No description available.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1963. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

No description available.

No description available.

Thesis (M.S.)--University of Wisconsin--Madison, 1965. / eContent provider-neutral record in process. Description based on print version record. Bibliography: l. 29-31.

Titre de l'écran-titre (visionné le 23 janvier 2024) / L'électrofilage est une méthode facile et économique qui utilise des forces électriques pour créer des fibres dont les diamètres varient de quelques nanomètres à quelques micromètres. Le procédé est polyvalent, fonctionne avec divers matériaux et produit des fibres aux propriétés uniques telles qu'une grande surface spécifique et une porosité élevée. Il peut également incorporer des charges pour des matériaux composites. En ajustant les paramètres et en modifiant le collecteur et le dispositif de filage, il est possible de créer diverses structures de fibres. Cette technique permet la production de matériaux auxétiques caractérisés par un coefficient de Poisson négatif. L'objectif de cette étude est d'explorer la création de membranes auxétiques à base de produits biosourcés et biodégradables par le biais du procédé d'électrofilage en solution, en mettant l'accent sur l'amélioration de leurs propriétés par l'incorporation de charges. Pour atteindre cet objectif, des membranes lisses et sans perles fabriquées à partir de poly(butylène succinate) (PBS) biosourcé ont été initialement produites par électrofilage en solution. La qualité et la structure de ces membranes ont été améliorées en introduisant du bromure de cétyltriméthylammonium (CTAB) en tant que tensioactif. Par la suite, des membranes PBS auxétiques avec des coefficients de Poisson négatifs aussi bas que -5,73 ont été fabriquées par électrofilage en solution. Les effets de la morphologie des fibres, de leur orientation, de leur alignement et de la direction des fibres par rapport à la rotation du collecteur sur les propriétés mécaniques des membranes résultantes, en mettant particulièrement l'accent sur le coefficient de Poisson, ont été étudiés. Les résultats ont révélé que le degré d'orientation des fibres et l'agencement des fibres dans les directions transversale et parallèle ont été identifiés comme les facteurs les plus importants contrôlant les propriétés mécaniques des membranes électrofilées. Enfin, des nanoplaquettes de graphène (GNP) ont été incorporées dans les matrices PBS par électrofilage en solution pour créer des membranes composites conductrices et auxétiques. En particulier, une membrane contenant 0,2% en poids de GNP et fabriquée à la vitesse de collecteur la plus élevée (9,96 m/s) a montré une conductivité électrique exceptionnelle (1,56x10⁻⁴ S/m) tout en ayant un coefficient de Poisson négatif (CPN) de -1,5 en tension. / Electrospinning is a facile and cost-effective method using electrical forces to create fibers with diameters ranging from nanometers to micrometers. It is versatile, working with various materials and produces fibers with unique properties such as high surface area and porosity. It can also incorporate fillers for composite materials. By adjusting the parameters and modifying the collector speed, it is possible to create diverse fiber structures. This technique enables the production of auxetic materials characterized by a negative Poisson's ratio. The aim of this study is to explore the creation of auxetic membranes that are biobased and biodegradable through the process of solution electrospinning, with an emphasis on improving their properties via filler addition. To achieve this objective, smooth and beadless membranes made from biobased poly(butylene succinate) (PBS) were initially produced through solution electrospinning. The quality and structure of these membranes were improved by adding cetyltrimethylammonium bromide (CTAB) as a surfactant. Subsequently, auxetic PBS membranes with negative Poisson's ratios as low as -5.73 were manufactured through solution electrospinning. The effect of fiber morphology, orientation, alignment, and the direction of fiber with respect to the collector's rotation on the mechanical properties of the resulting membranes was studied, with a particular focus on the Poisson's ratio. The results revealed that the level of fiber orientation and the arrangement of fibers in both transverse and parallel directions were identified as the most important factors controlling the mechanical properties of electrospun membranes. Finally, graphene nanoplatelets (GNP) were incorporated into the PBS matrix via solution electrospinning to create conductive and auxetic composite membranes. In particular, a membrane containing 0.2% w/v GNP and produced at the highest collector speed (9.96 m/s) showed exceptional electrical conductivity (1.56x10⁻⁴ S/m) while having a negative Poisson's ratio (NPR) of -1.5 in tension.

