Modeling of minimal systems based on ATP-Zn coordination for chemically fueled self-assembly

E Rossi and A Ferrarini and M Sulpizi, PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 25, 6102-6111 (2023).

DOI: 10.1039/d2cp05516c

Following nature's example, there is currently strong interest in using adenosine 5 '-triphosphate (ATP) as a fuel for the self-assembly of functional materials with transient/non-equilibrium behaviours. These hold great promise for applications, e.g. in catalysis and drug delivery. In a recent seminal work Maiti et al., Nat. Chem., 2016, 8, 725, binding of ATP to the metallosurfactant zinc hexadecyl-1,4,7-triazacyclononane (ZnC16 TACN(2+)) was exploited to produce ATP-fueled transient vesicles. Crucial to the complex formation is the ability of ATP to bind to the metal ion. As a first step to unveil the key elements underlying this process, we investigate the interaction of ATP with Zn2+ and with methyl-1,4,7-triazacyclononane (ZnCH3 TACN(2+)), using all-atom molecular dynamics simulations. The free energy landscape of the complex formation is sampled using well- tempered metadynamics with three collective variables, corresponding to the coordination numbers of Zn2+ with the oxygen atoms of the three phosphate groups. We find that the structure of the ternary complex is controlled by direct triphosphate coordination to zinc, with a minor role played by the interactions between ATP and CH3 TACN which, however, may be important for the build-up of supramolecular assemblies.

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