Thesis (Ph.D.) OGI School of Science & Engineering at OHSU, June 2008. / Includes bibliographical references.

Thesis, (Ph. D.)--Oregon Graduate Institute of Science and Technology, 1998.

Thesis (Ph. D.)--University of California, Riverside, 2009. / Includes abstract. Includes bibliographical references. Issued in print and online. Available via ProQuest Digital Dissertations.

The object of this research was to prepare substituted derivatives of various chalcones having the nitro group substituted in the 31-position, the idea being to help complete the series of chalcones having the nitro group in that position. This was to be done by condensing various substituted benzaldehydes with m-nitroacetophenone, using dry hydrogen chloride as a condensing agent. The properties of the resulting chalcones were then to be determined by observing color reactions, spectra, and other general physical properties.

Thesis (PhD)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: Complex polymers are defined by their distributive properties with respect to molecular weight, chemical composition, functionality and molecular topology. As a result, polymer properties are very frequently determined not only by one of these entities but by the correlation of two or more distributions. Aliphatic polyesters are industrially implemented in high performance coatings, paints and varnishes. However, it is typically difficult to correlate the resulting properties with the synthesis parameters as these polymers vary in reactivity and application properties. Copolyester synthesis by direct polyesterification is often assumed to produce randomized products due to the mechanisms involved in stepwise polymerization. The formation of cyclic products by intramolecular reactions of hydroxyl (OH) and carboxylic (COOH) functional groups, sidereactions such as transesterification, alcoholysis, and ester-ester interchange allow even further randomization, enabling a highly complex system. Therefore, in addition to molecular weight distribution, polyesters exhibit chemical composition, functionality type as well as branching distributions, classifying them as complex polymeric systems. The different methods of polymer chromatography in combination with sophisticated spectrometry techniques are useful tools for enabling the full description of the molecular heterogeneity of these complex polyesters. The present study entails method development of different modes of chromatography and mass spectrometry along with their combination, to facilitate the analysis of the various distributions of two model polyester systems, phthalic and maleic anhydride, respectively, in combination with propylene glycol. Gradient HPLC analysis enabled an oligomeric separation based on chemical composition of the respective anhydride/propylene glycol samples. Its off-line coupling to MALDITOF MS and ESI-QTOF MS revealed the presence of several distributions of varying endgroup functionality type and molecular weight distributions at different intervals throughout the polymerization. In addition, online gradient HPLC x size exclusion chromatography (2D-LC) was conducted to obtain the dual chemical composition-molecular weight (CCD-MWD) distribution. The combination of the different coupling techniques provided the opportunity to a more in-depth analysis of the structure-property relationships. / AFRIKAANSE OPSOMMING: Komplekse polimere word gedefinieer deur hul verdelings eienskappe ten opsigte van molekulêre massa, chemiese samestelling, funksionaliteit en molekulêre topologie. Gevolglik, word hul eienskappe dikwels bepaal deur nie net een van hierdie entiteite nie, maar ‘n korrelasie van twee of meer verdelings. Alifatiese poliësters word industrieel geϊmplimenteer in hoë werkverrigting bestrykings, verwe en politoere, dog is dit tipies moeilik om die uiteinde eienskappe met die verwante sintese parameters te korrelleer, aangesien die polimere varieer in reaktiviteit en toepassingseienskappe. Ko-poliëster sintese vanaf direkte poliësterivering word dikwels aanvaar om willekeurige produkte op te lewer as gevolg van die meganismes wat betrokke is tydens trapgroei polimerisasie. Die produsering van sikliese produkte weens intra-molekulêre reaksies van hidroksiel(OH) en karboksiel (COOH) verwante funksionele groepe, newereaksies soos transverestering, alkoholise en ester-ester verwisseling, het verdere ewekansigmaking tot gevolg wat ‘n hoog gekomplekseerde sisteem tot gevolg het. Benewens die molekulere massa verdeling, vertoon poliësters dus chemiese samestelling, funksionaliteit tipe so wel as vertakkings verdeling wat hul as komplekse polimeer sisteme klassifiseer. Die verskillende metodes van polimeer chromatografie in kombinasie met gesofistikeerde spektrometriese tegnieke dien as nuttige bronne vir die volledige beskrywing wat betref die molekulêre heterogeniteit van komplekse poliesters. Die huidige studie stel metode ontwikkeling van verskillende modus van chromatografie, massa spektrometrie sowel as hul aaneenvoeging bekend, om die die verskillende verdelings van twee model poliester sisteme, ftaal- en maleϊensuuranhidried onderskeidelik in kombinasie met propileenglikol, suksesvol te analiseer. Gradiënt hoë-druk vloeistof chromatografie (HPLC) analise het ‘n oligomeriese skeiding, gebaseer op die chemiese samestelling van die verskeie anhidried /propileenglikol monsters, opgelewer. Die nie-gekoppelde skakeling met matriks-assisteerdelaser/ desorpsie-ionisasie tyd-van-vlug (MALDI-TOF) en elektron-sproei-ionisasie kwadrupool-tyd-van-vlug (ESI-QTOF) massa spektrometrie het die teenwoordigheid van verskeie verdelings van varieërende endgroep funksionaliteit tipe en molekulêre verdelings by verskillende intervalle tydens die polimerisasie aan die lig gebring. Gekoppelde skakeling van gradient HPLC en grootte uitsluitings chromatografie is ook uitgevoer om die tweedelige chemiese samestelling-molekulere massa verdeling te bepaal. Aaneenvoeging van die verskeie skakelings tegnieke het die geleentheid gebied om ‘n deeglike studie van die struktuureienskappe verhoudinge suksesvol uit te voer.

