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.

The Fluidized Catalytic Cracking (FCC) is known for its ability to convert refinery wastes into useful fuels such as gasoline, diesel and some lighter products such as ethylene and propylene, which are major building blocks for the polyethylene and polypropylene production. It is the most important unit of the refinery. However, changes in quality, nature of crude oil blends feedstock, environmental changes and the desire to obtain higher profitability, lead to many alternative operating conditions of the FCC riser. There are two major reactors in the FCC unit: the riser and the regenerator. The production objective of the riser is the maximisation of gasoline and diesel, but it can also be used to maximise products like propylene, butylene etc. For the regenerator, it is for regeneration of spent or deactivated catalyst. To realise these objectives, mathematical models of the riser, disengage-stripping section, cyclones and regenerator were adopted from the literature and modified, and then used on the gPROMS model builder platform to make a virtual form of the FCC unit. A new parameter estimation technique was developed in this research and used to estimate new kinetic parameters for a new six lumps kinetic model based on an industrial unit. Research outputs have resulted in the following major products’ yields: gasoline (plant; 47.31 wt% and simulation; 48.63 wt%) and diesel (plant; 18.57 wt% and simulation; 18.42 wt%) and this readily validates the new estimation methodology as well as the kinetic parameters estimated. The same methodology was used to estimate kinetic parameters for a new kinetic reaction scheme that considered propylene as a single lump. The yield of propylene was found to be 4.59 wt%, which is consistent with published data. For the first time, a Z-factor correlation analysis was used in the riser simulation to improve the hydrodynamics. It was found that different Z factor correlations predicted different riser operating pressures (90 – 279 kPa) and temperatures as well as the riser products. The Z factor correlation of Heidaryan et al. (2010a) was found to represent the condition of the riser, and depending on the catalyst-to-oil ratio, this ranges from 1.06 at the inlet of the riser to 0.92 at the exit. Optimisation was carried out to maximise gasoline, propylene in the riser and minimise CO2 in the regenerator. An increase of 4.51% gasoline, 8.93 wt.% increase in propylene as a single lump and 5.24 % reduction of carbon dioxide emission were achieved. Finally, varying the riser diameter was found to have very little effect on the yields of the riser products.

Swedavia är ett statligt ägt bolag som äger och driver tio flygplatser i Sverige, varav Stockholm Arlanda Airport är en. Flygplatsen har ett miljötillstånd där ett utredningsvillkor kallat U4 finns. Prövotidsutredningen syftar främst till att utvärdera reningseffekten hos dagvattenanläggningarna vid flygplatsen, med slutgiltiga villkor om utsläpp av bl.a. organiska föreningar och näringsämnen. När det under vintertid bildas snö- och isbeläggningar på flygplanen och banorna riskerar det att delvis påverka den aerodynamiska förmågan men också orsaka otillräcklig friktion mellan flygplansdäcken och marken. För att förhindra att olyckor sker eller att plan inte lyfter används framför allt kaliumformiat och propylenglykol som av-isning och halkbekämpningsmedel. Följden av att använda dessa blir förhöjda halter löst TOC (Total Organic Carbon) i dagvattnet och det kan leda till syrefria förhållanden i recipienten, vilket i detta fall är Märstaån. Swedavia har, med det primära syftet att rena dagvattnet på av-isning-och halkbekämpningsmedel, anlagt flera dagvattenanläggningar på flygplatsområdet. Dessa består av dammar som genom biologisk nedbrytning och sedimentering ska rena vattnet med avseende på TOC. Enligt ett prövotidsvillkor som uppkom i samband med miljödomen för flygplatsen ska slutgiltiga halter bestämmas och den potentiella reningseffektiviteten av dagvattnet ska undersökas. Reningseffektiviteten har dock visat sig vara svår att fastställa då dammarna kontinuerligt fylls på med vatten och att vattnet leds förbi dammarna via bypass-funktion vid för stora vattenflöden. Då reningseffektiviteten i dammarna fortfarande inte är fastställd är denna studies syfte att utvärdera