John C. Crocker

Measurement of the hydrodynamic corrections to the Brownian motion of two colloidal spheres

The hydrodynamic coupling between two isolated 0.97 μm diameter polystyrene spheres is measured by reconstructing their Brownian motion using digital video microscopy. Blinking optical tweezers are used to facilitate data collection by positioning the spheres in the microscope’s focal plane and in close proximity to one another. The observed separation dependence of the spheres’ relative and center of mass diffusion coefficients agree with that predicted by low Reynolds number hydrodynamics and the Stokes-Einstein relation.

Nanoparticles at fluid interfaces: exploiting capping ligands to control adsorption, stability and dynamics.

Nanoparticle self-assembly at fluid-fluid interfaces has been traditionally exploited in emulsification, encapsulation and oil recovery, and more recently in emerging applications including functional nanomaterials and biphasic catalysis. We provide a review of the literature focusing on the open challenges that still hamper the broader applicability of this potentially transformative technology, and we outline strategies to achieve improved control over interfacial self-assembly of nanoparticles. First, we discuss means to promote spontaneous adsorption by tuning the interfacial energies of the nanoparticles with the fluids using capping ligands, and the occurrence of energy barriers. We then examine the interactions between interfacial nanoparticles and how they affect the formation of equilibrium interfacial suspensions versus non-equilibrium two-dimensional phases, such as weakly attractive glasses and gels. Important differences with colloidal interactions in a bulk suspension arise due to the discontinuity in solvent properties at the interface. For instance, ligand brushes rearrange in asymmetric configurations, and thus play a significant role in determining interparticle interactions. Finally, we briefly discuss the link between interfacial microstructure and the dynamic response of particle-laden interfaces, including interfacial rheology and the fate of nanoparticle monolayers upon out-of-plane deformation.

Direct measurements of DNA-mediated colloidal interactions and their quantitative modeling.

DNA bridging can be used to induce specific attractions between small particles, providing a highly versatile approach to creating unique particle-based materials having a variety of periodic structures. Surprisingly, given the fact that the thermodynamics of DNA strands in solution are completely understood, existing models for DNA-induced particle interactions are typically in error by more than an order of magnitude in strength and a factor of two in their temperature dependence. This discrepancy has stymied efforts to design the complex temperature, sequence and time-dependent interactions needed for the most interesting applications, such as materials having highly complex or multicomponent microstructures or the ability to reconfigure or self-replicate. Here we report high-spatial resolution measurements of DNA-induced interactions between pairs of polystyrene microspheres at binding strengths comparable to those used in self-assembly experiments, up to 6 kBT. We also describe a conceptually straightforward and numerically tractable model that quantitatively captures the separation dependence and temperature-dependent strength of these DNA-induced interactions, without empirical corrections. This model was equally successful when describing the more complex and practically relevant case of grafted DNA brushes with self-interactions that compete with interparticle bridge formation. Together, our findings motivate a nanomaterial design approach where unique functional structures can be found computationally and then reliably realized in experiment.

Self-assembly of colloidal crystals

Recently, there has been much progress in the self-assembly of colloidal crystals. Major advances include the growth of colloidal crystals on lithographically templated substrates, the synthesis of ordered macroporous materials starting with crystalline emulsions, the investigation of the role of entropy in hard sphere colloids in space and on earth, and the use of electrohydrodynamic forces to create ordered structures.

Entropically driven self–assembly and interaction in suspension

In this paper we present fundamental studies elucidating the role of entropy in particle suspensions. We focus on systems composed of large colloidal particles along with a second, usually smaller species such as a particle or polymer. We describe direct measurements of these interactions in suspension, and we systematically show how these forces can be used to control the self–assembly of colloidal particles. The paper provides a unified review of the experiments from our laboratory, and in a few cases touches on very recent results.

