Revealing Polymerization Kinetics with Colloidal Dipatch Particles.

Limited-valency colloidal particles can self-assemble into polymeric structures analogous to molecules. While their structural equilibrium properties have attracted wide attention, insight into their dynamics has proven challenging. Here, we investigate the polymerization dynamics of semiflexible polymers in 2D by direct observation of assembling divalent particles, bonded by critical Casimir forces. The reversible critical Casimir force creates living polymerization conditions with tunable chain dissociation, association, and bending rigidity. We find that unlike dilute polymers that show exponential size distributions in excellent agreement with Flory theory, concentrated samples exhibit arrest of rotational and translational diffusion due to a continuous isotropic-to-nematic transition in 2D, slowing down the growth kinetics. These effects are circumvented by the addition of higher-valency particles, cross linking the polymers into networks. Our results connecting polymer flexibility, polymer interactions, and the peculiar isotropic-nematic transition in 2D offer insight into the polymerization processes of synthetic two-dimensional polymers and biopolymers at membranes and interfaces.

Protein microparticles visualize the contact network and rigidity onset in the gelation of model proteins.

Protein aggregation into gel networks is of immense importance in diverse areas from food science to medical research; however, it remains a grand challenge as the underlying molecular interactions are complex, difficult to access experimentally, and to model computationally. Early stages of gelation often involve protein aggregation into protein clusters that later on aggregate into a gel network. Recently synthesized protein microparticles allow direct control of these early stages of aggregation, decoupling them from the subsequent gelation stages. Here, by following the gelation of protein microparticles directly at the particle scale, we elucidate in detail the emergence of a percolating structure and the onset of rigidity as measured by microrheology. We find that the largest particle cluster, correlation length, and degree of polymerization all diverge with power laws, while the particles bind irreversibly indicating a nonequilibrium percolation process, in agreement with recent results on weakly attractive colloids. Concomitantly, the elastic modulus increases in a power-law fashion as determined by microrheology. These results give a consistent microscopic picture of the emergence of rigidity in a nonequilibrium percolation process that likely underlies the gelation in many more systems such as proteins, and other strongly interacting structures originating from (bio)molecules.

Nonequilibrium master kinetic equation modeling of colloidal gelation.

We present a detailed study of the kinetic cluster growth process during gelation of weakly attractive colloidal particles by means of experiments on critical Casimir attractive colloidal systems, simulations, and analytical theory. In the experiments and simulations, we follow the mean coordination number of the particles during the growth of clusters to identify an attractive-strength independent cluster evolution as a function of mean coordination number. We relate this cluster evolution to the kinetic attachment and detachment rates of particles and particle clusters. We find that single-particle detachment dominates in the relevant weak attractive-strength regime, while association rates are almost independent of the cluster size. Using the limit of single-particle dissociation and size-independent association rates, we solve the master kinetic equation of cluster growth analytically to predict power-law cluster mass distributions with exponents -3/2 and -5/2 before and after gelation, respectively, which are consistent with the experimental and simulation data. These results suggest that the observed critical Casimir-induced gelation is a second-order nonequilibrium phase transition (with broken detailed balance). Consistent with this scenario, the size of the largest cluster is observed to diverge with power-law exponent according to three-dimensional percolation on approaching the critical mean coordination number.

Nonequilibrium continuous phase transition in colloidal gelation with short-range attraction.

The dynamical arrest of attractive colloidal particles into out-of-equilibrium structures, known as gelation, is central to biophysics, materials science, nanotechnology, and food and cosmetic applications, but a complete understanding is lacking. In particular, for intermediate particle density and attraction, the structure formation process remains unclear. Here, we show that the gelation of short-range attractive particles is governed by a nonequilibrium percolation process. We combine experiments on critical Casimir colloidal suspensions, numerical simulations, and analytical modeling with a master kinetic equation to show that cluster sizes and correlation lengths diverge with exponents  ~1.6 and 0.8, respectively, consistent with percolation theory, while detailed balance in the particle attachment and detachment processes is broken. Cluster masses exhibit power-law distributions with exponents  -3/2 and  -5/2 before and after percolation, as predicted by solutions to the master kinetic equation. These results revealing a nonequilibrium continuous phase transition unify the structural arrest and yielding into related frameworks.