Structural and dynamic heterogeneity in associative networks formed by artificially engineered protein polymers

This work investigates static gel structure and cooperative multi-chain motion in associative networks using a well-defined model system composed of artificial coiled-coil proteins. The combination of small-angle and ultra-small-angle neutron scattering provides evidence for three static length scales irrespective of protein gel design which are attributed to correlations arising from the blob length, inter-junction spacing, and multi-chain density fluctuations. Self-diffusion measurements using forced Rayleigh scattering demonstrate an apparent superdiffusive regime in all gels studied, reflecting a transition between distinct "slow" and "fast" diffusive species. The interconversion between the two diffusive modes occurs on a length scale on the order of the largest correlation length observed by neutron scattering, suggesting a possible caging effect. Comparison of the self-diffusive behavior with characteristic molecular length scales and the single-sticker dissociation time inferred from tracer diffusion measurements supports the primarily single-chain mechanisms of self-diffusion as previously conceptualized. The step size of the slow mode is comparable to the root-mean-square length of the midblock strands, consistent with a single-chain walking mode rather than collective motion of multi-chain aggregates. The transition to the fast mode occurs on a timescale 10-1000 times the single-sticker dissociation time, which is consistent with the onset of single-molecule hopping. Finally, the terminal diffusivity depends exponentially on the number of stickers per chain, further suggesting that long-range diffusion occurs by molecular hopping rather than sticky Rouse motion of larger assemblies. Collectively, the results suggest that diffusion of multi-chain clusters is dominated by the single-chain pictures proposed in previous coarse-grained modeling.