Interactions and Dynamics in Charge-Stabilized Colloids

Perhaps the most remarkable observation one can make about colloidal suspensions is that they exist at all. Particles dispersed in a fluid medium have a natural tendency to aggregate under the influence of van der Waals attraction. Yet the fortunes of a great many natural and industrial processes require colloidal particles to remain dispersed or at least to aggregate at a controlled rate. The existence of colloidal suspensions as varied as milk, inks, and metallic sols attests to the efficacy of a variety of stabilizing mechanisms. As early as 1809, Russel realized that many naturally occurring colloidal particles are charged. By the end of the century, Schultz and Hardy demonstrated that the resulting electro-static repulsions were strong enough to stabilize their suspensions against flocculating. This mechanism—arguably the best understood—continues to yield new surprises despite more than a century of analysis. The most recent burst of activity has been driven by the development of new and quite general techniques for measuring colloidal and macromolecular interactions. Its counterintuitive result—that like-charged particles some-times attract each other—may have ramifications in areas as diverse as protein crystallization, self-assembly of nano-structures, and the stabilization of industrial suspensions. This article touches briefly on the well-established theory of electrostatic stabilization in colloidal suspensions. The emphasis here is on the approximations that have provided the community with an analytical theory at the expense of overlooking recently discovered effects.

Driving diffusionless transformations in colloidal crystals using DNA handshaking

Many crystals, such as those of metals, can transform from one symmetry into another having lower free energy via a diffusionless transformation. Here we create binary colloidal crystals consisting of polymer microspheres, pulled together by DNA bridges, that induce specific, reversible attractions between two species of microspheres. Depending on the relative strength of the different interactions, the suspensions spontaneously form either compositionally ordered crystals with CsCl and CuAu-I symmetries, or disordered, solid solution crystals when slowly cooled. Our observations indicate that the CuAu-I crystals form from CsCl parent crystals by a diffusionless transformation, analogous to the Martensitic transformation of iron. Detailed simulations confirm that CuAu-I is not kinetically accessible by direct nucleation from the fluid, but does have a lower free energy than CsCl. The ease with which such structural transformations occur suggests new ways of creating unique metamaterials having structures that may be otherwise kinetically inaccessible.

Forced Desorption of Nanoparticles from an Oil–Water Interface

While nanoparticle adsorption to fluid interfaces has been studied from a fundamental standpoint and exploited in application, the reverse process, that is, desorption and disassembly, remains relatively unexplored. Here we demonstrate the forced desorption of gold nanoparticles capped with amphiphilic ligands from an oil-water interface. A monolayer of nanoparticles is allowed to spontaneously form by adsorption from an aqueous suspension onto a drop of oil and is subsequently compressed by decreasing the drop volume. The surface pressure is monitored by pendant drop tensiometry throughout the process. Upon compression, the nanoparticles are mechanically forced out of the interface into the aqueous phase. An optical method is developed to measure the nanoparticle area density in situ. We show that desorption occurs at a coverage that corresponds to close packing of the ligand-capped particles, suggesting that ligand-induced repulsion plays a crucial role in this process.

Line Optical Tweezers Instrument for Measuring Nanoscale Interactions and Kinetics

We describe an optical tweezers instrument for measuring short-ranged colloidal interactions, based on a combination of a continuous wave line optical tweezers, high speed video microscopy, and laser illumination. Our implementation can measure the separation of two nearly contacting microspheres to better than 4nm at rates in excess of 10kHz. A simple image analysis algorithm allows us to sensibly remove effects from diffraction blurring and microsphere image overlap for separations ranging from contact to at least 100nm. The result is a versatile instrument for measuring steric, chemical and single-molecular interactions and dynamics, with a force resolution significantly better than achievable with current atomic force microscopy. We demonstrate the effectiveness of the instrument with measurements of the pair interactions and dynamics of microspheres in the presence of transient molecular bridges of DNA or surfactant micelles.

Short- and long-range correlated motion observed in colloidal glasses and liquids

We use a confocal microscope to examine the motion of individual particles in a dense colloidal suspension. Close to the glass transition, particle motion is strongly spatially correlated. The correlations decay exponentially with particle separation, yielding a dynamic length scale of O(2?3?) (in terms of particle diameter ?). This length scale grows modestly as the glass transition is approached. Further, the correlated motion exhibits a strong spatial dependence on the pair correlation function g(r). Motion within glassy samples is weakly correlated, but with a larger spatial scale for this correlation.