Caroline Miesch

Kinetically trapped co-continuous polymer morphologies through intraphase gelation of nanoparticles.

We describe an approach to prepare co-continuous microstructured blends of polymers and nanoparticles by formation of a percolating network of particles within one phase of a polymer mixture undergoing spinodal decomposition. Nanorods or nanospheres of CdSe were added to near-critical blends of polystyrene and poly(vinyl methyl ether) quenched to above their lower critical solution temperature. Beyond a critical loading of nanoparticles, phase separation is arrested due to the aggregation of particles into a network (or colloidal gel) within the poly(vinyl methyl ether) phase, yielding a co-continuous spinodal-like structure with a characteristic length scale of several micrometers. The critical concentration of nanorods to achieve kinetic arrest is found to be smaller than for nanospheres, which is in qualitative agreement with the expected dependence of the nanoparticle percolation threshold on aspect ratio. Compared to structural arrest by interfacial jamming, our approach avoids the necessity for neutral wetting of particles by the two phases, providing a general pathway to co-continuous micro- and nanoscopic structures.

Multicompartment and multigeometry nanoparticle assembly

The directed or dynamic assembly of molecular components in solution is a simple and effective strategy to confine materials in desired geometries and length scales. We use a kinetic control strategy with block copolymer blending to construct complex nanoparticles through the demixing of unlike block copolymers within the same nanoscale particle. Successful nanoparticle construction relies on kinetic trapping of unlike block copolymers into the same nanoparticle with solution processing. Not only can we make nanoparticles with multiple internal compartments of a desired size, but we can also make nanoparticles of hybrid geometries (e.g. a blend of cylindrical and spherical geometries). These combination particles are kinetically trapped, non-equilibrium structures. However, the block copolymers are able to phase separate locally within the nanoscale particle, thus producing internal compartments and hybrid geometries.

Multifunctional nanoparticle-loaded spherical and wormlike micelles formed by interfacial instabilities.

Hybrid spherical and wormlike amphiphilic block copolymer micelles are formed through evaporation-induced interfacial instabilities of emulsion droplets, allowing the incorporation of pre-synthesized hydrophobic inorganic nanoparticles within the micelle cores, as well as co-encapsulation of different nanoparticles. This encapsulation behavior is largely insensitive to particle surface chemistry, shape, and size, thus providing a versatile route to fabricate multifunctional micelles.

Thermally Reversible Aggregation of Gold Nanoparticles in Polymer Nanocomposites through Hydrogen Bonding

The ability to tune the state of dispersion or aggregation of nanoparticles within polymer-based nanocomposites, through variations in the chemical and physical interactions with the polymer matrix, is desirable for the design of materials with switchable properties. In this study, we introduce a simple and effective means of reversibly controlling the association state of nanoparticles based on the thermal sensitivity of hydrogen bonds between the nanoparticle ligands and the matrix. Strong hydrogen bonding interactions provide excellent dispersion of gold nanoparticles functionalized with poly(styrene-r-2-vinylpyridine) [P(S-r-2VP)] ligands in a poly(styrene-r-4-vinyl phenol) [P(S-r-4VPh)] matrix. However, annealing at higher temperatures diminishes the strength of these hydrogen bonds, driving the nanoparticles to aggregate. This behavior is largely reversible upon annealing at reduced temperature with redispersion occurring on a time-scale of ~30 min for samples annealed 50 °C above the glass transition temperature of the matrix. Using ultraviolet-visible absorption spectroscopy (UV-vis) and transmission electron microscopy (TEM), we have established the reversibility of aggregation and redispersion through multiple cycles of heating and cooling.

Photo-sensitive ligands on nanoparticles for achieving triggered emulsion inversion.

A photocleavable ligand containing an o-nitroveratryl (oNV) linker was synthesized and used to functionalize CdSe quantum dots (QDs) to achieve liquid-liquid interface stabilization and the formation of stable water-in-oil (w/o) emulsion droplets. Ligand cleavage upon irradiation of the droplets at 365 nm led to an increase of QD hydrophilicity, and a subsequent emulsion inversion to give oil-in-water (o/w) droplets. The fluorescence of functionalized QDs, initially quenched due to the presence of the oNV group, is turned-on after irradiation and linker cleavage. Photocleavage was monitored by nuclear magnetic resonance (NMR) and Fourier-transform infrared (FT-IR) spectroscopy, and liquid-liquid interface stabilization was evaluated by interfacial tension measurements by pendant drop tensiometry.

Transition in Dynamics as Nanoparticles Jam at the Liquid/Liquid Interface

Nanoparticles (NPs) segregated to the liquid/liquid interface form disordered or liquid-like assemblies that show diffusive motions in the plane of the interface. As the areal density of NPs at the interface increases, the available interfacial area decreases, and the interfacial dynamics of the NP assemblies change when the NPs jam. Dynamics associated with jamming was investigated by X-ray photon correlation spectroscopy. Water-in-toluene emulsions, formed by a self-emulsification at the liquid/liquid interface and stabilized by ligand-capped CdSe-ZnS NPs, provided a simple, yet powerful platform, to investigate NP dynamics. In contrast to a single planar interface, these emulsions increased the number of NPs in the incident beam and decreased the absorption of X-rays in comparison to the same path length in pure water. A transition from diffusive to confined dynamics was manifested by intermittent dynamics, indicating a transition from a liquid-like to a jammed state.