This thesis addresses three issues. These are the self-assembly of block copolymer in selective solvents, hierarchical assembly of micelles or crosslinked micelles of block copolymers, and the application of block copolymers as solid state compatibilizers in polymer-based photovoltaic cells. Poly(acrylic acid)-block-(2-cinnamoyloxylethyl methacrylate)-block-poly(perfluorooctylethyl methacrylate) or PAA-b-PCEMA-b-PFOEMA self-assembles in solvent mixtures of α,α,α-trifluorotoluene (TFT) and methanol, which are selective towards PAA. At TFT volume fraction (fTFT) of 40 %, the copolymer forms vesicles at 70 oC and cylinders at 21 oC. These two structures inter-convert via meta-stable intermediates including jellyfish-like, tethered vesicular, and bilayer sheet-like structures. These structures occur in kinetic experiments involving quick temperature swing from 21 to 70 oC or vice versa and also in experiments involving annealing samples long at temperatures between 21 to 70 oC. Thus, they are meta-stable and point to complex pathways for the morphological transition. At fTFT = 10 %, the polymer forms vesicles with bumpy surface at 70 oC and toroids with sharp angles at 21 oC. Closely examined is how the liquid crystalline nature of the PFOEMA block affects the formation of these unique morphologies and their morphological transitions. Two types of hierarchical assembly of cylindrical micelles (cylinders) or crosslinked cylindrical micelles (fibers) of block copolymers are examined. First, carboxyl-bearing nanofibers of PAA-b-PCEMA and amino-bearing nanocylinders from poly(tert-butyl acrylate)-block-poly(2-cinnamoyloxyethyl methacrylate)-block-poly(2-dimethylamino-ethylmethacrylate), PtBA-b-PCEMA-b-PDMAEMA, are mixed in solvent. The two species firstly aggregate via electrostatic interaction. Upon heating and aging, the cylinders dissociate on the fibers and eventually evolve into composite multilayered cylindrical structures. Second, layer-by-layer (LBL) deposition of carboxyl- and amine-bearing nanofibers yielded multilayer films. These films detached from a substrate separate nanospheres based on their size and surface charge differences. Diblock copolymers poly(3-hexylthiophene)-block-poly(2-cinnamoyloxyethyl methacrylate-random-2-[6,6]-phenyl-C61-butyroyoxyethyl methacrylate) (T-C60C) and poly(3-hexylthiophene)-block-poly(2-acetoxyethyl methacrylate-random-2-[6,6]-phenyl-C61-butyroyoxyethyl methacrylate) (T-C60A) are synthesized and used as compatibilizers for polymer-based photovoltaic cells containing poly(3-hexylthiophene) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Both copolymers can stabilize the morphology of the active layer and thus the device performance. T-C60A in the active layer yields longer life-times and better initial performance of the devices, due to the matching of surface tensions between C60A and PCBM. / Thesis (Ph.D, Chemistry) -- Queen's University, 2013-02-05 13:45:04.189

No description available.

As a part of a larger effort towards the fundamental understanding of mechanical behaviors of polymers toughened by nanoparticles, this dissertation focuses on the structure-property relationship of epoxies modified with nano-sized poly(ethylene-altpropylene)- b-poly(ethylene oxide) (PEP-PEO) block copolymer (BCP) micelle particles. The amphiphilic BCP toughener was incorporated into a liquid epoxy resin and selfassembled into well-dispersed 15 nm spherical micelle particles. The nano-sized BCP, at 5 wt% loading, can significantly improve the fracture toughness of epoxy (ca. 180% improvement) without reducing modulus at room temperature and exhibits only a slight drop (ca. 5 �C) in glass transition temperature (Tg). The toughening mechanisms were found to be BCP micelle nanoparticle cavitation, followed by matrix shear banding, which mainly accounted for the observed remarkable toughening effect. The unexpected ?nano-cavitation? phenomenon cannot be predicted by existing physical models. The plausible causes for the observed nano-scale cavitation and other mechanical behaviors may include the unique structural characteristics of BCP micelles and the influence from the surrounding epoxy network, which is significantly modified by the epoxy-miscible PEO block. Other mechanisms, such as crack tip blunting, may also play a role in the toughening. Structure-property relationships of this nano-domain modified polymer are discussed. In addition, other important factors, such as strain rate dependence and matrix crosslink density effect on toughening, have been investigated. This BCP toughening approach and conventional rubber toughening techniques are compared. Insights on the decoupling of modulus, toughness, and Tg for designing high performance thermosetting materials with desirable physical and mechanical properties are discussed.

