<p>QC 20150323</p>

Atom transfer radical polymerization (ATRP) has proven to be a powerful technique to obtain polymers with narrow polydispersities and controlled molecular weight. It also offers control over chain-ends. The technique is the most studied and utilized of thecontrolled/”living” radical polymerization techniques since a large number of monomerscan be polymerized under simple conditions. ATRP can be used to obtain polymer graftsfrom multifunctional substrates. The substrates can be either soluble (i. e. based ondendritic molecules) or insoluble (such as gold or silicon surfaces). The large number ofgrowing chains from the multifunctional substrates increases the probability of inter-and intramolecular reactions. In order to control these kinds of polymerizing systems, andsuppress side-reactions such as termination, the concentration of propagating radicalsmust be kept low. To elaborate such a system a soluble multifunctional substrate, based on 3-ethyl-3-(hydroxymethyl)oxetane, was synthesized. It was used as a macroinitiatorfor the atom transfer radical polymerisation of methyl acrylate (MA) mediated byCu(I)Br and tris(2-(dimethylamino)ethyl)amine (Me6-TREN) in ethyl acetate at room temperature. This yielded a co-polymer with a dendritic-linear architecture. Since mostsolid substrates are sensitive to the temperatures at which most ATRP polymerisations are performed, lowering the polymerization temperatures are preferred. ATRP at ambienttemperature is always more desirable since it also suppresses the formation of thermally formed polymer. The macroinitiator contained approximately 25 initiating sites, which well mimicked the conditions on a solid substrate. The polymers had low polydispersity and conversions as high as 65% were reached without loss of control. The solid substrateof choice was cellulose fibers that prior to this study not had been grafted through ATRP.As cellulose fibers a filter paper, Whatman 1, was used due to its high cellulose content.The hydroxyl groups on the surface was first reacted with 2-bromoisobutyryl bromidefollowed by grafting of MA. Essentially the same reaction conditions were used that hadbeen elaborated from the soluble substrate. The grafting yielded fibers that were very hydrophobic (contact angles&gt;100°). By altering the sacrificial initiator-to-monomer ratiothe amount of polymer that was attached to the surface could be tailor. PMA with degreesof polymerization (DP’s) of 100, 200 and 300 were aimed. In order to control that thepolymerizations from the surface was indeed “living” a second layer of a hydrophilicmonomer, 2-hydroxymethyl methacrylate (HEMA), was grafted onto the surface. Thisdramatically changed the hydrophobic behavior of the fibers. / QC 20100524

Lignocellulosic biomasses are an important source of chemical components such as cellulose, lignin and hemicelluloses, and can be used for a variety of purposes in both the pulp and paper and chemical conversion industries. Xylan, the main hemicellulose found in hardwood and grass plants, plays an important role during the pulping/pretreatment process reactions, including those used in 2nd generation bioethanol production. It may also play an important role in the production of certain novel materials. This thesis evaluates the composition of eucalyptus (Eucalyptus urophylla x Eucalyptus grandis), sugarcane bagasse and sugarcane straw, with a specific focus on the structure and properties of xylan. The chemical characterization of biomasses showed that sugarcane bagasse and straw contain larger amounts of extractives, ash and silica than eucalyptus. The large amount of silica leads to an overestimation of the Klason lignin content, if not corrected. By using a complete mass balance approach, sugarcane bagasse and straw were shown to contain smaller amounts of lignin (18.0% and 13.9%, respectively) than previously reported for these raw materials, and certainly a much smaller amount of lignin than was found in eucalyptus (27.4%). The hemicellulose content in sugarcane bagasse (28.7%) and straw (29.8%) was much higher than that in eucalyptus (20.3%). In order to investigate the structure of the xylan in greater detail, it was extracted with dimethyl sulfoxide from holocellulose, obtained by either peracetic acid or sodium chlorite delignification. The structure of the isolated xylans was confirmed by FTIR and 1H NMR analysis. In eucalyptus, the O-acetyl-(4-O-methylglucurono)xylan (MGX) was identified. This had a molar ratio of xylose units to branches of 4-O-methylglucuronic acid of 10:1.1 and a degree of acetylation of 0.39. All 4-O- methylglucuronic acid groups were attached to position O-2 of the xylose units, which had an acetyl group in position O-3. The acetyl groups were distributed in positions O-3 (64%), O-2 (26%) and O-2,3 (10%). The MGX had a molecular weight (Mw) of about 42 kDa. In bagasse and straw, arabinoxylan (AX) was identified. This had a molar ratio of xylose units to arabinosyl substitutions of 10:0.5 for bagasse and 10:0.6 for straw. A degree of acetylation was 0.29 and 0.08 for bagasse and straw, respectively. The arabinose units were attached preferentially to position O-3 in AX. In the xylan from bagasse, the acetyl groups were found in positions O-3 (60%), O-2 (13%) and O-2,3 (27%), while in the xylan from straw, the acetyl groups were distributed between positions O-3 (67%) and O-2 (33%). The AX had a molecular weight (Mw) of about 38 kDa and 30 kDa for bagasse and straw, respectively. The differences in the structure of xylan present in the various biomasses played an important role during hydrothermal pretreatment, which is often used as the first step in 2nd generation ethanol production. The varying amounts of uronic acid and acetyl groups resulted in different starting pH levels of liquor and, thus, affected the chemical transformation in the biomasses in different ways. The hydrothermal pretreatment resulted mostly in the removal and/or transformation of hemicelluloses, but also in the formation of a significant number of pseudo-lignin structures. In addition, in eucalyptus, pseudo-extractives structures were generated. The sugarcane straw showed the highest mass loss during the investigated pretreatment. / <p>QC 20151023</p>

