Modeling the Electric Double Layer at the Liposome Vesicle via Classical Density Functional Theory: Solution of Poisson's Equations for Curved Membranes.

The electric double layer at the liposome vesicle membrane has been investigated by a modified fundamental-measure theory in the framework of the restricted primitive model. An analytical equation has been obtained for the mean electrostatic potential (MEP) by solving Poisson's equation for curved membranes. This study investigates the influence of vesicle size, membrane thickness, surface charges, and electrolyte concentration on the structure, composition, and width of electric double layers (EDLs) on the inner and outer membrane walls. Our findings indicate that a thin and denser layer of ions is formed at the concave wall of the membrane (inner wall) compared to that at the outer membrane. As expected, the width of the diffuse layer decreases with the concentration and surface charge. Also, when the surface charges on both concave and convex walls are the same, the absolute value of MEPs on the inner membrane, concave wall, is greater than that on the convex wall. We have also investigated the diffuse potential, which decreases with concentration, membrane thickness, and cavity size, whereas it increases with surface charges. As we expect, the contact density of counterions at the inner concave wall of the vesicle cavity is always greater than the corresponding value at the convex wall, whereas this trend reverses for co-ions. Also, the contact density of counterions (co-ions) at the inner wall decreases (increases) with cavity size, whereas it increases at the outer wall (decreases). Finally, depletion of co-ions occurs at the membrane walls with enhancement in surface charges.

The effects of tautomerization and protonation on the adenine-cytosine mismatches: a density functional theory study.

In the present work, we demonstrate the results of a theoretical study concerned with the question how tautomerization and protonation of adenine affect the various properties of adenine-cytosine mismatches. The calculations, in gas phase and in water, are performed at B3LYP/6-311++G(d,p) level. In gas phase, it is observed that any tautomeric form of investigated mismatches is more stabilized when adenine is protonated. As for the neutral mismatches, the mismatches containing amino form of cytosine and imino form of protonated adenine are more stable. The role of aromaticity on the stability of tautomeric forms of mismatches is investigated by NICS(1)ZZ index. The stability of mispairs decreases by going from gas phase to water. It can be explained using dipole moment parameter. The influence of hydrogen bonds on the stability of mismatches is examined by atoms in molecules and natural bond orbital analyses. In addition to geometrical parameters and binding energies, the study of the topological properties of electron charge density aids in better understanding of these mispairs.