This thesis presents a study of polystyrene (PS) microgel (MG), hole transfer materials (HTMs) and perovskite solar cells (PSCs) and associated effects to combine them together to increase the stabilities of PSCs. PSCs are a disruptive technology which attract a lot of attention because of their remarkable power conversion efficiency (PCE). However, PSCs are very fragile and easy to be damaged by moisture and oxygen. The PS MGs are solvent-swellable, inherently colloidally stable, hydrophobic, and have good film-forming properties. In the study, we mixed PS MG with three different HTMs, poly(3-hexylthiophene) (P3HT), Poly[bis(4-phenyl)(2,5,6-trimethylphenyl)amine (PTAA) and 2,2',7,7'-Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD) to establish a diagram of concentrations of each component to form films. We investigated the morphology and light absorption and photoluminescence (PL) of HTM-MG films spin-coated from HTM-MG dispersions. The films containing flattened MG with an aspect ratio of around 10. MG islands containing packed particles were evident for both pure MG and P3HT-MG.

Hydrogels are cross-linked networks of highly hydrophilic polymer chains. When reduced to colloidal dimensions, particles of this sort are termed “microgels�? and both discrete particles and ensembles have intriguing properties. Microgels can be made to be susceptible to numerous environmental stimuli, such as temperature and pH. The resultant changes in the network hydration lead to characteristic swelling responses which can have great impact on properties of the gel network such as the porosity, hydrophilicity, stiffness, or particle-particle packing. The multitude of responsive stimuli; the architectural versatility of discrete particles; and the variety of particle ensembles have made the study of microgels and their assemblies a very rich field. Primarily due to their physiological softness and the aforementioned versatility, responsive microgels are of great interest as a material to address the daunting challenges facing the next generation of healthcare. This dissertation describes investigations into hydrogel nanoparticles and assemblies thereof, with the goals of expanding their utility in applications such as drug delivery and non-fouling interfaces through the development of novel materials to both extend their synthetic versatility and to probe their underlying properties. Physiologically-relevant degradable cross-linking within microgels is studied, though the incorporation of hydrolytically degradable or reduction-responsive cross-links. More complex structures are demonstrated for both types of cross-linking as synthetic and architectural control enables additional functional microgel designs. Microgel assemblies, particularly thin films, have been demonstrated to have numerous desirable properties for biological applications, such as reduced cell attachment, drug delivery, and self-healing capabilities. This dissertation includes additional fundamental studies of microgel films, both in their synthesis, such as methods for depositing films onto colloidal substrates, and in their application, as investigations into the origins and critical factors for self-healing films. Further, the cell-resistant properties of microgel multilayers are studied and evidence suggests that the viscoelastic or mobile character of the films is likely the main factor that directs cell adhesion. The work in this dissertation serves to both expand our toolset with regard to the functional synthesis of microgels and assemblies and to improve our fundamental understanding of phenomena of interest for a variety of potential applications. Both of these should serve to allow the enormous potential of hydrogel nanoparticles and their assemblies to be more efficiently tapped for a wide range of applications in the field of biomaterials.

This thesis presents an investigation of cationic microgels based on poly(N-vinylformamide-co-glycidyl methacrylate) (PNVF-GMA) and poly(N-vinylformamide-co-2-(N-vinylformamido) ethyl ether) (PNVF-NVEE). They arestudied in the context of future heteroaggregated doubly crosslinked (DX) microgelsfor damaged heart tissue repair. The microgel particles were synthesised fromPNVF-GMA, which is also a water swellable microgel. The PNVF-GMA particleshad a core-shell structure in which PNVF provides the core and PGMA creates thecross-linked shell. The morphology of particles is that of a “cane-ball” like shape. There are interconnected ridges, and this unusual morphology can be controlled bythe weight fraction of GMA used during preparation. The hydrolysed PNVF-GMA(H-PNVF-GMA) particles were both positively and negatively charged. Moreover,charge patch aggregation occurred at low ionic strength. However, these microgelswere colloidally unstable after water rinsing due to shell fragmentation. PNVF microgel particles containing (N-Vinylformamido) ethyl ether (NVEE) as acrosslinking agent were also studied to avoid the fragmentation of the particles. Thismicrogel was hydrolysed in alkali conditions to provide poly(vinylamine-co-bis(ethyl vinylamine) ether) (PVAM-BEVAME), which contains primary aminegroups. It is proposed from the data presented that the content of hydrolysis was veryhigh and the particles were stable after hydrolysis owing to the stability of etherlinkage in NVEE. These microgels were able to swell upon decreasing pH. ThePVAM-BEVAME microgel with 9 mol% of BEVAME was then used to formdoubly crosslinked (DX) microgel. To form the inter-particles crosslinking, the vinylgroups were included by functionalisation using glycidyl methacrylate (GMA)monomer. The vinyl groups of neighbouring particles were linked together via freeradical reaction. The DX microgel formed under physiological temperature andshowed extensive porosity. These DX microgels had good mechanical propertiesconfirmed by high storage modulus (G’). Moreover, the precursor gels wereinjectable which is favourable for future biomaterial applications. The study providesa new family of cationic microgel that may be suitable for a future heteroaggregatedDX microgel for heart tissue repair.

