Experimental Evidence for a Cluster Glass Transition in Concentrated Lysozyme Solutions.

Lysozyme is known to form equilibrium clusters at pH approximate to 7.8 and at low ionic strength as a result of a mixed potential. While this cluster formation and the related dynamic and static structure factors have been extensively investigated, its consequences on the macroscopic dynamic behavior expressed by the zero shear viscosity eta(0) remain controversial. Here we present results from a systematic investigation of eta(0) using two complementary passive microrheology techniques, dynamic light scattering based tracer microrheology, and multiple particle tracking using confocal microscopy. The combination of these techniques with a simple but effective evaporation approach allows for reaching concentrations close to and above the arrest transition in a controlled and gentle way. We find a strong increase of with increasing volume fraction phi with an apparent divergence at phi approximate to 0.35, and unambiguously demonstrate that this is due to the existence of an arrest transition where a cluster glass forms. These findings demonstrate the power of tracer microrheology to investigate complex fluids, where weak temporary bonds and limited sample volumes make measurements with classical rheology challenging.