Ohio Research Scholar in Science & Technology of Advanced Nanomaterials, Chemical Physics Interdisciplinary Program, Liquid Crystal Institute, Kent State University, Kent, OH 44242, USA
Prof. Torsten Hegmann
Ohio Research Scholar in Science & Technology of Advanced Nanomaterials, Chemical Physics Interdisciplinary Program, Liquid Crystal Institute, Kent State University, Kent, OH 44242, USA
Liquid crystal nanoscience, a field exploring the mutually beneficial combination of the unique properties of nanoscale materials and fluid, yet ordered liquid crystalline phases, is increasingly focusing on semiconductor quantum dots. In one major research thrust, the anisotropic properties of the liquid crystal host are sought to facilitate the assembly of quantum dots into arrays, in another, both size- and shape-dependent optical and electronic properties of quantum dots are used to manipulate optical, electro-optical and alignment properties of liquid crystalline materials. This feature article reviews recent accomplishments and new insights in this fascinating area of soft matter nanocomposites including work from our laboratory on a series of CdSe and CdTe quantum dots as additives in nematic liquid crystal hosts.
We here report on the optical, alignment and electro-optic properties of a nematic liquid crystal affected by the presence of semiconductor CdSe magic-sized nanocrystals (MSNCs). Three single-sized CdSe samples were tested, exhibiting bright bandgap photoluminescence (PL) with λmax ≈ 463 nm and ∼10 nm full width at half-maximum (fwhm). The three quantum dot (QD) samples were passivated with a monolayer of myristic acid. Two of them (QD1 and QD2) only vary in the amount of defects as indicated by different bandgap and deep trap PL. The third MSNC sample (QD3) is compositionally different, doped with Zn. These MSNCs with almost identical sizes were doped at different concentrations (1–5 wt%) into the nematic phase of 5-n-heptyl-2-(4-n-octyloxyphenyl)-pyrimidine (LC1). Only QD3 showed the formation of birefringent stripes surrounded by areas of homeotropic alignment between plain glass slides at all concentrations as observed for many other nanoparticle-doped nematic liquid crystals reported earlier by our group. In polyimide-coated glass slides favouring planar orientation of the nematic director, planar alignment was observed. Surprisingly, only the Zn-doped magic-sized QD3quantum dots (CdSe@Zn) significantly lower the dielectric anisotropy as well as the splay elastic constant of the nematic host, despite identical size and surface functionality, which highlights the tremendous effect of the nanocrystal core composition on the electro-optic properties of the nematic host. In addition, fluorescence confocal (polarizing) microscopy studies show the director field within and around the birefringent stripes and confirm locally elevated concentrations or aggregates of the MCNC that are otherwise randomly distributed in the nematic host.
Induction, transmission, and manipulation of chirality in molecular systems are well known, widely applied concepts. However, our understanding of how chirality of nanoscale entities can be controlled, measured, and transmitted to the environment is considerably lacking behind. Future discoveries of dynamic assemblies engineered from chiral nanomaterials, with a specific focus on shape and size effects, require exact methods to assess transmission and amplification of nanoscale chirality through space. Here we present a remarkably powerful chirality amplification approach by desymmetrization of plasmonic nanoparticles to nanorods. When bound to gold nanorods, a one order of magnitude lower number of chiral molecules induces a tighter helical distortion in the surrounding liquid crystal–a remarkable amplification of chirality through space. The change in helical distortion is consistent with a quantification of the change in overall chirality of the chiral ligand decorated nanomaterials differing in shape and size as calculated from a suitable pseudoscalar chirality indicator.
Size, shape, overall composition, and surface functionality largely determine the properties and applications of metal nanoparticles. Aside from well-defin
1 June 2014 in International Journal of Nanomedicine
Purpose: The present study examines the use of an external magnetic field in combination with the disruption of tight junctions to enhance the permeability of iron oxide nanoparticles (IONPs) across an in vitro model of the blood–brain barrier (BBB). The feasibility of such an approach, termed magnetic field enhanced convective diffusion (MFECD), along with the effect of IONP surface charge on permeability, was examined. Methods: The effect of magnetic field on the permeability of positively (aminosilane-coated [AmS]-IONPs) and negatively (N-(trimethoxysilylpropyl)ethylenediaminetriacetate [EDT]-IONPs) charged IONPs was evaluated in confluent monolayers of mouse brain endothelial cells under normal and osmotically disrupted conditions. Results: Neither IONP formulation was permeable across an intact cell monolayer. However, when tight junctions were disrupted using D-mannitol, flux of EDT-IONPs across the bEnd.3 monolayers was 28%, increasing to 44% when a magnetic field was present. In contrast, the permeability of AmS-IONPs after osmotic disruption was less than 5%. The cellular uptake profile of both IONPs was not altered by the presence of mannitol. Conclusions: MFECD improved the permeability of EDT-IONPs through the paracellular route. The MFECD approach favors negatively charged IONPs that have low affinity for the brain endothelial cells and high colloidal stability. This suggests that MFECD may improve IONP-based drug delivery to the brain.