The Buckling Spectra of Nanoparticle Surfactant Assemblies.

Fine control over the mechanical properties of thin sheets underpins transcytosis, cell shape, and morphogenesis. Applying these principles to artificial, liquid-based systems has led to reconfigurable materials for soft robotics, actuation, and chemical synthesis. However, progress is limited by a lack of synthetic two-dimensional membranes that exhibit tunable mechanical properties over a comparable range to that seen in nature. Here, we show that the bending modulus, B, of thin assemblies of nanoparticle surfactants (NPSs) at the oil-water interface can be varied continuously from sub-kBT to 106kBT, by varying the ligands and particles that comprise the NPS. We find extensive departure from continuum behavior, including enormous mechanical anisotropy and a power law relation between B and the buckling spectrum width. Our findings provide a platform for shape-changing liquid devices and motivate new theories for the description of thin-film wrinkling.

Direct observation of nanoparticle-surfactant assembly and jamming at the water-oil interface.

Electrostatic interactions between nanoparticles (NPs) and functionalized ligands lead to the formation of NP surfactants (NPSs) that assemble at the water-oil interface and form jammed structures. To understand the interfacial behavior of NPSs, it is necessary to understand the mechanism by which the NPSs attach to the interface and how this attachment depends on the areal coverage of the interface. Through direct observation with high spatial and temporal resolution, using laser scanning confocal microscopy and in situ atomic force microscopy (AFM), we observe that early-stage attachment of NPs to the interface is diffusion limited and with increasing areal density of the NPSs, further attachment requires cooperative displacement of the previously assembled NPSs both laterally and vertically. The unprecedented detail provided by in situ AFM reveals the complex mechanism of attachment and the deeply nonequilibrium nature of the assembly.

Reconfigurable Printed Liquids.

Liquids lack the spatial order required for advanced functionality. Interfacial assemblies of colloids, however, can be used to shape liquids into complex, 3D objects, simultaneously forming 2D layers with novel magnetic, plasmonic, or structural properties. Fully exploiting all-liquid systems that are structured by their interfaces would create a new class of biomimetic, reconfigurable, and responsive materials. Here, printed constructs of water in oil are presented. Both form and function are given to the system by the assembly and jamming of nanoparticle surfactants, formed from the interfacial interaction of nanoparticles and amphiphilic polymers that bear complementary functional groups. These yield dissipative constructs that exhibit a compartmentalized response to chemical cues. Potential applications include biphasic reaction vessels, liquid electronics, novel media for the encapsulation of cells and active matter, and dynamic constructs that both alter, and are altered by, their external environment.

Crystallization and flow in active patch systems.

Based upon recent experiments in which Janus particles are made into active swimmers by illuminating them with laser light, we explore the effect of applying a light pattern on the sample, thereby creating activity inducing zones or active patches. We simulate a system of interacting Brownian diffusers that become active swimmers when moving inside an active patch and analyze the structure and dynamics of the ensuing stationary state. We find that, in some respects, the effect of spatially inhomogeneous activity is qualitatively similar to a temperature gradient. For asymmetric patches, however, this analogy breaks down because the ensuing stationary state is specific to partial active motion.

Frictional dynamics of stiff monolayers: from nucleation dynamics to thermal sliding.

The inherently nonlinear dynamics of two surfaces as they are driven past each other, a phenomenon known as dry friction, has yet to be fully understood on an atomistic level. New experiments on colloidal monolayers forced over laser-generated substrates now offer the opportunity to investigate friction with single-particle resolution. Here, we use analytical theory and computer simulations to study the effect of thermal fluctuations on the stick-slip mechanism characteristic for the frictional response of a stiff colloidal monolayer on a commensurate substrate. By performing a harmonic expansion of the energy and employing elementary statistical mechanics, we map the motion of the monolayer onto a simple differential equation. Analytical expressions derived from our approach predict a transition from nucleation dynamics, where the monolayer moves in a sequence of activated hops over energy barriers, to "thermal sliding", in which the effective substrate barrier opposing the motion of the monolayer disappears due to thermal fluctuations, leading to continuous, uninterrupted sliding motion. Furthermore, we find that the average velocity of the monolayer for large driving forces obeys a simple scaling behavior that is consistent with the existence of a static friction. For small forces, however, nucleation provides a mode of motion that leads to a small but non-vanishing mobility of the monolayer. Data obtained from simulations confirm this picture and agree quantitatively with our analytical formulae. The theory developed here holds under general conditions for sufficiently strong inter-particle repulsions and it yields specific predictions that can be tested in experiments.