Late stage of the formation of a protein corona around nanoparticles in biofluids

Journal article, 2022

In biofluids containing various proteins, nanoparticles rapidly come to be surrounded by a nanometer-thick protein layer referred to as a protein corona. The late stage of this process occurs via replacement of proteins already bound to a nanoparticle by new ones. In the available kinetic models, this process is considered to include independent acts of protein detachment and attachment. It can, however, occur also at the level of protein pairs via exchange, i.e., concerted replacement of an attached protein by a newly arrived one. I argue that the exchange channel can be more important than the conventional one. To illustrate the likely specifics of the exchange channel, I present a kinetic model focused exclusively on this channel and based on the Evans-Polanyitype relation between the activation energies of the protein-exchange steps and the protein binding energies. The corresponding kinetics were calculated for three qualitatively different distributions of proteins in solution over binding energy (with a maximum or monotonously decreasing or increasing, respectively) and are found to be similar, with relatively rapid replacement of weakly bound proteins and slow redistribution of strongly bound proteins. The ratio of the timescales characterizing the evolution of weakly and strongly bound proteins is found to depend on the type of the binding-energy distribution.