Ischaemia-reperfusion (IR) injury is caused by the re-introduction of oxygen to organs, following periods of reduced blood flow (ischaemia). Whilst re-establishing blood flow (reperfusion) to the heart following myocardial infarction is vital for organ survival, this paradoxically leads to tissue damage. Mitochondria are at the heart of IR injury, with succinate dehydrogenase (SDH) a major player in orchestrating the damage. Succinate accumulates during ischaemia and is rapidly oxidised by SDH upon reperfusion, producing reactive oxygen species (ROS), leading to cellular death. I have investigated the development of drugs, aimed at targeting succinate metabolism to ameliorate IR injury. I firstly screened a range of compounds for their ability to inhibit SDH, having been chosen for their similar structures to succinate or the classical SDH inhibitor, malonate. Interestingly, only malonate and oxaloacetate showed potent SDH inhibition, thus were selected for further development. Malonate ester prodrugs with different properties were characterised. Hydrolysis rates of the esters differed greatly, with tuned, labile, malonate esters releasing malonate much more rapidly. Malonate esters were taken up into cells and hydrolysed to release malonate to different extents. Additionally, mitochondria-targetedmalonatemono and diesters were developed, each differing in mitochondrial and cellular uptake andmalonate release. Targeted and nontargeted malonate esters distributed into tissues in vivo, with preliminary in vivo work carried out on IR injury models, to assess for protective effects of the compounds. In addition, the physiological role of the tricarboxylic acid cycle metabolite, itaconate, was investigated. In lipopolysaccharide stimulated macrophages, itaconate has been reported to exert its effects by inhibition of SDH however, I found itaconate was a relatively poor SDH inhibitor, indicating other mechanisms of action. Current prodrugs of itaconate have many non-specific effects, not attributable to itaconate. I therefore characterised a novel itaconate prodrug and found it to be a much better surrogate, which could be subsequently used to elucidate roles for itaconate. Overall, I have shown the importance of ester selection for the prodrug delivery of dicarboxylate molecules and developed methods to improve their biological delivery.

A small amount of poly(trimethylene succinate) (PTSu) were copolymerized or blended with poly(butylenes succinate) (PBSu) in this study. The range of intrinsic viscosity for PBSu and PBSu-enriched copolymers are between 1.62 and 0.97 dL/g; number-average molecular weights are in the range of 2.5x104 and 11.9x104 g/mol with polydispersity indices ranging from 1.52 to 3.94. Copolymer composition is calculated from 1H and 13C NMR spectra, and the distribution of BS and TS units in these copolymers are supported to be random from the evidence of a single glass transition temperature (Tg) and a randomness value close to 1.0. Tg of PBSu is -40.8 ¢XC. The Tg values of copolymers and blends increased with TS contents. The melting temperature (Tm) and the exothermic heat of crystallization of blends were not strongly affected by blending with PTSu. The values of Avrami exponent (n) for PBSu, copolymers and blends ranging from 2.3 to 3.1 indicate that heterogeneous nucleation with three-dimensional growth and homogeneous nucleation with two-dimensional growth might happen during the crystallization process. Multiple melting behavior was observed for PBSu, PBSu- enriched copolyesters and blends. Their peak temperatures are denoted as Tm1, Tm2 and Tm3 in order of increasing temperature. Tm1 corresponds to the melting temperature of the so-called annealing peak which might be resulted from the competition between continuous melting and re-crystallization. In contrast the peak at Tm2 is attributed to the melting of the primary crystals formed during isothermal crystallization. The peak at Tm3 may arise from the melting of re-crystallized primary crystals. Equilibrium melting temperatures were determined by the Hoffman-Weeks linear extrapolations which yield of 127.4 ¢XC for PBS, 125.7 ¢XC for PBTSA95/05, 120.6 ¢XC for PBTSu90/10, 128.6 ¢XC for PBSu/PTSu 98/02, 127.0 ¢XC for PBSu/PTSu 95/05 and 125.5 ¢XC for PBSu/PTSu 90/10. The thickness coefficient ( ) is located between 0.77 and 0.80. Three characteristics temperatures of thermal degradation, defined as temperature of thermal degradation at begining (Tstart), weight losses of 2% (Tloss2%) and maximum degradation rate (Tmax), were employed to characterize the thermal stability of polyesters and blends. The Tloss2% and Tstart values of PBTSu90/10 are higher than the values of the others because of its unusually high molecular weight. Wide-angle x-ray diffraction patterns were obtained after complete isothermal crystallization. Diffraction peaks are in the same positions, and these peaks become sharper and increase in intensity as the crystallization temperature increases. This indicates that during the heating process, only one crystal form appears and both of the crystallite size and perfect degree increase. The isothermal growth rate of PBSu spherulite increases from 0.01 £gm/sec at 103 ¢XC to 3.33 £gm/sec at 75 ¢XC. When the TS units increase, the spherulitic growth rates of PBTSu95/05 and PBTSu90/10 copolyesters decline dramatically. One of the reasons is that the incorporation of TS units into PBSu significantly inhibits the crystallization behavior of PBSu. Growth rates data were treated with Lauritzen-Hoffman secondary nucleation theory to find the regime transition. Using the Williams-Landel-Ferry (WLF) values, regime II to III transition is found at 95.1 ¢XC for PBSu, 84.4 ¢XC PBTSu95/05, and 77.1 ¢XC for PBTSu 90/10. All melt-crystallized specimens formed two dimensional axial-like spherulites with negative birefringence. Extinction bands were observed when PBSu, PBSu- enriched copolymers and blends specimens were crystallized at large undercooling.