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Malaria parasite infects more than 200 million people and about 435 000 succumb to the illness annually (WHO, 2019). Victims are mostly young children and pregnant women. It is transmitted by the bite of the infected female Anopheles mosquitoes. Indoor protection is provided by bed nets and residual spraying of insecticides. Mosquitoes typically bite ankles and feet most of the time (93%) whilst in outdoor settings. Long lasting insect-repellent anklets/bracelets/footlets may provide a strategy for reducing mosquito bites outdoors in the lower limb regions. This study considered long-lasting repellent anklets that may be used for outdoor protection against mosquito bites. Experiments were performed to investigate the incorporating of mosquito repellents into the thermoplastic polymers, poly(ethylene-co-vinyl acetate) (EVA) and linear low-density polyethylene (LLDPE). Two different mosquito repellents, namely DEET and Icaridin, were employed. The target was to develop cost-effective bracelets with long-lasting efficacy, i.e., slow release of the active ingredient over extended periods. In this way, it is expected to protect people from acquiring mosquito-borne diseases during the time they spend outdoors. The proposed concept utilises microporous polymer strands manufactured via conventional plastic extrusion processes. The internal open-cell polymer foam structure serves both as a reservoir and a protective environment for the active ingredient trapped inside. An outer dense skin layer covering the strands may provide the necessary diffusion barrier that controls the release of repellent at effective levels over a considerable period. The objective was achieved by phase separation via spinodal decomposition (SD), triggered by extruding the molten strands directly into ice-cold water. Thermogravimetric analysis (TGA) and solvent extraction confirmed that all of the repellents were embedded in the polymer matrices. Scanning Electronic Microscopy (SEM) confirmed the porous co-continuous repellent-polymer microstructure. The stability of the polymer matrix was studied by estimating the swelling and shrinkage of the polymer matrix. The release of the active ingredient in the polymer/repellent system was followed as a function of oven-ageing temperature and time. The kinetics of the release rate of the repellent from microporous polymer matrix strands was mathematically modelled using semi-empirical models. The performance of the repellent-based strands was evaluated using foot-in-cage repellence testing. Finally, an attempt was made to predict the phase diagrams of the LLDPE/repellent system on the basis of alkane/repellent systems data. The results confirmed that EVA and LLDPE are suitable scaffold matrices, acting as reservoirs, for liquid repellents that were released at a constant rate. As expected, the repellent swelled EVA more than LLDPE. As a result, it also shrank significantly more when the repellent was released, i.e. EVA showed poor dimensional stability compared to LLDPE. The semi-empirical repellent release models were found valuable as they provided insights into the way that the repellent was being released. They allowed differentiating between diffusion and relaxation mechanisms. It was found that repellence efficacy can be maintained for more than 90 days. Future developments of sandals and anklets based on this approach may assists in preventing outdoor mosquito bites, thereby decreasing malaria infection rates. / Thesis (PhD)--University of Pretoria, 2019. / Deutsche Forschungsgemeinschaft (DFG) Grant AN 212/22-1 / Chemical Engineering / PhD / Unrestricted

Indiana University-Purdue University Indianapolis (IUPUI) / A Polyvinylchloride surface was modified by coating a biocompatible, hydrophilic and antibacterial polymer by a mild surface modification method. The surface was first activated and then functionalized, followed by coating with polymer. The surface functionality was evaluated using cell adhesion, bacterial adhesion and bacterial viability for polymers with antibacterial properties. 3T3 mouse fibroblast cells were used for cell adhesion, Pseudomonas aeruginosa, Escherichia coli, and Staphylococcus aureus were used for bacterial adhesion in the first study, Pseudomonas aeruginosa and Staphylococcus aureus were used for bacterial adhesion and antibacterial activity in the second study. Chapter 2 reports how we synthesized, immobilized and evaluated a novel hydrophilic polymer with anti-fouling properties onto surface of polyvinylchloride via an effective and mild surface coating technique. The polyvinylchloride surface was first activated by azidation as well as amination, and then tethering a newly synthesized hydrophilic and biocompatible polyvinylpyrrolidone having pendent reactive succinimide functionality onto the surface. Results show that the coated hydrophilic polymer significantly reduced the 3T3 fibroblast cell adhesion as well as the adhesion of the three bacterial species. Chapter 3 reports how we prepared, immobilized and evaluated an antibacterial and anti-fouling polymer onto polyvinylchloride surface following an efficient and simple method of surface modification. The surface coated with a terpolymer constructed with N-vinylpyrrolidone, 3,4-Dichloro-5-hydroxy-2(5H)-furanone derivative and succinimide residue was evaluated with cell adhesion, bacterial adhesion and bacterial viability. Surface adhesion was evaluated with 3T3 mouse fibroblast cells and two bacterial species. Also, antibacterial activity was evaluated by bacterial viability assay with the two bacterial species. Results showed that the polymer-modified polyvinylchloride surface exhibited significantly decreased 3T3 fibroblast cell adhesion and bacterial adhesion. Furthermore, the modified polyvinylchloride surfaces exhibited significant antibacterial functions by inhibiting bacterial growth with bactericidal activity. Altogether, we have successfully modified the surface of polyvinylchloride using a novel efficient and mild surface coating technique. The first hydrophilic polymer-coated polyvinylchloride surface significantly reduced cell adhesion as well as adhesion of three bacterial species. The second hydrophilic and antibacterial polymer-coated polyvinylchloride surface demonstrated significant antibacterial functions by inhibiting bacterial growth and killing bacteria in addition to significantly reduced 3T3 fibroblasts and bacterial adhesions.

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