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.
Douglas
Jack F
JF
Polymers Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, USA.
Dudowicz
Jacek
J
Freed
Karl F
KF
D019277:Entropy; D007700:Kinetics; D008956:Models, Chemical; D011108:Polymers / Q000737:chemistry*; D011506:Proteins / Q000737:chemistry* / Q000302:isolation & purification / Q000378:metabolism; D012996:Solutions
D011108:Polymers; D011506:Proteins; D012996:Solutions