Benjamin Stokes

Phase Transition-Driven Nanoparticle Assembly in Liquid Crystal Droplets

When nanoparticle self-assembly takes place in an anisotropic liquid crystal environment, fascinating new effects can arise. The presence of elastic anisotropy and topological defects can direct spatial organization. An important goal in nanoscience is to direct the assembly of nanoparticles over large length scales to produce macroscopic composite materials; however, limitations on spatial ordering exist due to the inherent disorder of fluid-based methods. In this paper we demonstrate the formation of quantum dot clusters and spherical capsules suspended within spherical liquid crystal droplets as a method to position nanoparticle clusters at defined locations. Our experiments demonstrate that particle sorting at the isotropic–nematic phase front can dominate over topological defect-based assembly. Notably, we find that assembly at the nematic phase front can force nanoparticle clustering at energetically unfavorable locations in the droplets to form stable hollow capsules and fractal clusters at the droplet centers.

Plasmon-actuated nano-assembled microshells

We present three-dimensional microshells formed by self-assembly of densely-packed 5u2009nm gold nanoparticles (AuNPs). Surface functionalization of the AuNPs with custom-designed mesogenic molecules drives the formation of a stable and rigid shell wall, and these unique structures allow encapsulation of cargo that can be contained, virtually leakage-free, over several months. Further, by leveraging the plasmonic response of AuNPs, we can rupture the microshells using optical excitation with ultralow power (<2u2009mW), controllably and rapidly releasing the encapsulated contents in less than 5u2009s. The optimal AuNP packing in the wall, moderated by the custom ligands and verified using small angle x-ray spectroscopy, allows us to calculate the heat released in this process, and to simulate the temperature increase originating from the photothermal heating, with great accuracy. Atypically, we find the local heating does not cause a rise of more than 50u2009°C, which addresses a major shortcoming in plasmon actuated cargo delivery systems. This combination of spectral selectivity, low power requirements, low heat production, and fast release times, along with the versatility in terms of identity of the enclosed cargo, makes these hierarchical microshells suitable for wide-ranging applications, including biological ones.

Nanoparticle microstructures templated by liquid crystal phase-transition dynamics

Liquid crystal (LC) phase transition dynamics can be used as a powerful tool to control the assembly of dispersed nanoparticles. Tailored mesogenic ligands can both enhance and tune particle dispersion in the liquid crystal phase to create liquid crystal nano-composites - a novel type of material. Soft nanocomposites have recently risen to prominence for their potential usage in a variety of industrial applications such as photovoltaics, photonic materials, and the liquid crystal laser. Our group has developed a novel phase-transition-templating process for the generation of micron-scale, vesicle-like nanoparticle shells stabilized by mesogenic ligand-ligand interactions. The mesogenic ligand’s flexible arm structure enhances ligand alignment with the local LC director, providing control over the dispersion and stabilization of nanoparticles in liquid crystal phases. In this paper we explore the capsule formation process in detail, generating QD-based capsules over a surprisingly wide range of radii. We demonstrate that the initial nanoparticle concentration and cooling rate are important parameters influencing capsule size. By increasing particle concentration of nanoparticles and reducing the cooling rate we developed large shells up to 96±19 μm in diameter whereas decreasing concentration and increasing the cooling rate produces shells as small as 4±1 μm.