Brownian dynamics
(BD) has been applied as a comprehensive tool to model sedimentation
and diffusion of nanoparticles in analytical ultracentrifugation (AUC)
experiments. In this article, we extend the BD algorithm by considering
space-dependent diffusion and solvent compressibility. With this,
the changes in the sedimentation and diffusion coefficient from altered
solvent properties at increased pressures are accurately taken into
account. Moreover, it is demonstrated how the concept of space-dependent
diffusion is employed to describe concentration-dependent sedimentation
and diffusion coefficients, in particular, through the Gralen coefficient
and the second virial coefficient. The influence of thermodynamic
nonideality on diffusional properties can be accurately simulated
and agree with well-known evaluation tools. BD simulations for sedimentation
equilibrium and sedimentation velocity (SV) AUC experiments including
effects of hydrodynamic and thermodynamic nonideality are validated
by global evaluation in SEDANAL. The interplay of solvent compressibility
and retrieved nonideality parameters can be studied utilizing BD.
Finally, the second virial coefficient is determined for lysozyme
from SV AUC experiments and BD simulations and compared to membrane
osmometry. These results are in line with DLVO theory. In summary,
BD simulations are established for the validation of nonideal sedimentation
in AUC providing a sound basis for the evaluation of complex interactions
even in polydisperse systems.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.