Rare Earth Elements (REEs: La–Lu, Y, and Sc) are critical components for technological innovations, therefore more effective methods for the domestic extraction and purification of REEs are in ever-increasing demand. Metal-chelating polymers have great potential in these applications due to their relatively low cost and high affinity for target elements. However, while much research has focused on specific ligands attached to polymers, little is known about the effect of polymer architecture itself on metal chelation. This dissertation reports recent progress in the design, synthesis, and application of polymers for the chelation of various REEs. In addition to synthesizing a series of metal-chelating polymers, we elucidated the thermodynamics of binding using isothermal titration calorimetry (ITC) to gain insight into the specific relationship between polymer structure and metal binding. ITC enables the direct measurement of the binding affinity (Ka), enthalpy changes (ΔH), and stoichiometry of the interactions between macromolecules and metal ions in solution. The thermodynamics of metal chelation underpins many technologies for REE extraction. Consequently, elucidating these parameters enables the rational design of future materials. / Doctor of Philosophy / Rare-Earth Elements (REEs) are critical metals used in many modern technologies, therefore more effective methods for the recovery and purification of REEs are in ever-increasing demand. Metal-chelating polymers—materials that can bind metals—have great potential in these applications due to their relatively low cost and high affinity for target elements. However, while much research has focused on the specific metal-binding group attached to the polymer, little is known about the effect of polymer architecture itself on metal chelation. This dissertation reports recent progress in the design, synthesis, and application of materials that bind to various REEs. In addition to synthesizing a series of metal-binding polymers, we measured the heat absorbed or produced during metal-binding interactions. These experiments produced fundamental insights into the interactions between the polymers, metals ions, and water molecules in solution. Overall, this work produces a depiction of the polymer–metal binding process, which enables insight into each polymer's properties as a metal-binding material. Future researchers can use these guidelines to develop the next generation of materials for the extraction of these critical metals.

Thesis (PhD (Chemistry and Polymer Science))--Stellenbosch University, 2008. / The research presented in this dissertation was concerned with the living radical polymerization (LRP) of an amphiphilic, water-soluble, bi-substituted and biologically compatible acrylamide derivative, namely n-acryloylmorpholine (NAM). The primary objective of this research was the synthesis of novel block copolymers containing poly(dimethylsiloxane) (PDMS) and various chain lengths of poly(acryloylmorpholine) (polyNAM) using a LRP technique, namely reversibleaddition fragmentation chain transfer (RAFT) polymerization. This is the first report on the synthesis of these block copolymers using RAFT polymerization. These novel siloxane block copolymers were synthesized using a monohydroxyterminated PDMS material which had to first be modified into a thiocarbonylthiocontaining moiety in order for it to be used as macromolecular chain transfer agent (macroCTA) in the RAFT copolymerization with NAM. Suitable reaction conditions for the synthesis of these novel block copolymers had to, firstly, be determined, and secondly, optimized. In order to determine suitable reaction conditions, a series of homopolymerizations with NAM were first performed in order to compare which chain transfer agent (CTA), solvent, temperature etc. could possibly be best suited for the block copolymerizations of PDMS-b-polyNAM. Reported in this work is the first account of the homopolymerization of NAM and 2-(dodecylsulfanyl)thiocarbonylsulfanyl-2-methyl propionic acid (DMP) as CTA using RAFT polymerization. The resulting novel siloxane block copolymers are amphiphilic in nature and the existence of these structures was confirmed by size exclusion chromatography/multiangle light scattering (SEC/MALS), proton nuclear magnetic resonance (1H-NMR) spectroscopy, gel elution chromatography (GEC) and transmission electron microscopy (TEM). Interesting phase behaviour was observed in the latter technique.

