Competitive adsorption of multiple proteins to nanoparticles: the Vroman effect revisited
AbstractProteins adsorbed from the blood plasma change nanoparticles interactions with the surrounding biological environment. In general, the adsorption of multiple proteins has a non-monotonic time dependence, that is, proteins adsorbed at first may slowly be replaced by others. This ‘Vroman effect’ leads to a highly dynamic protein corona on nanoparticles that profoundly influences the immune response of the body. Thus, the temporal evolution of the corona must be taken into account when considering applications of nanocarriers in, e.g., nanomedicine or drug delivery. Up to now, the Vroman effect is explained solely in terms of diffusion: Smaller proteins which diffuse faster are adsorbed first, while larger ones, having a stronger interaction with the surface, are preferred at equilibrium. Here we use dynamic density functional theory (DDFT) including steric and electrostatic interactions to provide a full model for the temporal evolution of the protein corona. In particular, we demonstrate that proper consideration of all interactions leads to Vroman-like adsorption signatures in widely different scenarios. Moreover, consideration of energetic terms predicts both competitive as well as cooperative adsorption. In this way, DDFT provides a reacher picture of the evolution of the dynamic protein corona.