This study focuses on the development of novel two-stage esterification-transesterification synthesis of biodiesel from used cooking oil (UCO) using novel heterogeneous catalysts. The esterification of the UCO was investigated using three types of ion exchange resins catalysts including Purolite D5081, Purolite D5082 and Amberlyst 15. Of all the catalysts investigated, Purolite D5081 resin showed the best catalytic performance and was selected for further optimisation studies. From the optimisation study, it was found that the external and internal mass transfer resistance has negligible effect on the esterification reaction. At the optimum reaction conditions, Purolite D5081 achieved 92% conversion of FFA. During reusability study, the conversion of FFA dropped by 10% after each cycle and it was found that progressive pore blockage and sulphur leaching were dominant factors that decreased the catalytic performance of the Purolite D5081 catalyst. A kinetic modelling for FFA esterification was carried out using Purolite D5081 as a catalyst. Three types of kinetic models were investigated i.e. pseudo homogeneous (PH), Eley-Rideal (ER) and Langmuir-Hinshelwood-Hougen-Watson (LHHW). Experimental data obtained from the batch kinetic studies was successfully represented by the PH model and a good agreement between experimental and calculated values was obtained. The activation energy for esterification and hydrolysis reaction was found to be 53 and 107 kJ/moL. The transesterification of pre-treated cooking oil (P-UCO) was investigated using various types of heterogeneous catalysts including Purolite CT-122, Purolite CT-169, Purolite CT-175, Purolite CT-275, Purolite D5081, Diaion PA306s and Cs-supported heteropolyacids catalysts. Of all the catalysts investigated, Diaion PA306s catalyst showed the highest conversion of triglycerides and was selected for further optimisation studies. At the optimum reaction conditions, Diaion PA306s achieved ca. 75% of triglycerides conversion. During the reusability study, Diaion PA306s catalyst gave a similar conversion of triglycerides after being reused once. Therefore, it was concluded that the resin can be used several times without losing catalytic activity. Several purification methods have been investigated and dry washing method was chosen as the best alternative for biodiesel purification.

Neste trabalho mostramos que o método de purificação empregando a coluna ANX Sepharose FF, alternando eluições com CaCl2 (pseudoafinidade) e NaCl, permite obter concentrados do complexo protrombínico e do fator VIII em uma etapa cromatográfica. Testamos as colunas ANX e Q Sepharose FF, monolito QA e membrana Sartobind Q e os tampões citrato, MES e Bis-Tris. Empregando a ANX Sepharose FF e o tampão citrato as proteínas do complexo protrombínico eluiram com CaCl2 25 mM e o FVIII com NaCl 500mM. A recuperação da atividade de FVIII foi de cerca de 60% e o fator de purificação de 220 vezes. Na fração contendo as proteínas do complexo protrombínico foram identificadas por espectrometria de massas a presença de fibrinogênio, proteína C4 do complemento e C4b Binding Protein. A análise das frações mostra que a presença destas proteínas não é devido à variação da concentração de CaCl2, possivelmente se deve à difusão lenta destas através da resina. Mais de 99% das proteínas do plasma não são adsorvidas na coluna e podem ser purificadas em etapas posteriores. / In this study we showed that the purification method employing the anion exchange column ANX Sepharose FF, and alternating CaCl2 (pseudoaffinity) and NaCl elutions, allows us to obtain concentrates of prothrombin complex proteins and factor VIII in a single chromatographic step. We tested the ANX, Q Sepharose FF and QA monolithic column and Sartobind Q membrane and the citrate, MES and Bis-Tris buffers. Using ANX Sepharose FF and the citrate buffer the prothrombin complex proteins eluted with 25 mM CaCl2 and FVIII with 500 mM NaCl. FVIII activity recovery was approximately 60% with a purification factor of 220. In the fraction containing the prothrombin complex proteins presence of fibrinogen, complement C4 and C4bBinding Protein were identified by mass spectrometry. Analysis of the fractions showed that their presence is not due to the variation of concentration of CaCl2, but possibly due to their slow diffusion through the resin. More than 99% of the plasma proteins are not adsorbed in the column and can be purified in following chromatographic steps.

