Three series copolyesters [poly(butylene succinate-co-propylene succinate) (PBPSu), poly(butylene succinate-co-2-methyl-1,3-propylene succinate) (PBMPSu) and poly(ethylene succinate-co-butylene succinate) (PEBSu)] and their homopolyesters [poly(butylene succinate) (PBSu), poly(ethylene succinate) (PESu), poly(propylene succinate) (PPSu) and poly(2-methyl-1,3-propylene succinate) (PMPSu)] were synthesized by a two-step reaction (esterification and polycondensation) with titanium tetraisopropoxide as the catalyst. Molecular weights of all synthesized polyesters were determined by intrinsic viscosity and gel permeation chromatography (GPC) measurements. The values of intrinsic viscosity (0.97 ~ 1.62 dL/g) and relative molecular weight (2.4x10000 ~ 11.9x10000 g/mol) indicate that these polyesters can be made into films without complications. Compositions and sequence distributions of copolyesters were determined by analyzing the spectra of 1H NMR and 13C NMR. The randomness values of these copolyesters are closed to 1.0 that represents random sequence distribution of the comonomers. Thermal properties and stabilities were characterized using differential scanning calorimeter (DSC) and thermogravimetric analyzer (TGA), respectively. All copolyesters exhibited a single glass transition temperature (Tg). For PBPSu copolyesters, incorporating propylene succinate units to PBSu not only narrows the window between Tg and melting temperature (Tm), but also retards the cold crystallization ability, thereby lowering the crystallinity to a considerable extent. This phenomenon also occurred in PBMPSu and PEBSu copolyesters when the 2-methyl-1,3-propylene succinate (MPS) and butylene succinate (BS) units were incorporated into PBSu and PESu, respectively. Tstart is the temperature of first detectable deviation from the derivative curve of weight loss. Tstarts of all synthesized polyesters around 240 £jC, higher than the temperature of polycondensation reaction (220 £jC), demonstrates that there is no necessity of using a thermal stabilizer during the synthesis of these polyesters. Additionally, the thermal stability does not vary significantly with compositions in the same series polyester. Wide-angle X-ray diffractograms (WAXDs) at room temperature were obtained from polyesters crystallized isothermally at a temperature around 5-20 £jC below their melting temperatures. WAXD patterns of two series polyesters elucidated that the incorporation of PS or MPS units into PBSu markedly inhibits the crystallization behavior of PBSu. The phenomenon also occurred in PEBSu copolyesters when BS units were incorporated into PESu. Results of WAXD and DSC measurements showed that PMPSu is a amorphous polyester. The retarding effect on crystallization by methyl substituents on the polymer chain is efficient.

Yes / We have used literature values for the solubility of vitamin K3 in organic solvents to obtain Abraham descriptorsfor vitamin K3. Although these descriptors themselves are not exceptional in any way, when combined withequations that we have already set out, they lead to the prediction of important properties of vitamin K3.These include the vapor pressure and heat of sublimation (necessary for the analysis of data on the concentrationof vitamin K3 in ambient air), and the partitions air-water, air-blood, air-lung, air-fat, air-skin, water-lipid, water-membrane, water-skin, as well as permeation from water through skin. Values of the partitions into biologicalphases are all quite large by comparison to those for organic compounds in general.

