Heterogeneous kinetics of the loop formation of a single polymer chain in crowded and disordered media

The cytoplasmic volume of cells is occupied and crowded by a variety of macromolecules, such as proteins and cytoskeleton structures. Such diverse macromolecules make the cell cytoplasm not only structurally heterogeneous but also dynamically heterogeneous: Some macromolecules may diffuse freely inside cell cytoplasm at certain timescales while others hardly diffuse. Studies on the effects of the dynamic heterogeneity on reaction kinetics have been limited even though the effects of the crowdedness and structural heterogeneity were investigated extensively. In this study, we employ a simple model of mixtures of mobile and immobile matrix particles, tune the degree of dynamic heterogeneity by changing the fraction of immobile matrix particles, and investigate reaction kinetics in such heterogeneous media. We employ the loop formation of a single polymer chain as a model reaction and perform Langevin dynamics simulations. We find that the free-energy barrier of the loop formation is decreased as the systems become more crowded with matrix particles. But the free-energy barrier is not sensitive to the dynamic heterogeneity. As dynamic heterogeneity increases with an increase in the fraction of immobile matrix particles, however, the diffusivity of the system decreases significantly. The decrease in the diffusion (due to the dynamic heterogeneity) and the decrease in the free-energy barrier (due to the crowdedness) lead together to a complicated trend of the loop formation kinetics. As the volume fraction of immobile matrix particles reaches a critical value at the percolation transition, the reaction kinetics becomes significantly heterogeneous and the survival probability distribution of the chain loop formation becomes stretched-exponential. We also illustrate that the heterogeneous reaction rate near the percolation transition relates closely to the structures of local pores in which the polymer is located.