reningseffekten och om den kan förbättras. Ett inkubationsförsök för nedbrytning gjordes med en experimentuppställning där vattenprover från Arlanda inkuberades i 3 olika temperaturer (5°C, 10°C och 23°C) med kategorierna låg/hög TOC-halt och med/utan tillsats av makronäringsämnena fosfor och kväve (N och P), enligt Redfield förhållandet 106:16:1. Försöket pågick i 33 dagar och kontinuerliga vattenprover togs för att sedan analysera TOC-halten. Resultatet visade att näringstillsats, enligt Redfieldförhållandet, inte hade någon statistisk signifikant påverkan på nedbrytningshastigheten vid 5°C och 10°C. Det fanns dock en statistisk signifikant skillnad vid 23°C, vilket tyder på att näringstillsats är gynnsamt för nedbrytningen vid högre temperaturer. Vid jämförelser mellan nedbrytningshastigheterna vid olika temperaturer fanns det en statistisk signifikant skillnad mellan proverna, förutom för kategorin med hög initialhalt utan näring. Vid låg initialhalt och en temperatur på 5°C, 10°C och 23°C kunde en reduktion av TOC på 65-73%, 83-86% samt 80-90% för respektive temperatur observeras efter en inkubationstid på 33 dagar. För proverna som startade med hög initialhalt i temperaturerna 5°C, 10°C reducerades TOC med 4-42% och 11-16%, och för 23°C skiljde sig nedbrytningen mellan kategorierna näringstillsats/ingen näringstillsats. Utan näring ökade TOC-halten med 38% och med näring reducerades den med 88 % efter 33 inkubationsdagar. En ökning av halten tyder på felkällor i metoden. Nedbrytningshastigheten och tiden för 100% nedbrytning vid låg och hög initialhalt för olika förutsättningar för hela perioden var mellan 0.34-1.02 mg/l respektive 8.45-11.47 mg/l TOC per dag samt 30-47 respektive 39-84 dagar. Efter en vecka var spannet mellan nedbrytningshastigheter för låga och höga initialhalter 1.63-6.98 mg/l respektive 33.21-83.28 mg/l TOC per dag och reningskapacitetenefter en vecka var 33-100% respektive 30-81%. De förbättringar som kan föreslås, baserat på resultatet i studien, är att se över möjligheten att ha ett kostnadseffektivt uppvärmt system, eventuellt genom att nyttja spillvärme på flygplatsen. Vid uppvärmning kan ett alternativ vara att tillföra näringsrikt avloppsvatten, för att upprätthålla en effektiv nedbrytning. Om detta inte är möjligt bör man överväga möjligheten att introducera ett ytterligare reningssteg, som ett biofilter som reducerar TOC-halten innan vattnet lagras i dammarna. Mer studier krävs dock för att kunna dra välgrundade slutsatser från arbetet, eftersom det i studien uppkommit osäkerheter i resultatet. / Swedavia is a state-owned company that owns and operates ten airports in Sweden, of which Stockholm Arlanda Airport is one. The airport has an environmental permit where an investigation condition called U4 exists. The investigation condition primarily aims to evaluate the treatment of stormwater at the airport, with final conditions regarding emissions of e.g. organic compounds and nutrients. Snow and ice deposits form on airplanes and runways during winter, this affects the aerodynamic ability of the airplanes and cause insufficient friction between the airplane tires and the ground. To prevent crashes or planes not taking off, anti-icing agents such as mono propylene glycol and potassium formate are being used. The consequence of using these agents is increased levels of dissolved organic material in the stormwater and in the worst case this can lead to oxygen depletion in the recipient, which in this case is Märstaån. Swedavia has, with the primary purpose of purifying stormwater, built several stormwater facilities in the airport area. These consist of ponds that through biological decomposition depletes the water of the dissolved organic material. According to the trial period investigation, the final conditions for the storm water should be decided and the potential TOC-removal efficiency from the storm water needs to be evaluated. However, it has been hard to establish how well the ponds reduction of TOC work since water continuously fills up the ponds and because water sometimes gets bypassed when there are high flows. Since the reduction of TOC in the ponds is still not determined, the the purpose of this study was to evaluate the TOC-removal efficiency and whether it can be improved. Experimental incubations for degradation of TOC where conducted with water samples from Arlanda, incubated