Polyaniline (PANI), when doped with small-molecule acids, is an attractive candidate for organic and polymer electronics because of its high electrical conductivity. Its utility as functional components in electrical devices, however, has been severely restricted because such PANI has limited processibility stemming from its limited solubility in common solvents. To overcome this barrier, we have developed water dispersible PANI that is template polymerized in the presence of a polymer acid, poly(2-acrylamido-2-methyl-1-propanesulfonic acid), or PAAMPSA. The polymer acid serves two roles: it acts as a dopant to render PANI conductive and excess water soluble pendant groups provide dispersibility of PANI in aqueous media. While the introduction of polymer acids renders the conducting polymer processible, such gain in processibility is often accompanied by a significant reduction in conductivity. As such, PANI that is doped with polymer acids has only seen limited utility in organic electronics. Given the promise of conducting polymers in organic electronics in general, this thesis focuses on the elucidation of processing-structure-property relationships of PANI-PAAMPSA with the aim of ultimately improving the electrical conductivity of polymer acid-doped PANI. By controlling the molecular weight and molecular weight distribution of the polymer acid template, we have improved the conductivity of PANI-PAAMPSA from 0.4 to 2.5 S/cm. The conductivity increases with decreasing molecular weight of PAAMPSA, and it further increases with narrowing the molecular weight distribution of PAAMPSA. Strong correlations between the structure and the conductivity of PANI-PAAMPSA are observed. In particular, the crystallinity of PANI increases with increasing the conductivity of PANI-PAAMPSA. Given that the crystallinity qualifies the molecular order in PANI-PAAMPSA, we observe a linear correlation between molecular order and macroscopic charge transport in PANI-PAAMPSA. PANI-PAAMPSA forms electrostatically stabilized sub-micron particles during polymerization due to strong ionic interactions between the sulfonic acid groups of PAAMPSA and aniline. When cast as films, the connectivity of these particles must play an important role in macroscopic conduction. The size and size distribution of PANI-PAAMPSA particles is strongly influenced by the molecular characteristics of polymer acid template. Templating the synthesis of PANI-PAAMPSA with a higher molecular weight PAAMPSA results in larger particles, and templating with a PAAMPSA having a larger molecular weight distribution results in a large size distribution in the particles. Because conduction in PANI-PAAMPSA films is governed by how these particles pack, the macroscopic conductivity of PANI-PAAMPSA films increases with increasing particle density, that is reducible from the molecular characteristics of PAAMPSA. Moreover, PANI-PAAMPSA particles are structurally and chemically inhomogeneous. The conductive portions of the polymer preferentially segregate to the particle surface. Conduction in these materials is therefore mediated by the particle surface and conductivity thus scales superlinearly with particle surface area per unit film volume. We further have improved the electrical conductivity of PANI-PAAMPSA by more than two orders of magnitude via post-processing solvent annealing with dichloroacetic acid (DCA). Since DCA is a good plasticizer for PAAMPSA and its pKa is lower than that of PAAMPSA (pKas of DCA and PAAMPSA are 1.21 and 2.41, respectively, at room temperature), DCA can effectively moderate the ionic interactions between PANI and PAAMPSA, thereby relaxing the sub-micron particulate structure arrested during polymerization. PANI-PAAMPSA can thus rearrange from a “compact coil” to an “extended chain” conformation upon exposure to DCA. Efficient charge transport is thus enabled through such “extended chain” PANI-PAAMPSA structure. DCA-treated PANI-PAAMPSA exhibits an average conductivity of 48 S/cm. The DCA treatment is not only specific to PANI-PAAMPSA. This treatment can also enhance the conductivity of commercially-available poly(ethylene dioxythiophene) that is doped with poly(styrene sulfonic acid), or PEDOT-PSS. Specifically, DCA-treated PEDOT-PSS exhibits a conductivity of 600 S/cm; this conductivity is the highest among polymer acid-doped conducting polymers reported so far. PANI-PAAMPSA can effectively function as anodes in organic solar cells (OSCs) whose active layer is a blend of poly(3-hexylthiophene), P3HT, and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Specifically, the OSCs with PANI-PAAMPSA anodes exhibit an average short circuit current density of 1.95 mA/cm², open circuit voltage of 0.52 V, fill factor of 0.38, and efficiency of 0.39 %. The use of DCA-treated PANI-PAAMPSA as anodes increases device performance (i.e., short circuit current density and thereby efficiency) of OSCs by approximately two and a half fold. The OSCs with DCA-treated PANI-PAAMPSA anodes exhibit short circuit current density and efficiency as high as 4.95 mA/cm² and 0.97 %, respectively. We demonstrated several factors that govern the electrical conductivity of polymer acid-doped conducting polymers. Design rules, such as those illustrated in this study, can enable the development of conducting polymers that is not only easily processible from aqueous dispersions, but also sufficiently conductive for electronic applications, and should bring us closer to the realization of low-cost organic and polymeric electronics. / text