Conjugated polymers hold tremendous potential as low-cost, solution processable materials for electronic applications such organic light-emitting diodes and photovoltaics. While the concerted efforts of many research groups have improved the performance of organic electronic devices to near-relevant levels for commercial exploitation over the last decade, the overall performance of organic light-emitting diode and organic photovoltaic devices still lags behind that of their traditional, inorganic counterparts. Realizing the full potential of organic electronics will require a comprehensive, molecular-level understanding of conjugated polymer photophysics. Studying pure, well-defined, and reproducible conjugated polymer materials should enable these efforts; unfortunately, conjugated polymers are typically synthesized by metal-catalyzed step-growth polycondensation reactions that do not allow for rigorous control over polymer molecular weight or molecular weight distribution (i.e., dispersity). Chain-growth syntheses of conjugated polymers would not only allow for precise control over the aforementioned polymer metrics such as molecular weight and dispersity, but could also potentially create new applications by enabling the preparation of more advanced macromolecular structures such as block copolymers and surface grafted polymers. Our efforts toward realizing these goals as well as toward exploiting chain-growth methodologies to better understand fundamental conjugated polymer photophysics and self-assembly will be presented. / text

The synthesis of well-defined polymer nanoparticles will have immediate applications in the biomedical industry as nanocontainers for the controlled delivery and release of water insoluble drugs. The ability to control molecular weight, particle morphology and chemical functionality and to obtain polymeric nanoparticles with narrow molecular weight and particle size distributions is paramount for their application-specific design. Two synthetic approaches were investigated in the synthesis of well-defined polymer nanoparticles, emulsion polymerization and self assembly. The successful implementation of Reversible Addition-Fragmentation Chain Transfer (RAFT) in emulsion polymerization was the first challenge faced when controlling nanoparticle molecular weight and size. Initially we showed that successful ‘living’ emulsion polymerizations of styrene could be carried out using a non-ionic surfactant. The success was achieved when preparing polymers of low molecular weight (5 and 9 K targeted Mn’s with polydispersities (PDIs) below 1.2). Deviation from ideal ‘living’ behavior occurred when targeting Mn’s greater than 20 K (at 100 % conversion). The ‘degassing technique’ was then investigated as an avenue to generate stable polystyrene nanoparticles by emulsion polymerization without the addition of surfactant (residual surfactant can result in detrimental effects on product quality). The polymerization of this emulsion system in the presence of a low reactive RAFT agent was ‘living’ in nature. In the presence of a high reactive RAFT agent the emulsion system showed ‘living’ nature, however, secondary nucleation occurred, which resulted in broad molecular weight distribution (MWD). Thus, the emulsion polymerization approach to preparing well-defined polymer nanoparticles was giving less than desirable results. An alternative method to prepare polymer nanoparticles with controlled chemical composition and morphology is to self assemble pre-synthesized block copolymers in water. This approach has several significant advantages over the emulsion systems: (i) all polymer chains are of near uniform chain length and chemical composition, (ii) the ratio between the hydrophobic and hydrophilic polymers can easily be controlled, (iii) chemical functionality can be located in different morphological regions, (iv) a wide range of 3-dimensional structures apart from spheres can be prepared (i.e. rods and vesicles), and (v) additives such as surfactant, stabilizers and residual monomer usually found after an emulsion polymerization are not required in the self assembly methodology. These advantages justify our shift in strategy. The only disadvantage of the self assembly process is that one cannot reach high weight fractions of polymer in water and is usually limited to below 2 wt-%, where as emulsion polymerizations can allow weight fractions of polymer close to 50 wt-%. Well-defined amphiphilic 4-arm star polyacrylic acid-block-polystyrene (PAA-b-PSTY) copolymers, prepared by RAFT solution polymerization, were dispersed in water to form core-shell micelles, in which the shell consisted of tethered PAA loops. The entropic penalty for having such loops resulted in a less densely packed PSTY core when compared to linear diblock copolymers of the same arm length. The surface of the shell was irregular due to the tethering points, but when cleaved the PAA chains extended to form a regular and relatively uniform corona. Controlling the polymer architecture enabled the synthesis of polymer micelles with tethered PAA loops, which could be opened to form uniform corona when desired. Three-miktoarm star and dendrimers with miktoarms consisting of PSTY, polytert-butyl acrylate (PtBA), polymethyl acrylate (PMA) and PAA were then synthesized using a combination of Atom Transfer Radical Polymerization (ATRP) and Huisgen 1,3-dipolar cycloaddition ‘click’ reactions. In all reactions, the stars and dendrimers were well-defined with PDIs lower than 1.09. This was the first step in the synthesis of well-defined highly ordered polymer structures. The synthesis of such structures demands high level of purity at each synthetic step eliminating the possibility of side reactions, which as of consequence lowers product yields. The synthesis and use of reactive solid supports to remove excess linear polymer to increase the yields of polymeric 3-arm stars and dendrimers was employed. These supports are a cheap approach to scavenge polymeric species with either azido or alkynyl functionality, after which the solid support can be filtered away from the product. These supports aided the synthesis of 3rd generation polymeric dendrons and dendrimers consisting of homopolymer PSTY with either solketals or alcohols at the periphery, diblock PSTY and PtBA, and amphiphilic diblock. The methodology used to construct these structures was a combination of ATRP to produce linear polymers with telechelic functionality, with the subsequent use of this functionality to join the polymers together via ‘click’ reactions. Micellization of the amphiphilic structures in water produced polymer nanoparticles of uniform size. The dendrimer nanoparticles were 18 nm in diameter, consisting of 19 individual dendrimers. The dendrimers most probably have no mutual interpenetration and thus pack uniformly to form the micelles. The dendron nanoparticles were 21 nm with an aggregation number of 43 dendrons per micelle, which suggests they form cone-like structures and self-assemble to form crew-cut micelles. Using a convergent approach polymer structures with unprecedented chemical diversity (hydrophobic or amphiphilic) and complexity (G2 miktoarm dendrimers with a degradable core) consisting of PSTY, PMA, PtBA and PAA were then synthesized with high purity using copper wire as the ‘click’ catalyst.

