Crowding induced self-assembly and enthalpy-entropy compensation.

We develop a general virial expansion to describe the influence of molecular additives on the equilibrium self-assembly of proteins or other supermolecularly assembling species M in solution. When specialized to high molar mass polymer additives, the cross-virial coefficient between the polymer and M, which dominates this effect, is found to vanish at a particular temperature T_{Theta} corresponding to an enthalpy-entropy compensation condition. Specifically, the increased stability of the assembled form of M, due to the modification of the entropy of the assembly by repulsive polymer-protein interactions, is progressively compensated by attractive interactions that alter the enthalpy of assembly.