Structure and Thermodynamics of Linear, Ring, and Catenane Polymers in Solutions and at Liquid-Liquid Interfaces

In recent decades, advances in the syntheses of mechanically interlocked macromolecules, such as catenanes, have led to much greater interest in the applications of these complexes, from molecular motors and actuators to nanoscale computational memory and nanoswitches. Much remains to be understood, however, regarding how catenated ring compounds behave as a result of the effects of different solvents as well as the effects of solvent/solvent interfaces. In this work, we have investigated, using molecular dynamics simulations, the effects of solvation of poly(ethylene oxide) chains of different topologies─linear, ring, and [2]catenane─in two solvents both considered favorable toward PEO (water, toluene) and at the water/toluene interface. Compared to ring and [2]catenane molecules, the linear PEO chain showed the largest increase in size at the water/toluene interface compared to bulk water or bulk toluene. Perhaps surprisingly, observations indicate that the tendency of all three topologies to extend at the water/toluene interface may have more to do with screening the interaction between the two solvents than with optimizing specific solvent-polymer contacts.