Graduation date: 1998

SeaWiFS was collecting ocean color data since 1997. This means chlorophyll-a data for more than ten years. Since, SeaWiFS Chl-a data is validated for Black Sea this data set can be used for analysis. Nevertheless, the data is not gap free due to cloud effect. One of the main objectives of this work is to obtain a gap free, complete Chl-a data set for the Black Sea. For this purpose DINEOF method will be used.

The synthesis of highly ordered carbonaceous materials, including carbon nanofibers, has been the subject of a disparate and burgeoning literature over the past decade. Growth of carbon nanotubes via an atypical catalytic route, the decomposition of halogenated reactants as chlorobenzene (CB) over 10% (w/w) Ni/SiO2 is investigated. The C (carbon) yield and structural order are a function of reaction time and temperature. Greater degree of structural order and C yield is observed from CB relative to benzene, suggesting Cl/catalyst interaction(s) and metal site restructuring. Evaluation of the effect of H2 on C growth from CB reveals that C yield is sensitive to % (v/v) H2 with selectivity maxima at 40% (v/v) H2. Further, C yield is significantly influenced by the nature of the heteroatom substituent on the benzene ring; presence of strong electron withdrawing groups favors C yield and weak electron withdrawing or donating groups favors competing side reactions. The effect of the strong electron withdrawing group, Cl, varies with the chemical structure of the carbon source. Presence of Cl promotes C yield in the case of aromatic and straight chained (aliphatic) compounds whereas it promotes formation of benzene in the case of cyclic (aliphatic) compounds. Results are interpreted in term of substituent/ catalyst interaction and the mechanism of solid C formation. Further, effect of % (v/v) H2 on C growth characteristics varies significantly with the precursor. The C growth characteristics are strongly dependent on the nature of the support used, as demonstrated for the following supports: SiO2, Ta2O5, Al2O3, NaY, activated carbon and graphite at 10% (w/w) Ni loading. Ni/SiO2 results in maximum C yield. Variation in Ni loading significantly influences the C yield; higher loading favors greater C yield. C grown on Ni/NaY was found to be relatively more structured to C obtained on the other supports. EDX analysis of the carbon product was used to assess the possibility of Cl intercalation and it reveals presence of 0.4 at% Cl on carbon grown on Ni/Al2O3.

Thesis (Ph.D)--Biomedical Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Murthy, Niren; Committee Member: Bellamkonda, Ravi; Committee Member: Davis, Michael; Committee Member: May, Sheldon; Committee Member: Milam, Valeria. Part of the SMARTech Electronic Thesis and Dissertation Collection.

