Detailed
molecular dynamics (MD) simulations of aqueous solutions of short
DNA minicircles ranging in size from 30 to 180 bp were performed for
the investigation of the structure and dynamics at an atomistic level,
by employing the recently developed parmbsc1 force field. The resulting
MD trajectories were analyzed for the determination of local conformation
in terms of backbone torsion angles and interbase pair helical parameters,
and very good agreement was observed with respect to relevant experimental
data. Minor groove hydration exhibits a bimodal structure for all
nucleobases, with water molecules residing in the first subshell of
hydration forming a highly ordered, chiral water layer that conforms
to the topological state of DNA, even adopting a twisted, figure-eight
shape in the case of 180 bp minicircles. The mean-squared radius of
gyration of the simulated DNA minicircles was found to scale with
the number of base pairs, N
bp, as ⟨R
g
2⟩ ∼ N
bp
2ν with ν ≈ 0.83,
a scaling exponent in-between the values corresponding to a rigid
rodlike behavior and the 3D self-avoiding walk limit for flexible
chains. Ultrashort and very stiff 30 bp minicircles exhibit an unexpectedly
pronounced degree of anisotropic diffusion, a phenomenon that is attenuated
as the molecular length increases due to the emergence of out-of-plane
bending motions.