The goal of this work is to examine the applicability of the Lauritzen-Hoflinan (LH) surface nucleation theory to the crystallization kinetics of poly(ε-caprolactone), PCL. This theory has successfully predicted a number of experimental observations such as the temperature dependence of spherulitic growth rates and the inverse relation between undercooling and the lamellar thickness. Claims have appeared in the literature that analysis of growth rate data using the LH theory does not yield physically meaningful parameters. This work will show that the lateral and fold interfacial free energy parameters, σ and σₑ, found by analysis with the LH theory are related to the chemical structure of the polymer chain in the case of PCL. The fold interfacial free energy is related to the chain stiffness, and a recent proposal relates σ to the characteristic ratio, C_∞. This work will examine the validity of the proposed relationship for the case of PCL. The effect of polymer chain architecture on the crystallization behavior was also investigated. The crystallization behavior of poly(ε-caprolactone) was compared and contrasted to that of a triblock copolymer containing (ε-caprolactone) blocks. / Ph. D.

Lignin, the second most abundant biopolymer on earth following cellulose, can be described as a million-ton, low cost, under-utilized resource. The use of lignin in polymeric products adds the highest value to the raw material. Production of engineering plastics from lignin is an attractive approach to the utilization of lignin. The use of lignin in structural materials is limited by its insolubility and its failure to undergo melt flow. A promising method to overcome the limitations is to chemically modify lignin by reaction with a low modulus substance, like an aliphatic ether. The reaction of lignin with propylene oxide (PO) produces a copolymer, hydroxypropyl lignin (HPL). Extensive studies have been directed toward the understanding of the chemistry and properties of HPL. A study of the process design is necessary to examine the economics of lignin propoxylation. This work includes the chemical and kinetic analysis of the lignin propoxylation reaction as well as the modelling of a semibatch polymerization process; the design of a lignin propoxylation pilot plant; and a preliminary study of an industrial plant. Two models for the lignin propoxylation reaction are proposed and analyzed to produce a mathematical description of the reaction process. The design of the pilot plant involves (a) the process design, which includes a material balance, a flow sheet, and a listing of the equipment; and (b) the economic analysis in which estimates of capital cost and operating costs are discussed. The scale-up to industrial production gives an estimate of the characteristics of a continuous process. This study constitutes a substantial contribution to the development of a new technology dealing with Engineering Plastics from Lignin. / Master of Science

Saturated steam (SS) and propylene oxide (PPO) fumigation are two common methods to improve microbiological quality and safety of tree nuts. Validation of these processes is needed to ensure adequate control of bacterial pathogens. Since pathogens cannot be studied in food processing environments, surrogates with resistance comparable to the pathogens needed to be identified. The objective was to investigate the suitability of Enterococcus faecium, Pediococcus acidilactici, and Staphylococcus carnosus as surrogate bacteria for Salmonella spp. on whole cashews and macadamia nuts, processed with SS or PPO. Whole cashews and macadamia nuts were co-inoculated with a cocktail of Salmonella enterica and one of the three potential surrogates. Nuts were dried to original aw, packaged in poly-woven bags (2.3 kg) and commercially processed using vacuum assisted steam at 80 ͦ C or PPO fumigation. Salmonella and the potential surrogates were enumerated by serial dilution, and plated onto TSA with overlay of XLT-4 (Salmonella) or media selective for the potential surrogates. Mean log reductions (CFU/g) of Salmonella and each potential surrogate were compared using a paired T-test. SS results: reduction of Salmonella (6.0 ± 0.14) was significantly larger than E. faecium (4.3± 0.12), or P. acidilactici (3.7± 0.14) on whole cashews. Salmonella (5.9 ± 0.18) was significantly larger than P. acidilactici (4.4± 0.18) on whole macadamia nuts. PPO results: reduction of Salmonella (7.3 ± 0.19) was significantly greater than E. faecium (6.4± 0.31), or P. acidilactici (6.3± 0.33) on whole macadamia nuts. Reduction of Salmonella was significantly greater than E. faecium and P. acidilactici reduction on cashews. P. acidilactici may be considered a surrogate for Salmonella reduction on whole macadamia nuts and whole cashews processed using SS at 80 ͦ C. E. faecium and P. acidilactici may be considered surrogates for Salmonella reduction on whole macadamia nuts and whole cashews processed using PPO. Reduction of St. carnosus exceeded that of Salmonella indicating it is not a suitable surrogate for Salmonella using either processing intervention. / Master of Science in Life Sciences

