Template-Dependent (Ir)reversibility of Noncovalent Synthesis Pathways

Abstract

Non-covalent synthesis aims at exploiting non-covalent interactions for the controlled hierarchical assembly of nanostructures. Just as the covalent synthesis of molecules is affected by the conditions under which the chemical reaction is carried out, the outcome of a non-covalent synthesis process can be likewise affected by the experimental pathway in case the assembled structures are kinetic, rather than thermodynamic, products. Here, we show that the ATP-templated formation of metallo-amphiphile assemblies results in different kinetically stable structures depending on the self-assembly pathway. Interconversion between the different assembled states is not possible and neither is ATP subject to enzymatic hydrolysis which would convert the system back to the unassembled state. The high stability of the different assembly states is a result of the strong interaction between ATP and the metallo-amphiphile. Indeed, the use of AMP as a weakly interacting template leads to thermodynamically stable assemblies which can be transitioned between different states. The results underline that control over the kinetic processes that regulate self-assembly is a fundamental tool for the hierarchical self-assembly of complex nanostructures and the development of energy-driven synthetic systems.