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 aim of this diplom thesis was development of the reverse phased high performance liquid chromatography (RP-HPLC) for analysis the aliphatic hydrocarbons with long chain and optimalization of this method. In theoretical part is described occurrence and properties of a hydrocarbons, also used separation methods and detectors - evaporative light scattering detector (ELSD) and matrix assisted laser desorption ionization with time of flight analyzer. In experimental part is described izolation of cuticular hydrocarbons from a fly Neobellieria bullata. It was study experimental conditions of separation and detection izolated hydrocarbons. It was performed deep optimalization of conditions on RP-HPLC - composition of mobile phase, gradient, mobile phase flow rate and column temperature. Method optimalization was done by ELSD. It was used kombination of two solvents to mobile phase - acetonitrile : ethylacetate, mobile phase stream 0,8 ml/min and column temperature 50řC were found as optimal conditions for analytical separation. This method were aplicated for analysis cuticular hydrocarbons from fly specie Neobellieria bullata. During separation were collected fractions and then fractions were determined on MALDI-TOF. It was found 37 aliphatic hydrocarbons which included 25 up to 47 carbons and 0 to 3...

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.

Yes / The present work deals with the flow-induced multiple orientations and crystallization structure of polymer melts under a complex flow field. This complex flow field is characteristic of the consistent coupling of extensional “pulse” and closely followed shear flow in a narrow channel. Utilizing an ingenious combination of an advanced micro-injection device and long chain aliphatic polyamides (LCPA), the flow-induced crystallization morphology was well preserved for ex-situ synchrotron micro-focused wide angle X-ray scattering (μWAXS) as well as small angle X-ray scattering (SAXS). An inverted anisotropic crystallization structure was observed in two directions: perpendicular and parallel to the flow direction (FD). The novel anisotropic morphology implies the occurrence of wall slip and “global” fountain flow under the complex flow field. The mechanism of structure formation is elucidated in detail. The experimental results clearly indicate that the effect of extensional pulse on the polymer melt is restrained and further diminished due to either the transverse tumble of fountain flow or the rapid retraction of stretched high molecular weight tails. However, the residual shish-kebab structures in the core layer of the far-end of channel suggest that the effect of extensional pulse should be considered in the small-scaled geometries or under the high strain rate condition.

No description available.

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.

L'Imagerie par Résonance Magnétique (IRM) est à l'heure actuelle la technique de visualisation préférentiellement choisie par les chirurgiens. Cependant, cette technique ne permet pas de visualiser des prothèses à base de polymères, qu'elles soient dégradables ou non. Afin de mieux évaluer la fixation, l'intégration tissulaire et le devenir de l'implantation de ces prothèses polymères, il serait souhaitable qu'elles soient visibles par IRM. Ce travail présente donc la conception et la synthèse de copolymères biocompatibles visibles par IRM destinés à être introduit dans la composition de prothèses pour applications temporaires ou permanentes. En utilisant la modification chimique en position alpha de fonction ester décrite précédemment par notre laboratoire, nous avons greffé de façon covalente et par une liaison stable un chélate du gadolinium (le DTPA) sur la chaîne de la PCL (dégradable) et du PAM (non dégradable). Le gadolinium a ensuite été complexé par le DTPA greffé préalablement. Ces nouveaux copolymères ont été caractérisés par RMN et CES, et le taux de gadolinium évalué par ICP-MS. Des images d'IRM ont été réalisées in vitro et in vivo sur des appareils contenant des aimants de 7 Teslas (recherche) et 1,5 Teslas (clinique). Ces images montrent qu'un treillis en polypropylène enduit de copolymère greffé par un complexe DTPA-gadolinium est visible par IRM, ce qui laisse entrevoir un large champ d'applications pour ce type de composé. / Magnetic Resonance Imaging (MRI) is currently the visualization technique that surgeons preferentially choose. However this technique does not allow the visualization of polymer-based prosthesis, whether they are degradable or not. In order to best assess adhesion, tissue integration and the future of implantation of these polymer prosthesis, it would be advisable to make them visible in IRM. This work presents the conception and the synthesis of biocompatible copolymers visible in IRM meant to be implanted under the form of prosthesis for temporary or permanent applications. Using the chemical modification in alpha position of ester function, previously described by our laboratory, we grafted a gadolinium chelate, in a covalent way and forming a stable bond on PCL (degradable) and PMA (non degradable) backbone. Gadolinium was then complexed by DTPA previously grafted. Those new copolymers were characterized with NMR and SEC, and the rate of gadolinium was assessed by ICP-MS. MRI images were taken in vitro and in vivo on devices containing 7-Teslas (research) and 1,5 Teslas (clinical) magnets. These images show a poly(propylene) mesh coated with grafted copolymer containing complex gadolinium which is visible in MRI. It will consequently improve the prospects of applications for this kind of MRI-visible compound.

The theoretical part of this diploma work is focused on the polymeric nanoparticles, their properties and advantages connected with them. There are introduced also particular types of organic and inorganic nanoparticles and methods of their preparation. The great attention was directed on biodegradable polymers in particular to poly lactic-co-glycolic acid, which was used in experimental part as carrier for base of terbinafine branched to tripentaerythritol. PLGA is the most suitable copolymer for practice because of good explored its physical, chemical and biological properties, methods of preparation and factors affecting degradation. The aim of this work was to find suitable emulsifier with suitable concentration for preparation of nanoparticles containing the base of terbinafine, suitable solvent for terpolymer and optimal concentration of emulsion to reach the highest yield of terbinafine without any exceptional loss. How it was mentioned, as carrier was used terpolymer of poly lactic-co-glycolic acid with tripentaerythritol. As technique of preparation of nanoparticles was used emulsification by evaporating of organic solvent (solvent evaporation method). During the experimental work we found out some of conclusions, it goes to reduce of polydispersity with increasing concentration of...