Propylene is the second most important starting chemical in the petrochemical industry after ethylene. Unlike ethylene, propylene readily undergoes substitution reactions including polymerisation, oxidation, halogenation, hydrohalogenation, alkylation, hydration, oligomerization and hydroformylation, which lead to a wide variety of important downstream products. One of the principal uses of propylene is to produce key chemicals from selective oxidation. In 2016, the world annual production of propylene is about 94 million tonnes, and the global proportion used to produce selective oxidation product is over 18%. They constitute a key part of the chemical industry and contribute towards substantial economic benefits. The application of Ag based heterogeneous catalysts to selective propylene oxidation is a key factor in the synthesis of nearly all downstream chemicals, however billions of pounds are lost every year due to unplanned reactor shutdown, safety control and environment unfriendly emission control as a results of inefficiency catalytic selectivity and activity. Despite, both theoretical and experimental research works have been intensively involved, the fundamental reason leading to these effects are not yet well understood. The work presented in this thesis explores a range of novel modification techniques that alter the activity of Ag nanocatalysts for selective propylene oxidation, especially in propylene epoxidation. Particular focus is placed on developing surface modified Ag catalysts through morphology control, surface architecture engineering with another sublayer metal. Using a combination of modelling, novel and traditional materials characterisation methods, it is found that these modification result in some significant electronic and/or geometric alterations to the Ag nanoparticles surface. The Ag-Ag bond distance can be dramatically enlarged by exposing a high-index Ag surface or a core-shell structure with monolayer Ag shell. When interacting with molecular oxygen, the molecular oxygen adsorption and dissociation behaviour is sensitive to the geometric changes in Ag surface. This leads to an enhanced selectivity toward propylene epoxidation than combustion resulting from preventing a C-H bond cleavage. Finally, be creating atomically dispersed Ag on zeolite, a completely different interaction between molecular oxygen and single atom Ag were discovered comparing to on a extensive silver surface. This leads to the observation of an excitingly new propylene oxidation reaction producing ethanol and CO₂ resulting from C=C bond cleavage. Overall, the research presented within this thesis demonstrated a number of methods for the intelligent design of novel heterogeneous Ag catalysts with remarkable activity and selectivity toward specific selective propylene oxidation. These modification methods are believed to be potentially applicable to a wide range of other catalytic reactions.

Zinc xanthates are active catalysts in stereoregular polymerization of propylene oxide and markedly more stable than that of known classical stereoregular catalysts. But steric control of zinc xanthates is weaker. To find more effective catalyst systems the isopropyl xanthates of Cu, Pb, Ni, Fe, Al and Sn are investigated and only copper (Cu(isoPr)Xt) and tin (Sn(isoPr)Xt) isopropyl xanthates were appeared to be active, but Cu(isoPr)Xt yielded only low molecular weight product. Therefore Sn(isoPr)Xt system was investigated in detail in polymerization of propylene oxide (PO). Polymerization of PO with this catalyst produced two contrasting polymers / high molar mass, crystalline (K-polymer) and low molar mass (D-polymer). Formation of double bonds in D-polymer was thought to be due to as an anionic process. Polymerization reactions were studied by changing polymerization conditions and reacting catalyst with predetermined amount of water. It&amp / #8217 / s found that Sn(isoPr)Xt have considerably low efficiency than that of Zn(isoPr)Xt catalyst. The yield linearly increases by increasing catalyst concentration. The propagation is competed by termination or transfer process hence overall activation energy is negative. Some mechanistic features of this system was also discussed. The catalytical activity of carbamates in this field has also been reported, without any information about catalytical efficiency and stereoregularity of the process. Therefore zinc diethyl dithiocarbamate was also studied and found as an active catalyst in stereoregular polymerization but it showed weaker efficiency in the PO polymerization than that of Zn(isoPr)Xt catalyst (about 12 times weaker).

