Circular Polycatenanes: Supramolecular Structures with Topologically Tunable Properties

Polycatenanes, macrochains of topologically interlocked rings with unique physical properties have recently gained considerable interest in supramolecular chemistry, biology, and soft matter. Most of the work has been, so far, focused on linear chains and on their variety of conformational properties compared to standard polymers. Here we go beyond the linear case and show that, by circularizing such macrochains, one can exploit the topology of the local interlockings to store twist in the system, significantly altering its metric and local properties. Moreover, by properly defining the twist (Tw) and writhe (Wr) of these macrorings we show the validity of a relation equivalent to the Călugăreanu-White-Fuller theorem Tw+Wr=const, originally proved for ribbonlike structures such as double stranded DNA. Our results suggest that circular polycatenanes with storable and tunable twist can form a new category of highly designable multiscale structures with potential applications in supramolecular chemistry and material science.