at 3 different temperatures (5°C, 10°C and 23°C) with the categories low/high TOC content and with/without addition of nutrients, according to the Redfield ratio 106:16:1. The experiment lasted 33 days and continuous water samples were taken to then analyze the TOC content. The result showed that nutrient addition according to the Redfield ratio had no statistically significant influence on the degradation, except at 23°C, which suggests that nutrient addition is beneficial at higher temperatures. When comparing the degradation rates at different temperatures, there was a statistically significant difference between the samples, except for the high initial content category without added nutrients. At a low initial content and a temperature of 5°C, 10°C and 23°C, a TOC-reduction of 65-73%, 83-86% and 80-90% was observed for the respective temperature after 33 days of incubation. For the samples that started with a high initial content in the temperatures 5°C, 10°C, a TOC removal of 4-42% and 11-16% was observed and for 23°C, the TOC-removal differed between the the samples without and with addition of nutrients. Without added nutrient, the TOC content increased by 38% and with added nutrient, it was reduced by 88 % after 33 days of incubation. An increase in the TOC content indicates sources of error in the method. The degradation rate and time to 100% degradation at low and high initial content for different conditions and the entire test period was between 0.34-1.02 mg/l respectively 8.45-11.47 mg/l TOC per day and 30-47 and 39-84 days respectively. After a week the range of degradation rates for low and high initial concentrations was 1.63-6.98 mg/l respectively 33.21-83.28 mg/l TOC per day and the TOC-removal capacity after one week was 33-100% respectively 30-83%. The improvements suggested, based on the results of the study, is to investigate the possibility of having a cost-effective heated pond system, possibly if there is waste heat to use from the airport. When heating, an alternative may be to add nutrient-rich wastewater, to maintain efficient degradation. If this is not possible, consideration should be given to the possibility of introducing an additional step for TOC-removal, such as a biofilter that reduces the TOC content before the water is stored in the ponds. However, more studies are required to draw well-founded conclusions from the study, as there were uncertainties in the results.

Thesis (MSc)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: Heterophasic ethylene-propylene copolymers, also known as impact polypropylene (PP) copolymers (IPCs) or heterophasic copolymers (HECOs), are a unique group of polyolefins produced through the copolymerisation of ethylene and propylene, with the aim of improving the impact properties of the PP homopolymer at low temperatures. Therefore, this polymer comprises of a PP homopolymer matrix with a dispersed rubbery copolymer phase. Due to their unique properties, HECO polymers have become commercially important materials, with a wide range of applications. Therefore a fundamental understanding of the processes and chemistry that affects their final macroscopic properties needs to be expanded. The main focus of this investigation was to understand why specific organic peroxides influence or interact differently with the various phases of HECO polymers, in order to utilize their properties to obtain HECO polymers with optimal and desired properties. Two HECO polymers with different ethylene contents were fractionated into three fractions (30, 100 and 130 °C), using preparative temperature rising elution fractionation (P-TREF). Each individual TREF fraction was degraded with two different types of organic peroxides, and then characterised using four different analytical tools. The changes in the molecular structures of the different fractions were investigated by Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The changes in comonomer sequence distributions were investigated by carbon 13 nuclear magnetic resonance spectroscopy (13C-NMR). Moreover, the degradation of the different fractions was investigated by high temperature size exclusion chromatography (HT-SEC). The investigation showed that the HECO polymers with different ethylene contents were uniquely altered. It was evident that the ethylene content influenced the degradation behaviour of