Publications by authors named "Caroline Miesch"

Nanoparticles may act as compatibilizing agents for blending of immiscible polymers, leading to changes in blend morphology through a variety of mechanisms including interfacial adsorption, aggregation, and nucleation of polymer crystals. Herein, we report an approach to define highly structured donor/acceptor networks based on poly(3-hexylthiophene) (P3HT) and CdSe quantum dots (QDs) by demixing from an insulating polystyrene (PS) matrix. The incorporation of QDs led to laterally phase-separated co-continuous structures with sub-micrometer dimensions, and promoted crystallization of P3HT, yielding highly interconnected P3HT/QD hybrid nanowires embedded in the polymer matrix.

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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.

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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.

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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.

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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.

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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.

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