Salt Modulated Structure of Polyelectrolyte-Macroion Complex Fibers

Physics – Condensed Matter – Soft Condensed Matter

Scientific paper

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18 pages, 15 figures

Scientific paper

The structure and stability of strongly charged complex fibers formed by complexation of a single long semi-flexible polyelectrolyte (PE) chain and many oppositely charged spherical macroions are investigated numerically at the ground-state level using a chain-sphere cell model. The model takes into account chain elasticity as well as electrostatic interactions between charged spheres and chain segments. Using a numerical optimization method based on a periodically repeated unit cell, we obtain fiber configurations that minimize the total energy. The optimal configurations exhibit a variety of helical structures for the arrangement of macroions including zig-zag, solenoidal and beads-on-a-string patterns. These structures are determined by a competition between attraction between spheres and the PE chain (which favors chain wrapping around the spheres), chain bending and electrostatic repulsion between chain segments (which favor unwrapping of the chain), and the interactions between neighboring sphere-chain complexes which can be attractive or repulsive depending on the system parameters such as medium salt concentration, macroion charge and chain length per macroion (linker size). At about physiological salt concentration, dense zig-zag patterns are found to be energetically most stable when parameters appropriate for the DNA-histone system in a chromatin fiber are adopted. In fact, the predicted fiber diameter in this regime is found to be around 30nm, which appears to agree with the thickness observed in in vitro experiments on chromatin. We also find a macroion density of 5-6 per 11nm which agrees with the zig-zag or cross-linker models of chromatin. Since our study deals primarily with a generic model, these findings suggest that chromatin-like structures should also be observable for PE-macroion complexes formed in solutions of DNA and synthetic nano-colloids of opposite charge.

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