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.

Revealing viscoelastic bending relaxation dynamics of isolated semiflexible colloidal polymers.

The viscoelastic properties of filaments and biopolymers play a crucial role in soft and biological materials from biopolymer networks to novel synthetic metamaterials. Colloidal particles with specific valency allow mimicking polymers and more complex molecular structures at the colloidal scale, offering direct observation of their internal degrees of freedom. Here, we elucidate the time-dependent viscoelastic response in the bending of isolated semi-flexible colloidal polymers, assembled from dipatch colloidal particles by reversible critical Casimir forces. By tuning the patch-patch interaction strength, we adjust the polymers' viscoelastic properties, and follow spontaneous bending modes and their relaxation directly on the particle level. We find that the elastic response is well described by that of a semiflexible rod with persistence length of order 1000 µm, tunable by the critical Casimir interaction strength. We identify the viscous relaxation on longer timescales to be due to internal friction, leading to a wavelength-independent relaxation time similar to single biopolymers, but in the colloidal case arising from the contact mechanics of the bonded patches. These tunable mechanical properties of assembled colloidal filaments open the door to "colloidal architectures", rationally designed (network) structures with desired topology and mechanical properties.