Minor amounts of monomers or homopolymer of poly(butylene succinate) (PBS) were copolymerized or blended with monomers or homopolymer of poly(ethylene succinate) (PES). PEBSA 95/05 represents a copolymer synthesized from a feed ratio of 95 mol% ethylene glycol and 5 mol% 1,4-butanediol with 100 mol% succinic acid. Copolymers PEBSA 90/10 and 50/50 were also synthesized. Blends of PES and PBS were prepared in solution with ratios of PES/PBS: 98/02, 95/05 and 90/10. Molecular weights of homopolymers and copolymers were measured using capillary viscometer and gel permeation chromatography. The results indicate that polyesters used in this study have high molecular weights. The chemical composition and the sequence distribution of co-monomers in copolyesters were determined using 1H NMR and 13C NMR. The distribution of ES and BS units in these copolyesters was found to be random from the evidence of a single Tg and a randomness value close to 1.0 for a random copolymer. Thermal properties of polyesters and blends were characterized using differential scanning calorimeter (DSC), temperature-modulated DSC (TMDSC) and thermogravimeter. For copolymers, melting point of PES significantly decreases from 100.9 to 94.5 to 89.8 oC with an increasing in BS units from 0 to 5 to 10 mol%. Blends keep the intrinsic melting points of PES and PBS homopolymers. There is no significant difference or no trend about the thermal stability of these polyesters and blends. Wide-angle X-ray diffractograms (WAXD) were obtained for specimens after complete isothermal crystallization. Diffraction peaks indicate that the crystal structure of PES is dominated in PES-enriched copolymers. However, PEBSA 50/50 displays weak diffraction peaks of the characteristic peaks of PBS homopolymer. Isothermal crystallization of copolyesters and blends were performed using DSC. Their crystallization kinetics and melting behavior after complete crystallization were analyzed. The n1 values of the Avrami exponent for copolyesters increased from 2.54 to 2.84 as the isothermal temperature (Tc) increased. The Hoffman-Weeks linear plots yielded an equilibrium melting temperature of 111.1 and 107.0 oC, respectively, for PEBSA 95/05 and 90/10. Homopolymer PES has an equilibrium melting temperature of 112.7 oC. For blends, the n1 value has a minimum at Tc of 40 oC then it increases with an increase in Tc or in PBS. At the same Tc, n1 increases slightly and the rate constant (k1) decreases when the ratio of PBS in blends increases. All of these blends gave an equilibrium melting temperature of 113.1 oC. Multiple melting behavior involves melting-recrystallization-remelting and various lamellar crystals. As Tc or BS unit in copolymer increases, the contribution of recrystallization slowly declines. Acetophenone was used a diluent for PES homopolymer. Five concentrations were used to estimate the melting point depression, and the heat of fusion of PES was obtained to have a value of 163.3 J/g according to Flory equation. Spherulitic growth rates of copolymers were measured at Tc between 30 and 80 oC using polarized light microscope (PLM). Maximum growth rates occurred at Tc around 50 oC. It is found that the growth rate of copolymer decreases significantly after randomly incorporating BS units into PES. Non-isothermal method at a cooling rate of 2, 4 or 6 oC/min was used to calculate the isothermal growth rates of copolymers. These continuous data fit very well with the data points measured isothermally. Growth rates data are separately analyzed using the Hoffman-Lauritzen equation. A regime II-III transition is found at 59.4 and 52.4 oC, respectively, for copolyesters PEBSA 95/05 and PEBSA 90/10. The results of DSC and PLM indicate that blend PES/PBS 98/02 not only retains the melting point and the crystallinity of PES homopolymer, but also increases the nucleation rate of this blend. The effect of blending 2 mol% PBS with PES on the biodegradability of PES is deserved to be investigated furthermore.