No description available.

Autophagy is a critical cellular maintenance machinery in cells, and prevents the accumulation of toxic protein aggregates, organelles or lipid droplets through degradation via the lysosome. In macro-autophagy, autophagosome first engulfs around aggregates or cellular debris and subsequently fuses with a lysosome that is sufficiently acidic (pH 4.5–5.5), where the contents are then degraded via lysosomal enzymes. Autophagy inhibition as a result of lysosomal acidification dysfunction (pH > 5.5) have been reported to play a major role in various diseases pathogenesis. Hence, there is a pressing need to target lysosomal pH to rescue autophagy. Nanoparticles are attractive materials which has been shown to be efficiently uptaken into cellular organelles and can serve as an agent to specifically localize into lysosomes and modulate its pH. Lipotoxicity, induced by chronic exposure to free fatty acids, and exposure to neurotoxins (e.g. MPP+), elevates lysosomal pH in pancreatic beta cells (Type II Diabetes, T2D) and hepatocytes (Non-alcoholic fatty liver disease, NAFLD), and PC-12 cells (Parkinson’s Disease), respectively. We first tested the lysosome acidification capability of photo-activable nanoparticles (paNPs) and poly (lactic-co-glycolic) acid nanoparticles (PLGA NPs) in a T2D model. Both NPs lowered lysosomal pH in pancreatic beta cells under lipotoxicity and improved insulin secretion function. However, paNPs only release acids upon UV trigger, limiting its applicability in vivo, while PLGA NPs degrade upon lysosome localization. We further showed that PLGA NPs are able to rescue MPP+ induced cell death in a PD model, though it has a slow degradation rate. To attain the most efficacious nanoparticle with a fast degradation and acidification rate, we synthesized acidic nanoparticles (acNPs) based on tetrafluorosuccinic and succinic acids to form optimized nanoparticles. The acNPs showed faster rescue of cellular function compared to PLGA NPs in the PD model. Finally, we tested the acNPs in NAFLD model, and where lysosomal pH reduction by acNPs restored autophagy, reduced lipid accumulation, and improved mitochondria function in high-fat diet mice. In sum, nanoparticles are of potential therapeutic interest for pathologies associated with lysosomal acidity impairment. Future studies include testing the acNPs in NASH disease model and clinical studies. / 2022-05-18T00:00:00Z

No description available.