the HECO polymers. The ability of the peroxide to affect certain regions of the HECO polymer more than others is highly dependent upon its miscibility with certain regions of the HECO polymers. The “visbreaking” efficiency of a specific organic peroxide appears to be primarily dependent on the number of “peroxy” groups it contains in its molecular structure. Stellenbosch University https://scholar.sun.ac.za / AFRIKAANSE OPSOMMING: Heterofase etileen-propileen ko-polimere, ook bekend as impak PP ko-polimere (IPCS) of heterofase ko-polimere (HECO), is 'n unieke groep poliolefiene geproduseer deur die ko-polimerisasie van etileen en propileen, met die doel op die verbetering in die impak eienskappe van die PP homopolimeer by lae temperature. Hierdie polimeer bestaan dus uit 'n PP homopolimeer matriks met 'n verspreide rubberagtige ko-polimeer fase. As gevolg van hul unieke eienskappe, is HECO polimere van kommersiële belang, met 'n wye verskeidenheid van toepassings. 'n Fundamentele begrip van die prosesse en chemie wat die finale makroskopiese eienskappe beïnvloed moet dus uitgebrei word. Die hooffokus van hierdie ondersoek was om te verstaan waarom spesifieke organiese peroksiede verskillende invloede en interaksies met die verskillende fases van HECO polimere het, om sodoende van hul eienskappe gebruik te maak om HECO polimere te verkry met optimale en gewenste eienskappe. Twee HECO polimere met verskillende etileen inhoud was gefraksioneer in drie fraksies (30, 100 en 130 °C), met behulp van preparatiewe temperatuur styging eluering fraksionering (P-TREF). Elke individuele TREF fraksie was gedegradeer met twee verskillende tipes organiese peroksiede en daarna gekarakteriseer deur vier verskillende analitiese metodes. Die veranderinge in molekulêre strukture van die verskillende fraksies was geondersoek met behulp van Fourier transform infrarooi spektroskopie (FTIR) en differensiële skandering kalorimetrie (DSC). Die veranderinge in ko-monomeer volgorde distribusie was bestudeer deur middel van kern magnetiese resonans spektroskopie (KMR). Verder was die degradasie van die verskillende fraksies met behulp van hoë temperatuur grootte uitsluitingschromatografie (HT-SEC) bestudeer. Die ondersoek het getoon dat die HECO polimere met verskillende etileen inhoud uniek gedegradeer was. Dus is dit duidelik genoeg dat die etileen inhoud die degradasie gedrag van die HECO polimere beïnvloed het. Die vermoë van die peroksied om sekere areas van die HECO polimeer meer as ander te beïnvloed is hoogs afhanklik van die mengbaarheid met sekere areas van die HECO polimere. Die "visbreking" doeltreffendheid van 'n spesifieke organiese peroksiede is meestal afhanklik van die aantal "peroksie" groepe in die molekulêre struktuur.

O objetivo do primeiro estudo foi avaliar a produção in vitro de embriões (PIVE) em vacas holandesas não lactantes submetidas a aspiração oocitária (OPU) posteriormente ao protocolo de superestimulação folicular similar ao descrito por Nivet et al. (2012) em comparação à realização da OPU em dia aleatório do ciclo estral. Para tal, vacas holandesas não lactantes e não gestantes foram distribuídas aleatoriamente em delineamento tipo crossover em Controle (n = 35), em que as vacas não foram tratadas com FSH, mas submetidas a uma sessão de aspiração em dia aleatório do ciclo estral; ou p-FSH (n = 35), em que, 36 horas após a OPU para sincronização da onda folicular, as vacas foram tratadas com p-FSH por 3 dias e 44 horas após, submetidas a sessões de OPU. O número total de complexos cumulusoócito (CCO) recuperados e o número de oócitos viáveis foram semelhantes entre os grupos controle e p-FSH. Além disso, não houve aumento na proporção de CCO viáveis (CCO viáveis / CCO total recuperado). Da mesma forma, não se detectaram diferenças no número de embriões / sessão de OPU e taxa de blastocistos. O protocolo de superestimulação folicular não melhorou a PIVE em vacas holandesas não lactantes. O experimento 2 testou a hipótese de que vacas leiteiras de alta produção se tornam cada vez mais resistentes à insulina com o avançar da lactação, e consequentemente, a qualidade do oócito é comprometida. Foram utilizadas vacas holandesas em 50 (51,5 ± 3,7; n = 30), 100 (102,3 ± 9,4; n = 30) e 150 (154,5 ± 18,9; n = 30) dias em lactação (DEL). Durante o teste de tolerância à glicose (TTG), não houve diferença entre grupos para