Electrostatic Interaction between Long, Rigid Helical Macromolecules at All Interaxial Angles

TL;DR

This paper develops exact and approximate formulas for electrostatic interactions between long, rigid helical macromolecules at various angles, revealing effects like torque and phase transition mechanisms relevant to DNA structures.

Contribution

It provides new explicit expressions for electrostatic interactions of helices with arbitrary angles and charge patterns, including effects of chirality and phase behavior.

Findings

Exact interaction energy formula for neutral helices in nonpolar media.

Approximate interaction energy for charged helices in electrolyte solutions.

Identification of torque effects and phase transition mechanisms in helical macromolecules.

Abstract

We derive formulae for the electrostatic interaction between two long, rigid macromolecules that may have arbitrary surface charge patterns and cross at an arbitrary interaxial angle. We calculate the dependence of the interaction energy on the interaxial angle, on the separation, and on the precise alignment of the charge pattern on one molecule with respect to the other. We focus in particular on molecules with helical charge patterns. We report an exact, explicit expression for the energy of interaction between net-neutral helices in a nonpolar medium as well as an approximate result for charged helices immersed in an electrolyte solution. The latter result becomes exact in the asymptotic limit of large separations. Molecular chirality of helices manifests itself in a torque that tends to twist helices in a certain direction out of parallel alignment and that has a nontrivial behavior at small interaxial angles. We illustrate the theory with the calculation of the torque between layers of idealized, DNA-like double helices in cholesteric aggregates. We propose a mechanism of the observed cholesteric-to-columnar phase transition and suggest an explanation for the observed macroscopic (0.4-5 um) pitch of the cholesteric phase of B-DNA.