This research work examines the process of block copolymer membrane fabrication by self-assembly combined by non-solvent induced phase separation. Self-assembly takes place from the preparation of the primordial solution until the moment of immersion in a non-solvent bath. These mechanisms are driven thermodynamically but are limited by kinetic factors. It is shown in this work how the ordering of the assembly of micelles is improved by the solution parameters such as solvent quality and concentration of block copolymer. Order transitions are detected, yielding changes in the morphology. The evaporation of the solvents after casting is demonstrated to be essential to reach optimum membrane structure. The non-solvent bath stops the phase separation at an optimum evaporation time.

No description available.

In this dissertation, we studied two-phase microfluidics as a platform for the controlled synthesis of drug delivery polymeric nanoparticles (PNPs). The block copolymer we studied was poly(ε-caprolactone)-block-poly(ethylene oxide) (PCL-b-PEO). The anticancer drug we studied was paclitaxel (PAX). First, we explored microfluidic control of nanoparticle structure (size, morphology, and core crystallinity) on PCL-b-PEO PNPs without loaded PAX. We demonstrated the reproducible variability of PCL-b-PEO nanoparticle size and morphology. Microfluidic control of nanoparticle size and morphology was found to arise from the interplay of flow-induced particle coalescence and breakup. Next, we demonstrated the linear dependence of PCL core crystallization on flow-rate. We attributed this dependence of PCL core crystallization on flow-induced crystallization. We then used our microfluidic device to control PAX-loaded PNP structure and function (small molecule loading efficiency, diffusional release kinetics, and cytotoxicity). At low drug loading ratios (r < 0.1), we demonstrated reproducible variability of PAX-loaded PNP size and morphology. With increasing flow rate we were able to manufacture PNPs of high aggregation number. We were also able to reproducibly demonstrate the linear dependence of PCL core crystallinity on flow rate. Furthermore, PAX loading efficiency was dependent on PNP size and morphology. Formulations which consisted of cylindrical and lamellar type morphologies typically had higher PAX loading efficiencies, than formulations which consisted of spherical structures. Next, we studied diffusional PAX release, increasing core crystallinity correlated with slowing diffusional PAX release kinetics. At high drug loading ratios (r > 0.1), we demonstrated reproducible control of PAX-loaded PNP structure and function. PCL core crystallinity was a major factor influencing PNP size and morphology. Samples with high core crystallinity formed PNP structures with low internal curvature. Furthermore, core crystallization had a large influence on PAX loading efficiency; as samples with high PAX loading efficiency correlated with low PCL core crystallinity. With respect to diffusional PAX release, we found that increasing PCL core crystallinity correlated with slowing diffusional PAX release kinetics. Next, we studied the cytotoxicity of our PAX-loaded PNPs using the MCF-7 cancer cell line. Due to the complex nature of the interactions between our PAX-loaded PNPs and the cancer cells, we were not able to elucidate the exact influence of flow rate on PNP cytotoxicity. / Graduate

This thesis includes three studies on related aspects of structure and function control for drug delivery block copolymer nanoparticles manufactured in segmented gas-liquid microfluidic reactors. First, the self-assembly of a series of photoresponsive poly(o-nitrobenzyl acrylate)-b-polydimethylacrylamide copolymers is conducted in the gas-liquid segmented microfluidic reactor at various flow rates. The resulting morphologies are found to be flow-variable and distinct from nanoparticles prepared off-chip by dropwise water addition. Photocleaving of the nanoparticles formed at different flow rates reveal flow-variable photodissociation kinetics. Next, we conduct a direct comparison between a commercially-available single-phase microfluidic mixer and the two-phase, gas-liquid segmented microfluidic reactor used in our group, with respect to nanoparticle formation from a typical block copolymer identified for drug delivery applications, polycaprolactone-b-poly(ethylene oxide). The two-phase chip yields morphologies and core crystallinities that vary with flow rate; however, the same parameters are found to be flow-independent using the single-phase mixer. This study provides the first direct evidence that flow-variable structure control is a unique feature of the two-phase chip design. Finally, we investigate structure and function control for paclitaxel (PAX)-loaded nanoparticles prepared from a series of poly(6-methyl caprolactone-co-ε-caprolactone)-block-poly(ethylene oxide) copolymers with variable 6-methyl caprolactone (MCL) content. For all MCL-containing copolymers, off-chip preparations form nanoparticles with no measurable crystallinity, although PAX loading levels are higher and release rates are slower compared to the copolymer without MCL. Both off-chip and on-chip preparations yield amorphous spheres of similar size from MCL-containing copolymers, although on-chip nanoparticles showed slower release rates, attributed to more homogeneous PAX distribution due to faster mixing. / Graduate