qualquer variável relacionada à glicose circulante. No entanto, medidas de insulina circulante foram diferentes em vacas aos 150 DEL em comparação com 50 ou 100 DEL, tais como: maior insulina basal, pico, Δ máx de insulina e AUC 5-60. Porém, não houve diferença entre os grupos para o número ou percentagem de oócitos viáveis. Assim, as vacas desenvolveram resistência à insulina com o aumento do DEL. No entanto, o aumento da resistência à insulina não foi associado com alteração detectável na qualidade dos oócitos aspirados de folículos pequenos e médios. O experimento 3 foi para avaliar se o aumento de insulina circulante durante os períodos de pré e pós desvio folicular aumenta o desenvolvimento inicial e final, do folículo, bem como do corpo lúteo (CL). Além disso, por induzir a ovulação de um folículo maior, o CL resultante de vacas com alta insulina circulante também é maior e mais esteroidogênico, refletindo em maiores concentrações circulantes de progesterona (P4). O delineamento experimental utilizado foi o quadrado latino em arranjo fatorial 2x2, em quatro grupos experimentais: 1) CC = água pré e pós desvio folicular (n = 16); 2) CP = água e propilenoglicol (PPG) pré e pós desvio folicular, respectivamente (n = 16); 3) PC = PPG e água pré e pós desvio folicular, respectivamente (n = 16) e 4) PP = PPG pré e pós desvio folicular (n = 16). O aumento agudo e transitório, durante os períodos de pré e pós desvio não aumentou o desenvolvimento folicular, luteal e concentrações plasmáticas de P4. / The aim of the first study was to evaluate the in vitro embryo production (IVEP) in nonlactating Holstein cows subjected to ovum pick-up (OPU) after ovarian superstimulation with a protocol similar to that described by Nivet et al. (2012) in comparison with OPU at a random day of the estrous cycle. Nonlactating Holstein cows were randomly assigned in a crossover design to: Control (n = 35) in which cows were not treated with p-FSH, but subjected to OPU at a random day of the estrous cycle; or p-FSH (n = 35), in which, 36 hours after OPU to synchronize follicle wave, the cows were treated with p-FSH for 3 days and 44 hours later, subjected to OPU sessions. The total number of cumulus-oocyte complex (COC) recovered and the number of viable oocytes were similar between control and p-FSH groups. In addition, there was no increase in the proportion of viable COC (viable COC / overall COC recovered). Likewise, we detected no differences in the number of embryos / OPU session and blastocyst rate. Follicle superstimulation protocol with p-FSH did not improve IVEP in nonlactating Holstein cows. Experiment 2 tested the hypothesis that high-producing dairy cows become increasingly resistant to insulin with advancing lactation, and consequently oocyte quality is compromised. We used Holstein cows at 50 (51.5 ± 3.7; n = 30), 100 (102.3 ± 9.4; n = 30) and 150 (n = 30 154.5 ± 18.9) days in milk (DIM). During the glucose tolerance test (GTT), there was no difference between groups for any variable related to circulating glucose. However, circulating insulin measurements such as basal insulin, peak insulin, Δ max and AUC 5-60 were higher for cows at 150 DIM. Nevertheless, there was no difference between groups for the number or percentage of viable oocytes. Therefore, although cows developed insulin resistance with increasing DIM, this has not been associated with detectable change in the quality of oocytes aspirated from small and medium follicles. The third experiment assessed whether the increase in circulating insulin during periods of pre- and post-follicle deviation increases the initial and final follicle size and corpus luteum (CL) volume. Moreover, by inducing ovulation of greater follicles, resulting in greater CL, cows with high circulating insulin also have higher circulating progesterone (P4). The experimental design was a Latin square in a 2x2 factorial arrangement in four groups: 1) CC = water pre and post follicle deviation (n = 16); 2) CP = water pre and propylene glycol (PPG) post follicle deviation (n = 16); 3) PC = PPG and water pre and post follicle deviation, respectively (n = 16), 4) PP = PPG pre and post follicle deviation (n = 16). Acute and transient circulating insulin increase during periods of pre and post follicle deviation has not affected follicle development, luteal volume or plasma concentrations of P4.

