Hierarchical Assemblies of Soft Matters From Polymers and Liquid Crystals on Structured Surfaces

Hierarchical, multifunctional materials hold important keys to numerous advanced technologies, including electronics, optics, and medicine. This thesis encompasses generation of hierarchical structures with novel morphologies and functions through self-assembly directed by lithographically fabricated templates. Here, two soft materials, amphiphilic random copolymers of photopolymerized acryloyl chloride (ranPAC) and smectic-A liquid crystal (SmA-LC) molecule, 4\u27(5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecaflu-orododecyloxy)-biphenyl-4-carboxylic acid ethyl ester, are synthesized as model systems to investigate the governing principles at the topographic surface/interface. The ranPAC can self-organize into nanomicelles with high regularity and stability, typically not possible in random copolymer systems. The morphology can be controlled by the photopolymerization conditions and solvent; the crosslinked shell makes the micelles robust against drying and storage. Using SU-8 micropillar arrays with spatially controlled surface chemistry as templates, we construct hierarchical microporous structures with tunable pore size and symmetry (e.g. square array), and uncover a new evaporative assembly method. By functionalizing the ranPAC nanovesicles with cationic poly(ethyleneimines), we encapsulate the anticancer drug, doxorubicin hydrochloride, and mRNA at a high payload, which are delivered to HEK 293T cells in vitro at a low cytotoxicity level. SmA-LC are characterized by arrangement of molecules into thin layers with the long molecular axis parallel to the layer normal, forming a close-packed hexagonal array of topological defects known as focal conic domains (FCDs) in a thin film. Using a series of SU-8 micropillar arrays with different size, shape, height, and symmetry as topological templates, we investigate the epitaxial and hierarchical assemblies of FCDs; whether the system favors confinement or pillar edge-pinning depends on balance of the elastic energy of LCs and the surface energy imposed by the template. The conservation of toric FCD (TFCD) textures over large LC thickness manifests a remarkably unique outcome of the epitaxial growth of TFCDs. On shorter pillars, however, the system favors the pinning of FCD centers near pillar edges while avoiding the opposing effect of confinement, leading to the break of the underlying symmetry of the pillar lattice, exhibiting tunable eccentricity, and a nontrivial yet organized array of defects balancing the elastic energy of LCs and the surface energy imposed by the template

Single solvent based film casting method for the production of porous polymer films

A single solvent based film casting process for fabricating porous polymer films was developed in this study. The porous film was produced by mixing concentrated polylactic acid/ chloroform solution (20 wt%) and fresh chloroform solvent followed by film casting. The average pore sizes of the films produced were seen to increase from 2.1 (±0.1) µm to 6.4 (±0.2) µm with increasing ratio of concentrated PLA solution and fresh solvent from 1:2 to 1:4. Functional groups of PLA after casting into porous film were confirmed via Fourier transform infrared (FTIR) spectroscopy analysis. Cytocompatibility studies (via Alamar Blue assessment) utilising MG-63 cells on the porous PLA films revealed an increase in cell metabolic activity up to 8 days post-seeding. In addition, these direct cell culture studies showed that the porous membranes supported cell adhesion and growth not only on the surface but also through the porous structures of the membrane, highlighting the suitability of these porous films in tissue engineering applications

In Situ Synthesis of Hybrid Aerogels from Single-Walled Carbon Nanotubes and Polyaniline Nanoribbons as Free-Standing, Flexible Energy Storage Electrodes

Hybrid aerogels consisting of interpenetrating single-walled carbon nanotubes and polyaniline (SWCNT/PANI) nanoribbons were prepared as free-standing, flexible lithium ion battery (LIB) electrodes. Assisted by camphorsulfonic acid, the anilinium cations formed complexation with micelles of dodecylbenzene sulfonate anions within the wet SWCNT network. Very thin PANI nanoribbons (thickness of 10–100 nm, width of 50–1000 nm, and length of 10–20 μm) were formed within the network after polymerization of aniline. By varying the concentration of aniline, we were able to fine-tune the morphologies of final PANI nanostructures, including nanoribbons, porous nanofibers, and nanoparticles. Specifically, SWCNT/PANI nanoribbon aerogels showed high capacity (185 mAh/g) and good cycle performance (up to 200 times), which could be attributed to synergistic effects of efficient ion/electron transport within the 3D carbon nanotubes network, shortened ion diffusion distance and optimized strain relaxation from nanoribbons and nanotubes, and effective penetration of electrolyte within interconnected nanopores in the network

Focal Conic Flower Textures at Curved Interfaces

Focal conic domains (FCDs) in smectic-A liquid crystals have drawn much attention, both for their exquisitely structured internal form and for their ability to direct the assembly of micromaterials and nanomaterials in a variety of patterns. A key to directing FCD assembly is control over the eccentricity of the domain. Here, we demonstrate a new paradigm for creating spatially varying FCD eccentricity by confining a hybrid-aligned smectic with curved interfaces. In particular, we manipulate interface behavior with colloidal particles in order to experimentally produce two examples of what has recently been dubbed the flower texture [C. Meyer et al., Focal Conic Stacking in Smectic A Liquid Crystals: Smectic Flower and Apollonius Tiling, Materials 2, 499, 2009MATEG91996-194410.3390/ma2020499], where the focal hyperbolæ diverge radially outward from the center of the texture, rather than inward as in the canonical éventail or fan texture. We explain how this unconventional assembly can arise from appropriately curved interfaces. Finally, we present a model for this system that applies the law of corresponding cones, showing how FCDs may be embedded smoothly within a “background texture” of large FCDs and concentric spherical layers, in a manner consistent with the qualitative features of the smectic flower. Such understanding could potentially lead to disruptive liquid-crystal technologies beyond displays, including patterning, smart surfaces, microlens arrays, sensors, and nanomanufacturing

Arrangement and SERS Applications of Nanoparticle Clusters Using Liquid Crystalline Template

Manipulation of nanomaterials such as nanoparticles (NPs) and nanorods (NRs) to make clusters is of significant interest in material science and nanotechnology due to the unusual collective opto-electric properties in such structures that cannot be found in the individual NPs. This work demonstrates an effective way to arrange NP clusters (NPCs) to make the desired arrays based on removable and NP-guidable liquid crystalline template using sublimation and reconstruction phenomenon. The position of the NPCs is precisely controlled by the defect structure of the liquid crystal (LC), namely toric focal conic domains (TFCDs), during thermal annealing to construct the LC and corresponding NPC structures. As a proof of concept, the surface-enhanced Raman scattering (SERS) activity of a fabricated array of gold nanorod (GNR) clusters is measured and shown to have highly sensitive detection characteristics essential for potential sensing applications

Creation of liquid-crystal periodic zigzags by surface treatment and thermal annealing

The orientation control of soft matter to create a large area single domain is one of the most exciting research topics in materials science. Recently, this effort has been extended to fabricate two- or three-dimensional structures for electro-optical applications. Here, we create periodic zigzag structures in liquid crystals (LCs) using a combination of surface treatment and thermal annealing. The LC molecules in the nematic (N) phase were initially guided by the alignment layer of rubbed polymers, which were quenched and subsequently annealed in the smectic A (SmA) phase to create periodic zigzag structures that represent modulated layer structures. Direct investigation of the zigzags was performed using microscopy and diffraction techniques, showing the alternately arranged focal conic domains (FCDs) formed. The resulting macroscopic periodic structures will be of interest in further studies of the physical properties of soft matters. © The Royal Society of Chemistry 2015close0