Primitive thioesterification/hydrolysis reaction cycles for dissipative assemblies

In recent years, chemically fueled assemblies which are constructed by using activation/deactivation reaction cycles have attracted more and more attention. These non-equilibrium assemblies show many interesting dynamic behaviors such as staying away from equilibrium and dissipating energy. Constructing diverse non-equilibrium assemblies could be a powerful tool to understand the basic chemical principles of life. However, the range of organic chemical reactions available for constructing diverse dissipative assemblies remains limited. Here we constructed a new primitive thioesterification/hydrolysis reaction cycle fueled by propylphosphonic anhydride (T3P) in aqueous solution by using a series of N-protected amino acids as the precursor molecules. The effect of concentration, pH and precursor structures to the reaction cycles are thoroughly investigated. We further found this reaction cycles can also drive transient and non-equilibrium molecular assemblies if appropriately designed precursor molecules are used. This reaction cycle presents a primitive metabolism-like reaction network to regulate molecular organization.