Structural, dynamic, and hydration properties of quercetin and its aggregates in solution.

Quercetin is a flavonoid present in the human diet with multiple health benefits. Quercetin solutions are inhomogeneous even at very low concentrations due to quercetin's tendency to aggregate. We simulate, using molecular dynamics, three systems of quercetin solutions: infinite dilution, 0.22 M, and 0.46 M. The systems at the two highest concentrations represent regions of the quercetin aggregates, in which the concentration of this molecule is unusually high. We study the behavior of this molecule, its aggregates, and the modifications in the surrounding water. In the first three successive layers of quercetin hydration, the density of water and the hydrogen bonds formations between water molecules are smaller than that of bulk. Quercetin has a hydrophilic surface region that preferentially establishes donor hydrogen bonds with water molecules with relative frequencies from 0.12 to 0.46 at infinite dilution. Also, it has two hydrophobic regions above and below the planes of its rings, whose first hydration layers are further out from quercetin (≈0.3 Å) and their water molecules do not establish hydrogen bonds with it. Water density around the hydrophobic regions is smaller than that of the hydrophilic. Quercetin molecules aggregate inπ-stacking configurations, with a distance of ≈0.37 nm between the planes of their rings, and form bonds between their hydroxyl groups. The formation of quercetin aggregates decreases the hydrogen bonds between quercetin and the surrounding water and produces a subdiffusive behavior in water molecules. Quercetin has a subdiffusive behavior even at infinite dilution, which increases with the number of molecules within the aggregates and the time they remain within them.

Electric dichroism transients of aqueous solutions of DNA.

In this work we develop a theory of reduced electric linear dichroism transients of DNA fragments in aqueous solution. The DNA fragments are modelled as rigid 'bent-rod molecules' (BRM) with the following physical parameters: electric charge, electric polarizability tensors and hydrodynamical ones, and the average transition probability tensor per molecule. In order to study the growth and decay of electric dichroism transients, the orientational distribution function of the molecules is needed. This function is obtained by solving the time-dependent Fokker-Planck equation in the presence of a low electric field E, using a perturbation method and the Fourier method with time-dependent coefficients. In our calculations the origin of the coordinate system is the mass centre of the BRM. With respect to this centre, the electric dipole moment of the molecule is zero. The developed theory adequately explains the experimental results. We show that the theoretical approach used in this work is equivalent to the one applied in the Brownian dynamics simulation work performed by Porschke and co-workers. We also analyse the effect of a possible electric dipole moment on the transients of the reduced electric linear dichroism in DNA bent fragments.