ABSTRACT
The redox properties of the actinides in aqueous solution are important for fuel production/reprocessing and understanding the environmental impact of nuclear waste. The redox potentials for U, Np, Pu, and Am in oxidation states from 0 up to VII (as appropriate) in aqueous solutions have been predicted at the density functional theory level with the B3LYP functional, Stuttgart small core pseudopotential basis sets for the actinides, and explicit (30H2O molecules)/implicit treatment of the aqueous solvent using the self-consistent reaction field COSMO and SMD approaches for the implicit solvation. The predictions of the structural parameters of clusters incorporating first and second solvation shells are consistent with the available experimental data. Our results are typically within 0.2 V of the available experimental data using two explicit solvation shells with an implicit solvent model. The use of the PW91 functional substantially improved the prediction of the Pu(VI/V) redox couple. The redox couples for An(VI/IV) and An(V/IV) which involve the addition of protons and removal of the actinyl oxygens led to slightly larger differences from an experiment. The An(IV/0) and An(III/0) couples were reliably predicted with our approach. Predictions of the unknown An(II/I) redox potentials were negative, consistent with expectations, and predictions for unknown An(VII/VI), An(III/II), and An(II/0) redox couples improve prior estimates.
ABSTRACT
Molecular dynamics simulations of mixtures of the ceramide nonhydroxy-sphingosine (NS), cholesterol, and a free fatty acid are performed to gain molecular-level understanding of the structure of the lipids found in the stratum corneum layer of skin. A new coarse-grained force field for cholesterol was developed using the multistate iterative Boltzmann inversion (MS-IBI) method. The coarse-grained cholesterol force field is compatible with previously developed coarse-grained force fields for ceramide NS, free fatty acids, and water and validated against atomistic simulations of these lipids using the CHARMM force field. Self-assembly simulations of multilayer structures using these coarse-grained force fields are performed, revealing that a large fraction of the ceramides adopt extended conformations, which cannot occur in the single bilayer in water structures typically studied using molecular simulation. Cholesterol fluidizes the membrane by promoting packing defects, and an increase in cholesterol content is found to reduce the bilayer thickness due to an increase in interdigitation of the C24 lipid tails, consistent with experimental observations. Using a reverse-mapping procedure, a self-assembled coarse-grained multilayer system is used to construct an equivalent structure with atomistic resolution. Simulations of this atomistic structure are found to closely agree with experimentally derived neutron scattering length density profiles. Significant interlayer hydrogen bonding is observed in the inner layers of the atomistic multilayer structure that are not found in the outer layers in contact with water or in equivalent bilayer structures. This work highlights the importance of simulating multilayer structures, as compared to the more commonly studied bilayer systems, to enable more appropriate comparisons with multilayer experimental membranes. These results also provide validation of the efficacy of the MS-IBI derived coarse-grained force fields and the framework for multiscale simulation.