Catalisadores baseados em óxidos metálicos têm sido muito utilizados nos últimos anos para a desidrogenação oxidativa de alcanos leves. Dentre os principais catalisadores, estão os sistemas contendo V2O5, Nb2O5 e Al2O3. O processo de desidrogenação oxidativa do propano (DOP) representa uma via alternativa importante para a produção de propileno sob menores temperaturas, porém sua prática vem sendo limitada pela diminuição dos valores de seletividade ao propeno com o aumento da conversão do reagente. Metais alcalinos, dentre eles o potássio, são frequentemente utilizados como promotores em reações de oxidação seletiva com o objetivo de proporcionar melhores seletividades catalíticas aos mecanismos de reação, devido à redução da acidez e ao aumento da basicidade na superfície dos catalisadores. O projeto proposto tem como objetivo principal criar uma metodologia de síntese de novos suportes Nb2O5-Al2O3 e catalisadores V2O5-Nb2O5-Al2O3 dopados com potássio a serem utilizados em processos petroquímicos para a produção de olefinas leves. Para tanto, as seguintes técnicas de caracterização foram utilizadas: espectrometria de absorção atômica, espectroscopia de emissão atômica com plasma indutivamente acoplado (ICP-OES), volumetria de N2, difratometria de raios X (DRX) e redução à temperatura programada (RTP). As características ácidas e/ou básicas e a atividade catalítica dos suportes e catalisadores foram medidas pelas reações de decomposição do isopropanol e de desidrogenação oxidativa do propano, respectivamente. / Catalysts based on metal oxides have been extensively used in recent years for the oxidative dehydrogenation of light alkanes. Among the main catalysts, there are the systems containing V2O5, Nb2O5 e Al2O3. The oxidative dehydrogenation of propane (ODH) provides a potential low-temperature route for the synthesis of propylene, but its practice has been limited by a marked decrease in propene selectivity with increasing conversion of reactant. Alkali metals, such as potassium, are frequently used as promoters in selective oxidation reactions with the objective of providing higher selectivity in catalytic reaction mechanisms, due to the reduced acidity and increasing basicity of the catalysts surface. The considered project has as major objective create a new synthesis methodology of Nb2O5-Al2O3 supports and V2O5-Nb2O5-Al2O3 potassium-doped catalysts to be used in petrochemical processes for the production of light olefins. For in such a way, the following characterization techniques were used: atomic absorption spectrometry, inductively coupled plasma optic emission spectroscopy (ICP-OES), N2 volumetry, X-ray diffractometry (XRD) and temperature programmed reduction (TPR). The properties acid and/or basic and the catalytic activity of supports and catalysts were evaluated by the isopropanol decomposition and oxidative dehydrogenation of propane reactions, respectively.

