In closed circular ribbonlike polymers such as deoxyribonucleic acid, twist and writhe are known to be largely determined by the polymer’s bending and torsional rigidities, and they must sum to a topological constant. Using molecular simulations and an analytically solvable Landau theory, we study the interplay between ribbon topology and chemically annealed charges in a model polyelectrolyte. We show that the repulsions between like-charged acidic sites trigger phase separation and coexistence of supercoiling domains, in turn unveiling a complex phase diagram and providing a route to control the properties of deoxyribonucleic acid-based materials.

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