Molecular Dynamics for the Optimal Design of Functionalized Nanodevices to Target Folate Receptors on Tumor Cells

by E. Donadoni, G. Frigerio, P. Siani, S. Motta, J. Vertemara, L. De Gioia, L. Bonati and C. Di Valentin
ACS Biomater. Sci. Eng. 2023, 9, 11, 6123-6137 View at Publisher
DOI: 10.1021/acsbiomaterials.3c00942

ACS_Biomaterias_Science_&_Engineering

Atomistic details on the mechanism of targeting activity by biomedical nanodevices of specific receptors are still scarce in the literature where mostly ligand/receptor pairs are modeled. Here, we use atomistic molecular dynamics simulations, free energy calculations and machine learning approaches on the case study of spherical TiO2 nanoparticles (NPs) functionalized with folic acid (FA) as the targeting ligand of the folate receptor (FR). We consider different FA densities on the surface and different anchoring approaches, i.e., direct covalent bonding of FA γ-carboxylate or through polyethylene glycol (PEG) spacers. By molecular docking, we first identify the lowest-energy conformation of one FA inside the FR binding pocket from the X-ray crystal structure, which becomes the starting point of classical MD simulations in a realistic physiological environment. We estimate the binding free energy to be compared with existing experimental data. Then, we increase complexity and go from the isolated FA to a nanosystem decorated with several FAs. Within the simulation time framework, we confirm the stability of the ligand-receptor interaction, even in the presence of the NP (with or without spacer), and no significant modification of the protein secondary structure is observed. Our study highlights the crucial role played by the spacer, by the FA protonation state and density, which are parameters that can be controlled during the nanodevice preparation step.