The topics of this study are as follows: (a) Poly(butylene succinate) (PBSu) rich random copolymers containing ~20% and ~50% trimethylene succinate (TS), PBTSu 80/20 and PBTSu 50/50 that were synthesized from 1,4-butanediol, 1,3-propanediol and succinic acid: The influence of minor TS units on the thermal properties and crystallization rate of PBSu was investigated. (b) Random copolymer of ~90% PBSu and ~10% poly(1,4-cyclohexanedimethylene succinate), PBCHDMSu 90/10, that was synthesized from 1,4-butanediol, 1,4-cyclohexanedimethanol and succinic acid: The influence of cyclohexene unit on the thermal properties and crystallization rate of PBSu was investigated. (c) Blends of PBSu and poly(trimethylene succinate) (PTSu) or poly(ethylene succinate) (PESu): The weight ratio PBSu and PTSu (or PESu ) were 1:1. The crystallization and morphology of blends (PBSu/PTSu 50/50 and PBSu/PESu 50/50) were investigated and compared with PBTSu 50 and PBESu 50/50. The chemical composition and the sequence distribution of co-monomers in copolyesters were determined using NMR. Thermal properties of polyesters and blends were characterized using differential scanning calorimeter (DSC) and temperature-modulated DSC (TMDSC). The crystallization kinetics and equilibrium melting temperature were analyzed with Avrami equation and Hoffman-Weeks linear extrapolation. The thermal stability of polyesters was analyzed by thermogravimeter (TGA) and polarized light microscope (PLM) under nitrogen. Wide-angle X-ray diffractograms (WAXD) were obtained for specimens after complete isothermal crystallization. The growth rates, regime transition temperature, morphology and phase separation were studied using polarized light microscope (PLM) with isothermal method or nonisothermal method. The morphology of specimens after chemical etching were investigated using atomic force microscope (AFM) and scanning electron microscope (SEM). The distribution of butylene succinate (BS) and TS units in PBTSu 80/20 was found to be random from the evidence of a single Tg and a randomness value close to 1.0 for a random copolymer. With the increasing of minor amounts of comonomers, the sequence length of butylene succinate decreases, and the crystallization rate and the degree of crystallinity drop. DSC heating curves of isothermal crystallized PBTSu 80/20 and PBCHDMSu 90/10 showed triple melting peaks. Multiple melting behaviors indicate that the upper melting peaks are associated with the primary and the recrystallized crystals, or the crystals with different lamellar thickness. As the Tc increases, the contribution of recrystallization slowly decreases and finally disappears. Hoffman-Weeks linear plots gave an equilibrium melting temperature of 113.5