Phospholipid liposome binding to hydrogel beads based on poly(N-isopropylacrylamide) (PNIPAM) is accomplished employing either avidin/biotin conjugation or hydrophobic modification of the microgels, and the ability to form single supported lipid bilayers is explored. The co-monomer acrylic acid (AA), evenly distributed or localized to the shell of the microgel, is included to facilitate post-polymerization chemical modification of the hydrogel beads. The degree of chemical modification of the microgels as well as the thermal behavior is monitored via 1H and 13C nuclear magnetic resonance (NMR). Liposomes composed of 1-palmitoyl-2-oleoyl-sn-glycero-3-phoshocholine (POPC) and a small amount of commercially available biotinylated-lipid are shown to bind as intact entities while sequestering internal contents to biotinylated hydrogel beads, utilizing avidin as the coupling agent. Under fusogenic conditions, these bound liposomes remain as individual vesicles. Alternatively, POPC liposomes are shown to bind to microgels modified to display single chain alkyl groups or cholesteryl moieties, and remain as intact vesicles. It is demonstrated that these liposomes become permeable at high hydrophobe content. Bound liposomes will fuse into larger structures under high hydrophobe content conditions, but remain permeable. The volume phase transition (VPT) characteristic of PNIPAM microgels is shown to influence the permeability of hydrophobically bound (low hydrophobe content), but not avidin/biotin conjugated, liposomes. The degree of liposome binding, as well as their resulting structures and permeability are investigated utilizing 31P NMR, fluorescence spectroscopy and microscopy. The microgel-bound liposome and microgel-supported lipid bilayer hybrid systems would be ideally suited to drug delivery and tissue engineering applications. The microgel-supported single lipid bilayer system would, in addition, potentially act as a cell model system for membrane dynamics and embedded amphiphile NMR studies.

Phospholipid liposome binding to hydrogel beads based on poly(N-isopropylacrylamide) (PNIPAM) is accomplished employing either avidin/biotin conjugation or hydrophobic modification of the microgels, and the ability to form single supported lipid bilayers is explored. The co-monomer acrylic acid (AA), evenly distributed or localized to the shell of the microgel, is included to facilitate post-polymerization chemical modification of the hydrogel beads. The degree of chemical modification of the microgels as well as the thermal behavior is monitored via 1H and 13C nuclear magnetic resonance (NMR). Liposomes composed of 1-palmitoyl-2-oleoyl-sn-glycero-3-phoshocholine (POPC) and a small amount of commercially available biotinylated-lipid are shown to bind as intact entities while sequestering internal contents to biotinylated hydrogel beads, utilizing avidin as the coupling agent. Under fusogenic conditions, these bound liposomes remain as individual vesicles. Alternatively, POPC liposomes are shown to bind to microgels modified to display single chain alkyl groups or cholesteryl moieties, and remain as intact vesicles. It is demonstrated that these liposomes become permeable at high hydrophobe content. Bound liposomes will fuse into larger structures under high hydrophobe content conditions, but remain permeable. The volume phase transition (VPT) characteristic of PNIPAM microgels is shown to influence the permeability of hydrophobically bound (low hydrophobe content), but not avidin/biotin conjugated, liposomes. The degree of liposome binding, as well as their resulting structures and permeability are investigated utilizing 31P NMR, fluorescence spectroscopy and microscopy. The microgel-bound liposome and microgel-supported lipid bilayer hybrid systems would be ideally suited to drug delivery and tissue engineering applications. The microgel-supported single lipid bilayer system would, in addition, potentially act as a cell model system for membrane dynamics and embedded amphiphile NMR studies.

