Dissipative self-assembly of vesicular nanoreactors

Abstract

Dissipative self-assembly is exploited by nature to control important biological functions, such as cell division, motility and signal transduction. The ability to construct synthetic supramolecular assemblies that require the continuous consumption of energy to remain in the functional state is an essential premise for the design of synthetic systems with lifelike properties. Here, we show a new strategy for the dissipative self-assembly of functional supramolecular structures with high structural complexity. It relies on the transient stabilization of vesicles through noncovalent interactions between the surfactants and adenosine triphosphate (ATP), which acts as the chemical fuel. It is shown that the lifetime of the vesicles can be regulated by controlling the hydrolysis rate of ATP. The vesicles sustain a chemical reaction but only as long as chemical fuel is present to keep the system in the out-of-equilibrium state. The lifetime of the vesicles determines the amount of reaction product produced by the system.

Non-equilibrium steady states in supramolecular polymerization

“…In analogy with recent studies261112 we explored the possibility to perform multiple transient experiments by refuelling with ATP. However, when adding a second aliquot of ATP to the same solution (Fig.…”

“…The latter is a potent λPP inhibitor36 that likely prevents the dephosphorylation of p2-PDI . The poisoning due to accumulation of waste is a ubiquitous problem for chemically fuelled supramolecular systems in (semi)batch conditions261112. To resolve the poisoning problem we dialysed the solution (Fig.…”

“…Artificial supramolecular assemblies have been developed in the recent years where a monomer can be switched from assembling to nonassembling or vice versa by direct chemical modification234, by enzymes5678 or mediated by chelation of nucleobases9101112. More recently, this has resulted in transient assemblies for which the lifetime of the assembled state can be programmed in advance.…”

“…More recently, this has resulted in transient assemblies for which the lifetime of the assembled state can be programmed in advance. Moreover, these systems can be reactivated by addition of a fresh aliquot of the chemical fuel, resulting in a new cycle of transient assembly236111213 (also called a batch excursion in the phase space14). However, waste from the fuel conversion is not usually removed from the system that over longer times interferes with the assembly process.…”

How and why kinetics, thermodynamics, and chemistry induce the logic of biological evolution

“…1). These structures therefore result from dissipative self-assembly for which fascinating examples have been provided in the recent literature [19–21]. In biology, one of the most typical examples of this kind of assembly processes can be found in the dynamics of the cytoskeleton.…”