This research explored different catalytic cracking zeolite additives to improve propylene selectivity and minimize dry gas yield. A comprehensive study of the effect of zeolite structure, pore system and crystal size on maximizing propylene production in FCC unit and the effect of post synthetic modifications on the physicochemical properties and cracking activity of ZSM-5 was investigated using X-ray diffraction (XRD), pyridine adsorption fourier transform infra-red (FTIR), 27Al and 29Si magic-angle spinning nuclear magnetic resonance (MAS NMR) and the catalytic cracking using n-heptane, as a model compound for heavy naphtha. The catalytic performances of these additives were evaluated in a fixed-bed reactor unit using n-heptane as a model compound for naphtha at temperatures 450 - 500 oC and W/F 38 - 92 gcat.h/mol. A range of zeolites were tested with ZSM-5 showing the optimum results at high feed conversion. Further studies on ZSM-5 crystal size illustrated that nano ZSM-5 (300 nm) was superior compared to the regular ZSM-5 (2000 - 4000 nm) in achieved conversion level and propylene selectivity. These improvements were attributed to the shorter path lengths for the reactant reducing diffusion constraints significantly. Modifying nano ZSM-5 acidity using steaming, acid leaching and silanation showed significant improvement over nano ZSM-5 parent. Mild steaming of nano ZSM-5 improved both n-heptane conversion and propylene selectivity whilst severe steaming only improved propylene selectivity. This work attempted to address the often discussed catalytic activity enhancement from mild steaming and identified newly created moderate acid sites as the source of increased activity. Dealumination by acid leaching decreased the total aluminium content of nano ZSM-5 and changed the Brønsted/Lewis ratio. Increasing the B/L ratio, increased the conversion and propylene selectivity. In addition, this research focussed for the first time on the silanation of nano ZSM-5 and its effect on n-heptane cracking, in particular, propylene and dry gas selectivity. Silica was deposited on the external surface of nano ZSM-5 neutralising the acidic sites and as a result, dry gas yield was significantly decreased due to the elimination of non-selective cracking. However, the trade off with conversion was high.

Catalisadores baseados em óxidos metálicos têm sido muito utilizados nos últimos anos para a desidrogenação oxidativa de alcanos leves. Dentre os principais catalisadores, estão os sistemas contendo V2O5, Nb2O5 e Al2O3. O processo de desidrogenação oxidativa do propano (DOP) representa uma via alternativa importante para a produção de propileno sob menores temperaturas, porém sua prática vem sendo limitada pela diminuição dos valores de seletividade ao propeno com o aumento da conversão do reagente. Metais alcalinos, dentre eles o potássio, são frequentemente utilizados como promotores em reações de oxidação seletiva com o objetivo de proporcionar melhores seletividades catalíticas aos mecanismos de reação, devido à redução da acidez e ao aumento da basicidade na superfície dos catalisadores. O projeto proposto tem como objetivo principal criar uma metodologia de síntese de novos suportes Nb2O5-Al2O3 e catalisadores V2O5-Nb2O5-Al2O3 dopados com potássio a serem utilizados em processos petroquímicos para a produção de olefinas leves. Para tanto, as seguintes técnicas de caracterização foram utilizadas: espectrometria de absorção atômica, espectroscopia de emissão atômica com plasma indutivamente acoplado (ICP-OES), volumetria de N2, difratometria de raios X (DRX) e redução à temperatura programada (RTP). As características ácidas e/ou básicas e a atividade catalítica dos suportes e catalisadores foram medidas pelas reações de decomposição do isopropanol e de desidrogenação oxidativa do propano, respectivamente. / Catalysts based on metal oxides have been extensively used in recent years for the oxidative dehydrogenation of light alkanes. Among the main catalysts, there are the systems containing V2O5, Nb2O5 e Al2O3. The oxidative dehydrogenation of propane (ODH) provides a potential low-temperature route for the synthesis of propylene, but its practice has been limited by a marked decrease in propene selectivity with increasing conversion of reactant. Alkali metals, such as potassium, are frequently used as promoters in selective oxidation reactions with the objective of providing higher selectivity in catalytic reaction mechanisms, due to the reduced acidity and increasing basicity of the catalysts surface. The considered project has as major objective create a new synthesis methodology of Nb2O5-Al2O3 supports and V2O5-Nb2O5-Al2O3 potassium-doped catalysts to be used in petrochemical processes for the production of light olefins. For in such a way, the following characterization techniques were used: atomic absorption spectrometry, inductively coupled plasma optic emission spectroscopy (ICP-OES), N2 volumetry, X-ray diffractometry (XRD) and temperature programmed reduction (TPR). The properties acid and/or basic and the catalytic activity of supports and catalysts were evaluated by the isopropanol decomposition and oxidative dehydrogenation of propane reactions, respectively.