No description available.

Hydrogels are water-swellable cross-linked polymeric networks that are capable of incorporating a variety of functionalities and responsivities. The stable colloidal form of a hydrogel is known as a microgel and ranges in size from the nano- to the micrometer scale. Microgels can exhibit similar properties to hydrogels, but the colloidal size of the microgel creates differences in their responsive behavior, such as faster reaction kinetics, as compared to their macrogel counterpart. Microgels have been explored for a broad range of applications, either as individual entities or within large scale assemblies. Although these materials have shown a great deal of utility and versatility, microgels have also demonstrated a great deal of complexity due to the fact that they exhibit both polymeric and colloidal properties. This so-called polymer/colloid duality creates intricacies in characterizing the behavior of these materials, especially when coupled with an oppositely charged component within multilayered assemblies. In this dissertation, work is focused primarily on building a greater fundamental understanding of microgels and their behavior within large scale assemblies. This is done through the development of new characterization techniques or through a direct visualization of the interactions of microgels with their surrounding environment with emphasis on their interaction with an oppositely charged linear polyelectrolyte. From these studies, a more developed fundamental understanding of microgels and their assembly into complex structures is obtained, and these findings will aide in the development of future applications of microgel assemblies.

Two series monodispersed nanoparticles of hydroxylpropyl cellulose (HPC) and functionalized poly-N-isopropylamide (PNIPAM) particles have been synthesized and used as building blocks for creating three-dimensional networks, with two levels of structural hierarchy. The first level is HPC nanoparticles were made from methacrylated or degradable cross-linker attached HPC. These nanoparticles could be stabilized at room temperature by residual methacrylate or degradable groups are present both within and on the exterior of HPC nanoparticles. Controlled release studies have been performed on the particle and networks .The nearly monodispersed nanoparticles have been synthesized on the basis of a natural polymer of hydropropylcellulose (HPC) with a high molecular weight using the precipitation polymerization method and self-assembly of these particles in water results in bright colors. The HPC nanoparticles can be potential using as crosslinkers to increase the hydrogels mechanical properties, such as high transparency and rapid swelling/de-swelling kinetics. The central idea is to prepare colloidal particles containing C=C bonds and to use them as monomers - vinylparticles, to form stable particle assemblies with various architectures. This is accomplished by mixing an aqueous suspension of hydrogel nanoparticles (PNIPAM-co-allylamine) with the organic solvent (dichloromethane) to grow columnar crystals. The hydrogels with such a unique crystal structure behavior not only like the hydrogel opals, but also have a unique property: anisotropy.

No description available.

<p> Temperature sensitive microgel latexes of poly (N-isopropylacrylamide) cross-linked with N-N'methylene bisacrylamide (BA) were prepared and characterized by Dynamic Light Scattering, Titration and Electrophoresis. The study of gels, including temperature sensitive gels, is limited by the large size of traditional bulk gels which are slow to respond to changes and are difficult to measure. An alternative system, which may be easier to study, is a microgel latex which would constitute small particles of gel which would respond quickly to changes in their environment and could also be measured using colloidal measuring techniques like dynamic light scattering and particle electrophoresis.</p> <p> Monodisperse and stable microgel latex particles were prepared by reacting Nisopropylacrylamide (NIPAM) monomer with a cross-linking agent BA in water at 70°C with a surfactant (sodium dodecylsulfate) present. Latexes prepared without surfactant were polydisperse.</p> <p> Characterization of the poly (NIPAM) particles by dynamic light scattering at several different temperatures showed that the particles go through a transition from a water swollen gel at low temperature to a shrunken gel with a low water content at high temperature. The transition occurs about 32°C. The degree of swelling of the poly (NIPAM) particles can be expressed by the Flory-Huggins Interaction parameter c and is dependent upon the level of cross-linking agent included.</p> <p> Titration and electrophoresis results indicate that the particles contain about 0.39 Coulombs per gram of polymer of carboxylic and sulfuric charged end groups which are distributed throughout the particle.</p> / Thesis / Master of Engineering (MEngr)