Orientadores: Eduardo Augusto Caldas Batista, Antonio José de Almeida Meirelles / Dissertação (mestrado) - Universidade Estadual de Campinas, Fauldade de Engenharia de Alimentos / Made available in DSpace on 2018-08-17T21:09:08Z (GMT). No. of bitstreams: 1 Fonseca_LucianaAparecidaAndradePreviato_M.pdf: 1748931 bytes, checksum: 613a144c2469dfa664248bafa33dc2ac (MD5) Previous issue date: 2011 / Resumo: Dados de equilíbrio são úteis para o projeto e otimização de processos que envolvem separação de fases, como destilação e extração. Os álcoois superiores são subprodutos do processo de destilação relacionados com o aroma de bebidas alcoólicas e que, quando purificados podem agir como solvente. Esse estudo tem por objetivo a obtenção de dados isobáricos de Equilíbrio Líquido-Vapor (ELV) para sistemas binários e ternários envolvendo álcoois superiores. Dados de Equilíbrio Líquido-Vapor foram medidos para os sistemas binários compostos por 2-propanol/2-metil-1-butanol a 560 e 760 mmHg e para os sistemas ternários compostos por 2-propanol/1-butanol/3-metil-1-butanol e 2-propanol/2-metil-1-propanol/2-metil-1butanol, ambos a 760 mmHg. As medidas experimentais foram realizadas em ebuliômetro Fischer (VLE 602) e as composições das fases foram determinadas por cromatografia gasosa. A consistência termodinâmica dos dados de ELV binário P-T-x-y foi avaliada pelo teste de área e teste de van Ness-Fredenslund e os resultados comprovaram a boa qualidade dos dados de ELV determinados nesse trabalho. Os parâmetros de interação binária dos modelos NRTL, Wilson e UNIQUAC foram ajustados aos dados experimentais dos sistemas binários utilizando-se o software comercial Aspen Plus 12.1. Os resultados mostram uma boa descrição do ELV por esses modelos. Esses parâmetros foram ainda utilizados para descrever ELV dos sistemas ternários. Esses últimos resultados mostram uma boa concordância entre os dados experimentais e os calculados / Abstract: Equilibrium data are useful for design and optimization of processes involving phase separation, such as distillation and extraction. The higher alcohols are byproducts of the distillation process related to the flavor of alcoholic beverages and that when purified can act as a solvent. This study aims to obtain isobaric Vapor-Liquid Equilibrium (VLE) data for binary and ternary systems involving higher alcohols. Vapor Liquid Equilibrium were measured for the binary system composed by 2-propanol/2-methyl-1-butanol at 560 and 760 mmHg and for the ternary systems composed by 2-propanol/1-butanol/3-methyl-1-butanol and 2-propanol/2-methyl-1-propanol/2-methyl-1butanol, both at 760 mmHg. The experimental measurements were performed in a Fischer ebulliometer (VLE 602) and the phase compositions were determined by gas chromatography. Thermodynamic consistency of the VLE binary data P-T-x-y was evaluate by area test and van Ness-Fredenslund test and the results proved the good quality of the VLE data determined in this work. The binary interaction parameters of the NRTL, Wilson and UNIQUAC models were fitted to the experimental binary VLE data in the commercial software Aspen Plus 12.1. The results show a good description of the VLE data. These parameters were used to describe the VLE data for the ternary systems and the results show a good agreement between experimental and calculated data / Mestrado / Engenharia de Alimentos / Mestre em Engenharia de Alimentos

Several novel polymer monoliths for the analysis of peptides and proteins were synthesized using polyethylene glycol diacrylate (PEGDA) as crosslinker. Photo-initiated copolymerization of polyethylene glycol methyl ether acrylate and PEGDA yielded an inert monolith that could be used for size exclusion liquid chromatography of peptides and proteins. This macroscopically uniform monolith did not shrink or swell in either water or tetrahydrofuran. More importantly, it was found to resist adsorption of both acidic and basic proteins in aqueous buffer without any organic solvent additives. A strong cation-exchange polymer monolith was synthesized by copolymerization of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and PEGDA. A ternary porogen (water, methanol and ethyl ether) was found suitable to prepare a flow-through monolith with moderate pressure drop in aqueous buffer. The resulting monolith showed excellent ion exchange capillary liquid chromatography of peptides using a simple salt gradient. Extremely narrow peaks were obtained for the analysis of synthetic peptides, natural peptides and a protein digest. A peak capacity of 179 was achieved. Although the poly(AMPS) monolith demonstrated extraordinary performance, one main drawback of this monolith was its relatively strong hydrophobicity. A decrease in hydrophobicity was achieved by using more hydrophilic monomers (e.g., sulfoethyl methacrylate or vinyl sulfonic acid). The most hydrophilic poly(vinyl sulfonic acid) monolith provided high resolution cation-exchange liquid chromatography of protein standards and lipoproteins. Use of the new PEGDA biocompatible crosslinker over the conventional ethylene glycol dimethacrylate crosslinker for the preparation of polymer monoliths was found to be advantageous for the analysis of biological compounds in several chromatography modes.