<p>Hereditary ichthyosis is a collective name for many dry and scaly skin disorders ranging in frequency from common to very rare. The main groups are autosomal recessive lamellar ichthyosis, autosomal dominant epidermolytic hyperkeratosis and ichthyosis vulgaris, and x-linked recessive ichthyosis. Anhidrosis, ectropion and keratodermia are common symptoms, especially in lamellar ichthyosis, which is often caused by mutations in the transglutaminase 1 (TGM1) gene. The aim of this work was to study patients with different types of ichthyosis regarding (i) the patho-aetiology (TGM1 and electron microscopy [EM] analysis), (ii) skin signs and symptoms (clinical score and subjective measure of disease activity), (iii) quality of life (questionnaires DLQI, SF-36 and NHP and face-to-face interviews) and (iv) a search for new ways of topical treatment. Patients from Sweden and Estonia with autosomal recessive congenital ichthyosis (n=83) had a broader clinical spectrum than anticipated, but a majority carried TGM1 mutations. Based on DNA analysis and clinical examinations the patients were classified into three groups, which could be further subdivided after EM analysis. Our studies indicate that patients with ichthyosis have reduced quality of life as reflected by DLQI and by some domains of SF-36, by NHP and the interviews. All the interviewees reported that their skin disease had affected them negatively to varying degrees during their entire lives and that the most problematic period was childhood. All patients with ichthyosis use topical therapy. In a double-blind study creams containing either 5% urea or 20% propylene glycol were found inferior to a cream formulation containing lactic acid 5% and propylene glycol 20% both regarding clinical improvement and thinning of the skin barrier. Improved topical therapy may reduce the need of more toxic, oral drugs. Future studies should elucidate whether this increases the quality of life of ichthyosis patients, especially if combined with more detailed information about the aetiology and inheritance of the diseases.</p>

Hereditary ichthyosis is a collective name for many dry and scaly skin disorders ranging in frequency from common to very rare. The main groups are autosomal recessive lamellar ichthyosis, autosomal dominant epidermolytic hyperkeratosis and ichthyosis vulgaris, and x-linked recessive ichthyosis. Anhidrosis, ectropion and keratodermia are common symptoms, especially in lamellar ichthyosis, which is often caused by mutations in the transglutaminase 1 (TGM1) gene. The aim of this work was to study patients with different types of ichthyosis regarding (i) the patho-aetiology (TGM1 and electron microscopy [EM] analysis), (ii) skin signs and symptoms (clinical score and subjective measure of disease activity), (iii) quality of life (questionnaires DLQI, SF-36 and NHP and face-to-face interviews) and (iv) a search for new ways of topical treatment. Patients from Sweden and Estonia with autosomal recessive congenital ichthyosis (n=83) had a broader clinical spectrum than anticipated, but a majority carried TGM1 mutations. Based on DNA analysis and clinical examinations the patients were classified into three groups, which could be further subdivided after EM analysis. Our studies indicate that patients with ichthyosis have reduced quality of life as reflected by DLQI and by some domains of SF-36, by NHP and the interviews. All the interviewees reported that their skin disease had affected them negatively to varying degrees during their entire lives and that the most problematic period was childhood. All patients with ichthyosis use topical therapy. In a double-blind study creams containing either 5% urea or 20% propylene glycol were found inferior to a cream formulation containing lactic acid 5% and propylene glycol 20% both regarding clinical improvement and thinning of the skin barrier. Improved topical therapy may reduce the need of more toxic, oral drugs. Future studies should elucidate whether this increases the quality of life of ichthyosis patients, especially if combined with more detailed information about the aetiology and inheritance of the diseases.