The reactions which give the products ethylene oxide, vinyl alcohol, vinyl aldehyde and vinyl radical for ethylene oxidation and the reactions which give propylene oxide, propanal, acetone and pi-allyl radical for propylene oxidation were investigated by using Density Functional Theory (DFT) method with B3LYP/LanL2DZ and 6-31g(d,p) basis sets in Gaussian&rsquo / 03 software. Silver and silver oxide were used as catalyst surface cluster models. Surface comparison was made for silver (111), (110) and (100) surfaces. Ethylene oxidation reaction was studied on these silver surfaces. Oxygen effect on ethylene oxide formation reaction was also investigated on silver (111) surface. Ethylene and propylene oxidation reactions were completed on both Ag13(111) and Ag14O9(001) surface clusters. VASP software which utilizes periodic plane wave basis sets was also used to compare trends of reactions for ethylene and propylene oxidations obtained by using Gaussian&rsquo / 03 software. According to results, silver (110) surface is more active for ethylene oxide formation than (111) and (100) surfaces. Hill site of (110) surface is much more active than hollow site of (110) surface since oxygen atom weakly adsorbed on hill site. Ethyl aldehyde and vinyl alcohol can not be formed on Ag(111) surface because of those higher activation barriers while ethylene oxide can be formed on cluster. Activation barrier for ethylene oxide formation decreases with increasing oxygen coverage on Ag(111) surface. Ethylene oxametallocycle intermediate molecule was not formed on Ag2O(001) surface while it is formed on surface oxide structure on Ag(111). Ethyl aldehyde and vinyl alcohol are not formed on silver oxide (001) surface. For propylene oxidation, &amp / #928 / -allyl formation path has the lowest activation barrier explaining why silver is not a good catalyst for the propylene oxide formation while it is a good catalyst for the ethylene oxide formation. This situation is valid for silver oxide. Propylene oxide selectivity increased in the gas phase oxidation. The qualitative relative energy trend obtained by VASP software is the similar with that of calculations obtained by using GAUSSIAN&rsquo / 03 software.

The synthesis of high molecular weight copolymer of carbon disulphide (CS2) and propylene oxide (PO) has not reported in literature. In the present work, zinc isopropyl xanthate (Zn(Xt)2) was used as catalyst for the copolymerisation of PO and CS2 into high copolymer. However, the product can be fractionated into high and low molecular weight components. High molecular weight copolymer was rubbery products, but low molecular weight copolymers were oily products containing cyclic dithiocarbonates. Copolymers were characterized by elemental, end group analysis, DSC, TGA, GPC, Light Scattering, UV, IR, NMR spectroscopy, polarized microscopy and refractometry. Copolymerization process was zeroth order with respect to monomers, and its non-terminated but suffered from several types of transfer reactions. As a result of transfer reactions S-(C=S)-S, O-(C=S)-O, O-(C=O)-O groups in the backbone of copolymer and SH groups at the chain terminals and cyclic dithiocarbonates are formed. Apart from SH groups, OH and double bonds were found and their amounts were determined at the chain terminals. Copolymers with high mole fractions of PO units (F1) in the copolymer are crystallized in the shape of Malta&amp / #8217 / s Cross. Melting points of products were obtained from DSC. The F1 values are calculated from elemental analysis as well as zeroth order rate constants and from melting point of the crystals. All three results were in close agreement and changed between 0.9 &amp / #8211 / 0.7. However, these ratios depend on reaction conditions (temperature, catalyst and monomer concentrations, time and dielectric constant of reaction medium). A mechanism for coordination-copolymerization on the basis of above observation was proposed.