For many years the problem of separating aliphatic and aromatic compounds has been at the forefront of the petroleum and oil refining industries. This separation is often effected using liquid-liquid extraction or extractive distillation. Both of these processes require the addition of a solvent to bring about separation. The aims of this work were to investigate the use of "mixed" solvents, such as those used in the Arosolvan process, for their application in liquid-liquid extraction and extractive distillation as well as to provide related thelmodynamic data for systems containing mixed solvents. In the last part of this work, a computer program was developed to theoretically predict the effectiveness of a number of solvents on a user-defined separation. The solvents used for liquid-liquid extraction were chosen based on their similarities to those in the Arosolvan process and were of the form, {N-methyl-2-pyrollidone (NMP) + glycerol, a glycol or water} where the glycol was either monoethylene glycol (MEG), diethylene glycol (DEG) or triethylene glycol (TEG). The additives were combined in various mixing ratios to NMP to determine a mixing ratio for which the effect of the solvent is possibly optimized (a list of all solvents and mixing ratios used are presented in this work). Solvent selectivity and the range of compositions over which separation could occur determined the effectiveness of the solvents. This work dealt with the separation of n-hexane and toluene. In order to determine the selectivity and range of compositions, the liquid-liquid equilibria (LLE) of systems containing n-hexane + toluene + solvent had to be determined. LLE was measured using a simple equilibrium cell at 298 K and 1 atm. The phase separation boundaries (binodal curves) were determined using a titration method. The results obtained in this work showed an increase in the range of compositions over which the mixture of n-hexane and toluene could be separated (i.e a larger range of mixing ratios over which these components could be separated from each other) from the pure NMP solvent to the mixed solvent cases. This implies that there is a The range of compositions over which separation could be affected is given (for the solvents) in descending order: NMP + 50% glycerol> NMP + 10% water > NMP + 30% MEG > NMP + 5% water > NMP + 30% glycerol> NMP + 10% glycerol > NMP + 10% MEG > NMP + 10% DEG > NMP + 10% TEG > NMP + 5% DEG > 100% NMP. The selectivities of the solvents showed a remarkable increase from the pure NMP case to the mixed solvent cases. The maximum selectivity obtained for the NMP + 10% DEG system was over 1200 compared to a maximum selectivity of just 6 for the pure NMP system. The maximum selectivities obtained in descending order were as follows: NMP + 10% DEG > NMP + 10% TEG > NMP + 10% glycerol > NMP + 10% MEG > NMP + 30% MEG > NMP + 50% glycerol > NMP + 10% water > NMP + 5% water > NMP + 30% glycerol > NMP + 5% DEG > 100% NMP. The binodal curves were modelled using the Hlavaty, ,8-density and log-y functions. The maximum standard deviations obtained were 0.075, 0.078 and 0.05 for each of the functions respectively. The equilibrium data was modelled using the UNIQUAC and NRTL thermodynamic models and showed excellent agreement. This work showed better agreement to the NRTL functions due to the fact that the non-randomness parameter, a ij , may be chosen arbitrarily. The results obtained in this work indicate that the use of mixed solvents greatly increases the effectiveness ofNMP used for the separation of n-hexane and toluene. It is suggested that further studies be performed on a wider range of aliphatic and aromatic compounds in order to determine whether this is a generic behaviour or just true for n-hexane and toluene. The effectiveness of each solvent for extractive distillation was determined by its separation factor. In order to determine separation factors, the activity coefficients at infinite dilution (IDACs) had to be measured. This was done using a gas-liquid chromatography technique. The solvents employed in this study were NMP, Glycerol, MEG, TEG, NMP + 10% glycerol, NMP + 10% MEG, NMP + 10% DEG, NMP + 10% TEG. The solutes used were: pentane, heptane, hexane, toluene and benzene. The separation factors were determined for each alkane/aromatic pair per solvent. The pure solvent cases were then compared to the mixed solvent cases. The mixed solvents did not show results as promising for extractive distillation applications as they did for liquid-liquid extraction. TEG displayed the best selectivities for each of the alkane/aromatic separations except for the heptane/benzene pair, for which NMP + 10% glycerol proved to be the most effective solvent. When compared to the results obtained from the original UNIF AC model, the IDACs obtained in this work showed up to a 99% deviation. This is due to the fact that the model does not work well for all types of molecules and does not predict the equilibrium of "unlike" molecules adequately. It is suggested that other mixing ratios and different solvents be used to further investigate the effectiveness of mixed solvents for extractive distillation applications. It is further recommended that a computer aided data logging system be developed to determine residence times. This would not only provide more accurate results, but also provide a database for future reference. The computer program that was developed using the original UNIF AC method contains a database of 28 commonly used industrial solvents. This program enables the user to compare graphically the effectiveness of each of the solvents on the desired separation. Due to the limitations of the original UNIF AC method, the program does not work well for all types of molecules. However, the model can be changed without altering the prografnming structure to include a modified version of the UNIFAC model depending on the users needs. The program although written from an extractive distillation standpoint can be extended to include liquid-liquid equilibrium predictions. The main benefit of such a program is to eliminate time-consuming experimental work required to narrow down a long list of solvents required for a particular separation by theoretically predicting the best solvents for the job. The solvent database can also be expanded when new solvents become available or the user needs change / Thesis (M.Sc. Eng)-University of Natal, Durban, 2003.