Doctor of Philosophy / Department of Chemistry / Takashi Ito / Polymer thin films have played an important role in our everyday lives ranging from industrial to biomedical applications. In this thesis, two major topics based on polymer thin films including photopolymerized self-assembled monolayer and nanoporous thin films derived from diblock copolymer are discussed. In the first part of this thesis, a well-packed self-assembled monolayer with phosphonic acid as head group and diacetylenic functional group in the tail formed on AlGaN/GaN surface. According to water contact angle and UV/Vis absorption spectroscopy data, the stability of this self assembled monolayer on oxidized AlGaN/ GaN surface can be improved by photopolymerization of SAMs. The photopolymerization efficiency of the SAMs is effected by the position of polymerization functional group in the alkyl chain. In the second part of this thesis, PS-b-PMMA diblock copolymer thin films were prepared, characterized and applied as a template for electron transfer efficiency determination. The surface COOH group in nanoporous thin films derived from PS-b-PMMA were modified with ferrocene redox moieties having different linker lengths in the organic phase. The surface functionalization efficiency was quantitatively assessed by measuring the monovalent probe cations released from the surface COOH groups via cation-exchange processes using highly- sensitive analytical techniques including spectrofluorometry and inductively coupled plasma mass spectrometry (ICP-MS). The surface coverage of the redox moieties is an important parameter to determine the electron hopping efficiency. The electron propagation resulted from electron hopping across relatively large spacing that was controlled by the motion of anchored redox sites. The longer linker led to the larger physical displacement range of anchored ferrocene moieties, facilitating the approach of the adjacent ferrocene moieties within a distance required for electron self-exchange reaction. Faradic currents originating from redox-involved electron hopping through the ferrocene moieties anchored onto the insulator surface decreased with increasing the concentration of beta-cyclodextrin ([beta]-CD) in aqueous solution. The current could be recovered by adding redox-inactive guest molecules of [beta]-CD to the solution.

No description available.

The aim of this work is to fabricate nanostructured membranes from polysulfone-based block copolymers through self-assembly and non-solvent induced phase separation. Block copolymers containing polysulfone are novel materials for this purpose providing better mechanical and thermal stability to membranes than polystyrene-based copolymers, which have been exclusively used now. Firstly, we synthesized a triblock copolymer, poly(tert-butyl acrylate)-b-polsulfone-b-poly(tert-butyl acrylate) through polycondensation and reversible addition-fragmentation chain-transfer polymerization. The obtained membrane has a highly porous interconnected skin layer composed of elongated micelles with a flower-like arrangement, on top of the graded finger-like macrovoids. Membrane surface hydrolysis was carried out in a combination with metal complexation to obtain metal-chelated membranes. The copper-containing membrane showed improved antibacterial capability. Secondly, a poly(acrylic acid)-b-polysulfone-b-poly(acrylic acid) triblock copolymer obtained by hydrolyzing poly(tert-butyl acrylate)-b-polsulfone-b-poly(tert-butyl acrylate) formed a thin film with cylindrical poly(acrylic acid) microdomains in polysulfone matrix through thermal annealing. A phase inversion membrane was prepared from the same polymer via self-assembly and chelation-assisted non-solvent induced phase separation. The spherical micelles pre-formed in a selective solvent mixture packed into an ordered lattice in aid of metal-poly(acrylic acid) complexation. The space between micelles was filled with poly(acrylic acid)-metal complexes acting as potential water channels. The silver0 nanoparticle-decorated membrane was obtained by surface reduction, having three distinct layers with different particle sizes. Other amphiphilic copolymers containing polysulfone and water-soluble segments such as poly(ethylene glycol) and poly(N-isopropylacrylamide) were also synthesized through coupling reaction and copper0-mediated reversible-deactivation radical polymerization. Finally, phase inversion membranes were prepared from polytriazole-polysulfone random copolymers, which were obtained by “clicking” 1,2,3-triazole ring substituents bearing OH groups onto the polysulfone backbone via copperI-catalyzed azide-alkyne cycloaddition. The increased hydrophilicity of membranes imparted the higher water permeability and fouling resistance to the ultrafiltration membranes. Polytriazole-b-polysulfone-b-polytriazole triblock copolymer was synthesized by RAFT and post-polymerization click modification. Hydrogen bond-mediated self-assembly induced the formation of a nanostructured polytriazole-b-polysulfone-b-polytriazole / poly(acrylic acid)-b-polysulfone-b-poly(acrylic acid) blend membrane with a 1: 1 stoichiometric ratio of triazole and acid. String-like fused micelles with polytriazole/poly(acrylic acid) corona were present on the membrane surface, after immersion in a coagulation bath of copper2+ aqueous solution.