W. Benjamin Rogers

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.

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.

Producing monodisperse drug-loaded polymer microspheres via cross-flow membrane emulsification: the effects of polymers and surfactants.

Cross-flow membrane emulsification (XME) is a method for producing highly uniform droplets by forcing a fluid through a small orifice into a transverse flow of a second, immiscible fluid. We investigate the feasibility of using XME to produce monodisperse solid microspheres made of a hydrolyzable polymer and a hydrophobic drug, a model system for depot drug delivery applications. This entails the emulsification of a drug and polymer-loaded volatile solvent into water followed by evaporation of the solvent. We use a unique side-view visualization technique to observe the details of emulsion droplet production, providing direct information regarding droplet size, dripping frequency, wetting of the membrane surface by the two phases, neck thinning during droplet break off, and droplet deformation before and after break off. To probe the effects that dissolved polymers, surfactants, and dynamic interfacial tension may have on droplet production, we compare our results to a polymer and surfactant-free fluid system with closely matched physical properties. Comparing the two systems, we find little difference in the variation of particle size as a function of continuous phase flow rate. In contrast, at low dripping frequencies, dynamic interfacial tension causes the particle size to vary significantly with drip frequency, which is not seen in simple fluids. No effects due to shear thinning or fluid elasticity are detected. Overall, we find no significant impediments to the application of XME to forming highly uniform drug-loaded microspheres.

Kinetics and non-exponential binding of DNA-coated colloids

Transient bridges of DNA have been used to direct the self-assembly of colloidal particles into interesting soft materials, but the particle binding kinetics are often slow or anomalous. Using line optical tweezers, we quantify the dynamics of two DNA-coated microspheres as a function of DNA density and strength of the DNA-induced pair interaction potential. At high DNA density, the binding kinetics is limited by the rate of microsphere diffusion and displays the expected dependence on the interaction potential energy. At low DNA density, the particle binding kinetics is set by single molecular binding events and exhibits bound times having a non-exponential distribution, suggesting that individual DNA bridges may also have intrinsic non-exponential kinetics. A dynamic model that includes such dispersion in the lifetimes of molecular bridges reproduces our observations, while an alternative model based on fluctuations in DNA density does not.

Reply to Mognetti et al.: DNA handshaking interaction data are well described by mean-field and molecular models

We are grateful to our colleagues at Cambridge for their attention (1) to our recent article (2). Our major goal therein was to report precise measurements of colloidal interactions caused by DNA handshaking. Because no detailed models for our system were available, we constructed a mean-field model, itself a significant refinement of one we published (3) in 2005. In contrast to previous comparisons of theory and experiment, our model and data agreed quantitatively, using reasonable values of DNAs physical (3) and thermodynamic (4) properties. We agree with the Cambridge groups conclusion that no existing theoretical framework can provide an exact description of this complicated physical situation. We are baffled, however, by the logic of their claim that our comparatively simple model is not correct because it disagrees with the model described in their letter, despite both agreeing satisfactorily with the data (Fig. 1).

Photonic-crystal hydrogels with a rapidly tunable stop band and high reflectivity across the visible

We present a new type of hydrogel photonic crystal with a stop band that can be rapidly modulated across the entire visible spectrum. We make these materials by using a high-molecular-weight polymer to induce a depletion attraction between polystyrene-poly(N-isopropylacrylamide-co-bisacrylamide-co-acrylic acid) core-shell particles. The resulting crystals display a stop band at visible wavelengths that can be tuned with temperature at a rate of 60 nm/s, nearly three orders of magnitude faster than previous photonic-crystal hydrogels. Above a critical concentration of depleting agent, the crystals do not melt even at 40 degrees Celsius. As a result, the stop band can be modulated continuously from red (650 nm) to blue (450 nm), with nearly constant reflectivity throughout the visible spectrum. The unusual thermal stability is due to the polymer used as the depleting agent, which is too large to enter the hydrogel mesh and therefore induces a large osmotic pressure that holds the particles together. The fast response rate is due to the collective diffusion coefficient of our hydrogel shells, which is more than three orders of magnitude larger than that of conventional bulk hydrogels. Finally, the constant reflectivity from red (650 nm) to blue (450 nm) is due to the core-shell design of the particles, whose scattering is dominated by the polystyrene cores and not the hydrogel. These findings provide new insights into the design of responsive photonic crystals for display applications and tunable lasers.

A tunable line optical tweezers instrument with nanometer spatial resolution.

We describe a simple scanning-line optical tweezers instrument for measuring pair interactions between micrometer-sized colloidal particles. Our instrument combines a resonant scanning mirror and an acousto-optic modulator. The resonant scanning mirror creates a time-averaged line trap whose effective one-dimensional intensity profile, and corresponding trapping potential energy landscape can be programmed using the acousto-optic modulator. We demonstrate control over the confining potential by designing and measuring a family of one-dimensional harmonic traps. By adjusting the spring constant, we balance scattering-induced repulsive forces between a pair of trapped particles, creating a flat potential near contact that facilitates interaction measurements. We also develop a simple method for extracting the out-of-plane motion of trapped particles from their relative brightness, allowing us to resolve their relative separation to roughly 1 nm.

Effects of Contact-Line Pinning on the Adsorption of Nonspherical Colloids at Liquid Interfaces

The effects of contact-line pinning are well known in macroscopic systems but are only just beginning to be explored at the microscale in colloidal suspensions. We use digital holography to capture the fast three-dimensional dynamics of micrometer-sized ellipsoids breaching an oil-water interface. We find that the particle angle varies approximately linearly with the height, in contrast to results from simulations based on the minimization of the interfacial energy. Using a simple model of the motion of the contact line, we show that the observed coupling between translational and rotational degrees of freedom is likely due to contact-line pinning. We conclude that the dynamics of colloidal particles adsorbing to a liquid interface are not determined by the minimization of interfacial energy and viscous dissipation alone; contact-line pinning dictates both the time scale and pathway to equilibrium.

Breaking trade-offs between translucency and diffusion in particle-doped films

Particle-doped thin films that are translucent and diffusive have applications in cosmetics, coatings, and display technologies, but finding material combinations that produce these effects simultaneously is challenging: formulations tend to be either transparent or opaque. Using a combination of Mie scattering calculations and spectral transmission measurements on monodisperse colloidal suspensions, we demonstrate that the two characteristic optical properties of the films, total transmittance and haze, scale with the effective backscattering and forward scattering cross sections, both of which are properties of single particles. These scalings enable an efficient computational search for combinations of particle sizes, concentrations, and refractive indices that break the trade-off between translucency and diffusion. The optimum particle sizes and concentrations obey power-law dependences on the refractive index difference, a result of the interference condition for resonances in the scattering cross sections. The power laws serve as design equations for formulating particle-doped thin films.