Ergodic and non-ergodic phase transitions in globular protein suspensions

Abstract

The equilibrium and nonequilibrium phase behavior of a protein suspension is investigated as a function of strength of interparticle attraction and protein concentration. The equilibrium phase behavior suggests that the range of the particle attractions is a small fraction of their diameter. At volume fractions and strengths of attractions smaller than those characterizing the spinodal of a metastable fluid–fluid transition, the suspensions gel before they crystallize. At higher volume fractions and lower strengths of attraction, gels are formed first from which crystals nucleate over a period of time. However, at higher strength of attraction, crystals form first at lower volume fractions while gels are observed at higher volume fractions. We hypothesize that this behavior results from the competition between the rates of gelation and crystal nucleation. The location of the gel line is well predicted by mode coupling theories adapted for low volume fractions and square well fluids. At low strength of attraction, the gel line occurs at small supersaturations suggesting gels will be seen before nucleation. However, at higher strengths of attraction the gel line occurs at greatly increased supersaturations such that crystal nucleation can occur before the gel line is crossed. That mode coupling theories should predict gelation when crystallization does not intervene is tested by investigating the gel dynamics.