No description available.

Polylactic acid (PLA) resins of various molecular weights and molecular weight distributions were synthesized. Linear, narrow molecular weight distribution (MWD) PLA resins were synthesized, as well as resins containing both high molecular weight branched structures and low molecular weight chains and oligomers. Narrow MWD resins were synthesized for use as adhesives for corrugated paperboard and broad MWD resins were synthesized for use as a waterborne coating. PLA resins were dispersed for use as a waterborne coating. Success has been made at forming films utilizing various plasticizers and surfactants as well as polyvinyl alcohol as dispersing agents. A cold dispersion procedure realized the most success, as a 15% PLA waterborne formulation was achieved. Standard test methods show a high degree of grease resistance for the formulated coatings. A hot melt adhesive was also formulated utilizing blends of narrow MWD resins of various molecular weights. The hot melt adhesive showed a high degree of success as failure occurred at the substrate for the materials tested.

<p> Dramatic advances over the past decade have occurred in the use of cryogenic electron microscopy (cryoEM) to elucidate the structures of macromolecules at atomic resolution. Unfortunately, the sample preparation process is one of the most time-consuming and empirical methods in the cryoEM workflow. Each sample must be tediously optimized to resolve issues with particle aggregation, ice quality, particle orientation, and particle density to enable high-resolution reconstruction analysis. Post-polymerization modifications of synthetic aqueous bottlebrushes offer a promising approach to streamline the workflow for cryoEM sample preparation. Our approach utilizes synthetic bottlebrush materials comprised of flexible polymer scaffolds bearing grafted side-chains, armed with high affinity ligands at the distal termini of the grafted polymers along the polymer core. Development of water-soluble one-dimensional (1D) synthetic bottlebrush polymers has led to new advancements in the biomaterials, antimicrobial, nanomedicine, and responsive materials fields. These synthetic bottlebrush materials are favorable as they confer properties that linear polymers and small molecules cannot achieve. Moreover, structural manipulations employed during post-polymerization processes can afford bottlebrush polymers with distinguishable topologies for advanced functions. These 1D constructs can be synthesized by atom transfer radical polymerization (ATRP), reversible addition- fragmentation chain-transfer polymerization (RAFT), ring-opening polymerization (ROP), cationic ring-opening polymerization (CROP), anionic ring-opening polymerization (AROP) or ring opening metathesis polymerization (ROMP). The chemical composition of the molecule, number of monomer repeats, grafting density and topology influence the morphology and function of polymer brushes. Elongated, vesicular or micellar morphologies can be specifically tuned for the desired application of the material. The morphology of the polymers can also be manipulated by concentration effects. The morphologies of amphiphilic bottlebrush materials specifically, can typically be influenced by structural topology, solvent choice, or external conditions. ROMP is a living polymerization mechanism that can suffer from catalytic backbiting, causing a loss of livingness. The synthesis of aqueous bottlebrush polymers and the comparison of morphologies via AUC, DLS, AFM and TEM will be presented in this dissertation. The synthetic amphiphilic bottlebrush polymer family presented suffered a loss of livingness and ultimately displayed distinct morphologies, relative to chemical composition, solvent, and ultimately polymerization time. Post-polymerization 11 modifications such as backbone hydrolysis and single-walled carbon nanotube complexation promoted even more unique morphologies of bottlebrushes. These synthetic materials indicate use as promising reagents for cryoEM sample preparation.  </p>