Synthesis of Three-dimensional Polymer Nanostructures via Chemical Vapor Deposition

Abstract

Chemical vapor deposition (CVD) is a widely practiced methodology for preparing thin film polymer coatings, and the coatings can be applied to a broad range of materials, including three-dimensional solid structures and low-vapor pressure liquids. Reactive poly(p-xylylene) (PPX) coatings prepared by CVD can be used as a powerful tool for surface functionalization and bio-conjugation. The first portion of this dissertation serves to extend the use of CVD-based reactive PPX coatings as a surface functionalization strategy for the conjugation of biomolecules. Micro-structured PPX coatings having multiple surface reactive groups were fabricated. Multiple orthogonal click reactions were then employed to selectively immobilize galactose and mannobiose to the micro-structured polymer coatings. The presence of different types of carbohydrate enables lectins binding for examining ligands/cell receptor interactions. This dissertation also demonstrates the use of CVD-based reactive PPX coatings as intermediate layers to immobilize adenoviral vectors onto tissue scaffolds. The ability to tether adenoviral vectors on tissue scaffolds localizes the transduction near the scaffold surface and reduces acute toxicity and hepatic pathology cause by direct administration of the viral vector, providing a safe and efficient gene therapy delivery strategy. In the second portion of this dissertation, we explore the CVD of PPX onto surfaces coated with a thin layer of liquid crystal (LC). Instead of forming a conformal PPX coating encapsulating the LC layer, PPX assembled into an array of high-aspect ratio nanofibers inside the LC layer. The LC layer was demonstrated to act as a template where the anisotropic internal ordering of the LC facilitated the formation of nanofibers. The diameter of the nanofibers was in the range of 100 nm and could be tuned by type of LC template used, and the length of the nanofibers could be precisely controlled by varying the thickness of the LC film. The overall shape of the nanofibers could be controlled by the internal ordering of the LC template, as exemplified by the assembly of helical nanofibers using cholesteric LC as the template. PPX nanofibers could be applied to a broad range of materials, such as curved surface, metal meshes and microparticles. We successfully created nanofibers with different surface functionalities and utilized them to capture molecules of interest. We also demonstrated the synthesis of twisted nanofibers using chiral-substituted precursors. The direction and the degree of twisting of nanofibers could be controlled by the handedness and the enantiomeric excess of the chiral precursor. Finally, we showed that the LC-templated CVD method could be extended to fabricating nanofibers made of other CVD-based polymer systems, such as poly(lutidine) and poly(p-phenylene vinylene). Our work opens a new platform for designing functional polymer nanostructures with programmable geometry, alignment and chemistry. The polymer nanostructures can be attractive for applications ranging from sensors, affinity filtration, and catalytic supports.