No description available.

Superparamagnetic nanoparticles have potential applications in targeted drug delivery and as magnetic resonance imaging contrast agents. Magnetite clusters are of particular interest for these applications because they provide higher magnetic flux (under a magnetic field) than individual magnetite nanoparticles, are biocompatible, and their size and compositions can be controlled. This thesis involves the controlled synthesis and characterization of clusters composed of magnetite nanoparticles stabilized with an amphiphilic block copolymer. It outlines a method to design and form well-defined and colloidally stable magnetite clusters. A Multi Inlet Vortex mixer (MIVM) was used because it is a continuous process that yields particles with relatively narrow and controlled size distributions. In the MIVM, four liquid streams collide under turbulent conditions in the mixing chamber where clusters form within milliseconds. The formation of magnetite clusters was studied in the presence of amphiphilic block copolymers containing poly (ethylene oxide) to provide steric stabilization and control of size distributions using flash nanoprecipitation. First, the mixer was tested using β-carotene as a model compound to form nanoparticles stabilized with an amphiphilic triblock copolymer poly(propylene oxide)-b-poly(ethylene oxide) (F127) at different Reynolds numbers and supersaturation values. Size analysis was done using dynamic light scattering and nanoparticle tracking analysis techniques. The cluster structure was studied using electron microscopy and magnetite compositions were measured using thermogravimetric analysis. Finally, the stability of magnetite clusters was studied over time and the effect of an applied magnetite field on the colloidal stability was investigated. / Master of Science

Copolymers that contain terminal or pendent functional groups have great potential in the biomedical area due to their biocompatibility and tunable properties.1-3 In this research, two vinyl functional epoxides, vinyldimethylsilylpropyl glycidyl ether (VSiGE) and ethoxy vinyl glycidyl ether (EVGE), were synthesized. These heterobifunctional monomers were polymerizable via the epoxide groups and can be functionalized via thiol-ene reactions through the pendent vinyl groups. A series of amphiphilic block copolyethers based on poly(ethylene oxide) and poly(1,2-butylene oxide) that incorporate VSiGE or EVGE were synthesized and characterized. The vinyl ether and vinyl silane functional groups were functionalized after polymerization and the functional polymers formed pH-sensitive micelles in aqueous medium. The copolyethers were loaded with ritonavir yielding well-controlled nanoparticles. Poly(L-glutamic acid) is comprised of naturally occurring L-glutamic acid repeating units that are linked together with amide bonds. In this research, we have prepared magnetic block ionomer complexes based on poly(ethylene oxide)-b-poly(L-glutamic acid) copolymers. This is of interest due to the biocompatibility and biodegradable nature of the poly(L-glutamic acid) component of the backbone. Allyl- and thiol-functional poly(ethylene oxide)-b-poly(L-glutamic acid) copolymers were also synthesized and coated onto the surface of iron oxide nanoparticles. Allyl- and thiol-tipped single particles were reacted with each other to prepare magnetic clusters. Transverse relaxivities of the clusters were found to be significantly higher than that of single particles. One major problem in commercial development of therapeutic proteins is their poor transport across cellular membranes and biological barriers such as the blood-brain barrier (BBB). One solution to this problem is to modify proteins with amphiphilic block copolymers such as PEO-b-PPO-b-PEO, Pluronics®. However, it isn't possible to independently tune the two PEO block lengths with commercial Pluronics® since a difunctional PPO macroinitator is utilized to grow both PEO blocks simultaneously (HO-EOn-b-POm-b-EOn-OH). Another challenge is introducing functional group which allows post-polymerization functionalization for specific applications. In this study, a series of heterobifunctional asymmetric amino-EOn1-b-POm-b-EOn2-OH block copolymers (APs) with different molecular weights of each block were synthesized and the amino terminal group was conjugated to an antioxidant enzyme, Cu/Zn superoxide dismutase (SOD1). The conjugates were characterized and their cellular uptake was investigated. / Ph. D.