Modification of statistical threading in two-component pseudorotaxane melts using the amphiphilic approach and...

Recently we described a coarse-grained model of poly(ethylene oxide) and then employed that model to study the amount of spontaneous threading of cyclic molecules by linear chains in the melt [C. A. Helfer, G. Xu, W. L. Mattice, and C. Pugh, Macromolecules 36, 10071 (2003)]. Since the amount of statistical threading at equilibrium is small, there is interest in identifying physical changes in the system that will increase the threading. We now use that coarse-grained model to investigate the effect on threading of various hypothetical (but feasible) modifications to the two-component system of macrocycles and linear chains in the melt, and different confinement geometries, that can bring about correlations in the arrangement of the rings. Our work follows on the concept of an amphiphilic approach [C. Pugh, J.-Y. Bae, J. R. Scott, and C. L. Wilkins, Macromolecules 30, 8139 (1997)] for increasing the statistical threading in homopolyrotaxane melts. We investigate whether introducing such correlations in the macrocycles can increase the spontaneous threading. This paper shows that some of our modifications can yield more than double the amount of threading seen in purely statistical mixing.