course, chemical‐fuel powered self‐assembly is at the root of many processes taking place in natural life, including signal processing, cell migration, replication, and metabolism . Several other authors have successfully used chemical fuels in various reaction networks to drive functional operations under temporal control . Recently, as a typical chemical reaction network, the redox oscillations in the Belousov–Zhabotinsky (BZ) reaction has been used as the energy and radical source to drive a PISA process at room temperature.…”

“…[2,49,50] Several other authors have successfully used chemical fuels in various reaction networks to drive functional operations under temporal control. [49,51,52] Recently, as a typical chemical reaction network, the redox oscillations in the Belousov-Zhabotinsky (BZ) reaction has been Macromol. Rapid Commun.…”