Molecular systems topological phase

With monomeric molecules, the aggregation number of micelles is determined by equilibrium thermodynamics. In polymeric molecules, however, topological constraints are imposed on the system. If the degree of polymerization exceeds the aggregation number of the monomeric micelle, unsaturated sites of the polymeric molecules become available (directed to the aqueous phase) and inter-molecular interactions (agglomeration) occur. In the case of polymer with Mw= 6.23x105, typical surfactant behavior was found. 

It should also be noted that the stability of the distinct mesophases can be quite different. It seems that there is a significant effect of molecular shape and topology, stabilizing SmA phases in the system 41/43 and Colhex phases in the system 35/37. In addition, the mesophase stability is often reduced close to the transition to another mesophase (see Fig. 15). Hence, the order-disorder temperatures can only be roughly estimated based on segmental solubility parameters [24, 25]. 

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