Abrupt Transition from a Free, Repulsive to a Condensed, Attractive DNA Phase, Induced by Multivalent Polyamine Cations

We have investigated the energetics of DNA condensation by multivalent polyamine cations. Solution small angle x-ray scattering was used to monitor interactions between short 25 base pair dsDNA strands in the free supernatant DNA phase that coexists with the condensed DNA phase. Interestingly, when tetravalent spermine is used, significant inter-DNA repulsion is observed in the free phase, in contrast with the presumed inter-DNA attraction in the coexisting condensed phase. DNA condensation thus appears to be a discrete, first-order-like, transition from a repulsive gaseous to an attractive condensed solid phase, in accord with the reported all-or-none condensation of giant DNA. We further quantify the electrostatic repulsive potentials in the free DNA phase and estimate the number of additional spermine cations that bind to DNA upon condensation

Complexation of DNA with positive spheres: phase diagram of charge inversion and reentrant condensation

The phase diagram of a water solution of DNA and oppositely charged spherical macroions is studied. DNA winds around spheres to form beads-on-a-string complexes resembling the chromatin 10 nm fiber. At small enough concentration of spheres these "artificial chromatin" complexes are negative, while at large enough concentrations of spheres the charge of DNA is inverted by the adsorbed spheres. Charges of complexes stabilize their solutions. In the plane of concentrations of DNA and spheres the phases with positive and negative complexes are separated by another phase, which contains the condensate of neutral DNA-spheres complexes. Thus when the concentration of spheres grows, DNA-spheres complexes experience condensation and resolubilization (or reentrant condensation). Phenomenological theory of the phase diagram of reentrant condensation and charge inversion is suggested. Parameters of this theory are calculated by microscopic theory. It is shown that an important part of the effect of a monovalent salt on the phase diagram can be described by the nontrivial renormalization of the effective linear charge density of DNA wound around a sphere, due to the Onsager-Manning condensation. We argue that our phenomenological phase diagram or reentrant condensation is generic to a large class of strongly asymmetric electrolytes. Possible implication of these results for the natural chromatin are discussed.Comment: Many corrections to text. SUbmitted to J. Chem. Phy

Theory and simulations of toroidal and rod-like structures in single-molecule DNA condensation

DNA condensation by multivalent cations plays a crucial role in genome packaging in viruses and sperm heads, and has been extensively studied using single-molecule experimental methods. In those experiments, the values of the critical condensation forces have been used to estimate the amplitude of the attractive DNA-DNA interactions. Here, to describe these experiments, we developed an analytical model and a rigid body Langevin dynamics assay to investigate the behavior of a polymer with self-interactions, in the presence of a traction force applied at its extremities. We model self-interactions using a pairwise attractive potential, thereby treating the counterions implicitly. The analytical model allows to accurately predict the equilibrium structures of toroidal and rod-like condensed structures, and the dependence of the critical condensation force on the DNA length. We find that the critical condensation force depends strongly on the length of the DNA, and finite-size effects are important for molecules of length up to 10^5 {\mu}m. Our Langevin dynamics simulations show that the force-extension behavior of the rod-like structures is very different from the toroidal ones, so that their presence in experiments should be easily detectable. In double-stranded DNA condensation experiments, the signature of the presence of rod-like structures was not unambiguously detected, suggesting that the polyamines used to condense DNA may protect it from bending sharply as needed in the rod-like structuresComment: 10 pages, 7 figure

Reentrant Condensation of DNA induced by Multivalent Counterions

A theory of condensation and resolubilization of a dilute DNA solution with growing concentration of multivalent cations, N is suggested. It is based on a new theory of screening of a macroion by multivalent cations, which shows that due to strong cation correlations at the surface of DNA the net charge of DNA changes sign at some small concentration of cations N_0. DNA condensation takes place in the vicinity of N_0, where absolute value of the DNA net charge is small and the correlation induced short range attraction dominates the Coulomb repulsion. At N > N_0 positive DNA should move in the oppisite direction in an electrophoresis experiment. From comparison of our theory with experimental values of condensation and resolubilization thresholds for DNA solution containing Spe$^{4+}$, we obtain that N_0 = 3.2 mM and that the energy of DNA condensation per nucleotide is $0.07 k_B T$.Comment: 8 pages, 4 figures, references correcte

Confined chiral polymer nematics: ordering and spontaneous condensation

We investigate condensation of a long confined chiral nematic polymer inside a spherical enclosure, mimicking condensation of DNA inside a viral capsid. The Landau-de Gennes nematic free energy {\sl Ansatz} appropriate for nematic polymers allows us to study the condensation process in detail with different boundary conditions at the enclosing wall that simulate repulsive and attractive polymer-surface interactions. Increasing the chirality, we observe a transformation of the toroidal condensate into a closed surface with an increasing genus, akin to the ordered domain formation observed in cryo-microscopy of bacteriophages

Polymer induced condensation of dna supercoils

Macromolecular crowding is thought to be a significant factor driving DNA condensation in prokaryotic cells. Whereas DNA in prokaryotes is supercoiled, studies on crowding-induced DNA condensation have so far focused on linear DNA. Here we compare DNA condensation by poly(ethylene oxide) for supercoiled and linearized pUC18 plasmid DNA. It is found that supercoiling has only a limited influence on the critical amount of PEO needed to condense plasmid DNA. In order to pack DNA supercoils in condensates, it seems inevitable that they must be deformed in one way or another, to facilitate dense packing of DNA. Analytical estimates and Monte Carlo simulations indicate that packing of DNA supercoils in condensates is most likely facilitated by a decrease of the superhelical diameter rather than by unwinding of the supercoil

The pulling force of a single DNA molecule condensed by spermidine

In a recent experiment, a single DNA double helix is stretched and relaxed in the presence of spermidine, a short positive polyelectrolyte, and the pulling force is measured as a function of DNA extension. In a certain range of spermidine concentration, a force plateau appears whose value shows maximum as a function of spermidine concentration. We present a quantitative theory of this plateau force based on the theory of reentrant condensation and derive almost parabolic behavior of the plateau force as a function of the logarithm of the spermidine concentration in the range of condensation. Our result is in good agreement with experimental data.Comment: 4 pages, 4 figures. Small change in the text, no change in result