Não há dúvidas que a exitosa exploração do Cerrado só foi possível graças às pesquisas que desenvolveram tecnologias de correção e adubação específicas para esse ambiente. Apesar de estar consolidado como um dos principais ambientes de produção agropecuária do mundo, as pesquisas devem avançar contribuindo, cada vez mais, com aumento na eficiência do uso do fósforo (P), por ser o elemento mais limitante para produção agrícola nesse ambiente. Devido às características dos solos dessa região, parte do P aplicado é retido pelo solo em formas que as plantas não conseguem absorver, resultando na acumulação de quantidades significativas do nutriente no solo. Apesar de não ser um assunto relativamente novo e do grande número de trabalhos, o tema avaliação da disponibilidade de fósforo do solo ainda provoca dúvidas. Além dos estudos em que é avaliada a eficiência de diversos extratores como Mehlich-1 e resina de troca aniônica, outras técnicas passaram a ser utilizadas para esse fim. Estudos objetivando avaliar a distribuição (dinâmica) do fósforo nas diferentes frações do solo e as mudanças nessa distribuição em função do manejo aplicado aos cultivos e, também, do tempo de cultivo, têm sido conduzidos com crescente intensidade. Estudos também têm sido conduzidos buscando identificar as formas de acumulação de P no solo. Para isso, modernas técnicas espectroscópicas, como por exemplo, a espectroscopia baseada em luz synchrotron, têm sido utilizadas como uma poderosa ferramenta, auxiliando na identificação dos compostos presentes no solo. Face ao exposto, objetivou-se avaliar as alterações no fósforo disponível e nas frações e formas de fósforo em solo de Cerrado submetido ao manejo em semeadura direta com diferentes tempos de cultivo. Foram coletadas amostras compostas em quatro áreas que se encontravam no momento da coleta com 5, 8, 12 e 18 anos de cultivo desde a abertura das áreas, e também numa área sob vegetação nativa. O fósforo disponível foi extraído por Mehlich-1 e resina de troca aniônica. As amostras foram submetidas ao fracionamento químico de fósforo e espectroscopia de alta resolução da borda de absorção (XANES - X-ray absorption near edge structure). Observou-se que, de maneira geral, os teores de fósforo no solo foram sempre mais altos nas áreas cultivadas, principalmente na camada superficial, em comparação aos da área com vegetação nativa, o que reflete o impacto das adubações fosfatadas. A aplicação superficial do fertilizante fosfatado gerou nítidos gradientes de P no perfil do solo, principalmente para as frações lábeis e moderadamente lábeis, sendo essas frações as que sofreram maior influência do fertilizante quando comparadas às frações de menor disponibilidade. Considerando-se os mesmos extratores, os teores das frações orgânicas foram maiores em comparação às correspondentes frações inorgânicas. As formas de fósforo nos solos estudados foram predominantemente associadas ao alumínio e ao ferro, com destaque para o nutriente associado ao alumínio, sendo que, com o ferro, a associação ocorreu predominantemente por meio de fenômenos de adsorção em detrimento de fenômenos de precipitação. / There is no doubt that the successful exploitation of the Cerrado was only possible due to the research that developed specific correction and fertilization technologies to this particular environment. Due to the characteristics of soils in the region, part of applied phosphorus (P) is retained by the soil in plant unavailable forms, resulting in accumulation of significant amounts of nutrient in the soil. Despite not being a relatively new issue and the large number of research performed on this topic, the assessment of the soil P availability still raise important questions. In addition to studies in which the efficiency of various extractants have been tested, such as Mehlich-1 and anion exchange resin, other techniques are being used for this purpose. Studies for evaluating the P distribution (dynamic) in different soil fractions and the changes in this fractions due to the management applied to crops and also the time of cultivation have been conducted with increasing intensity. Studies have also been carried out in order to identify the forms of P accumulation in soils. For this purpose, modern spectroscopic techniques such as spectroscopy based on synchrotron light source, have been used as a powerful tool, assisting in the identification of P compounds presents in the soil. The aims of this study were to evaluate the changes in available, fractions and forms of P in soils of Cerrado with different times under no-till cultivation system. Composite soil samples were collected in four areas under 5, 8, 12 and 18 years of no-till cultivation since the areas were opened, and also in a area under native vegetation. The soil in the area was classified as Typic Hapludox and the areas were cultivated alternating crops of soybeans, corn and cotton. Available P was extracted by Mehlich - 1 and anion exchange resin. The samples were subjected to Hedley´s chemical fractionation of P and X- ray absorption near edge structure (XANES). It was observed that, in general, the levels of P in the soil were always higher in cultivated areas, mainly in the topsoil, when compared to the area under native vegetation, which reflects the impact of phosphate fertilization. Surface application of phosphate fertilizer produced sharp gradients of P in the soil profile, especially for both labile and moderately labile fractions, and these fractions suffered the greatest influence of fertilizer compared to fractions of lower availability. Considering the same extractants, the organic P fractions contents were higher compared to the corresponding inorganic fractions. Forms of phosphorus in soils were predominantly associated with aluminum (Al) and iron (Fe), especially P associated with Al, and with Fe the association occurred predominantly through adsorption phenomenon rather than precipitation reactions.

Não há dúvidas que a exitosa exploração do Cerrado só foi possível graças às pesquisas que desenvolveram tecnologias de correção e adubação específicas para esse ambiente. Apesar de estar consolidado como um dos principais ambientes de produção agropecuária do mundo, as pesquisas devem avançar contribuindo, cada vez mais, com aumento na eficiência do uso do fósforo (P), por ser o elemento mais limitante para produção agrícola nesse ambiente. Devido às características dos solos dessa região, parte do P aplicado é retido pelo solo em formas que as plantas não conseguem absorver, resultando na acumulação de quantidades significativas do nutriente no solo. Apesar de não ser um assunto relativamente novo e do grande número de trabalhos, o tema avaliação da disponibilidade de fósforo do solo ainda provoca dúvidas. Além dos estudos em que é avaliada a eficiência de diversos extratores como Mehlich-1 e resina de troca aniônica, outras técnicas passaram a ser utilizadas para esse fim. Estudos objetivando avaliar a distribuição (dinâmica) do fósforo nas diferentes frações do solo e as mudanças nessa distribuição em função do manejo aplicado aos cultivos e, também, do tempo de cultivo, têm sido conduzidos com crescente intensidade. Estudos também têm sido conduzidos buscando identificar as formas de acumulação de P no solo. Para isso, modernas técnicas espectroscópicas, como por exemplo, a espectroscopia baseada em luz synchrotron, têm sido utilizadas como uma poderosa ferramenta, auxiliando na identificação dos compostos presentes no solo. Face ao exposto, objetivou-se avaliar as alterações no fósforo disponível e nas frações e formas de fósforo em solo de Cerrado submetido ao manejo em semeadura direta com diferentes tempos de cultivo. Foram coletadas amostras compostas em quatro áreas que se encontravam no momento da coleta com 5, 8, 12 e 18 anos de cultivo desde a abertura das áreas, e também numa área sob vegetação nativa. O fósforo disponível foi extraído por Mehlich-1 e resina de troca aniônica. As amostras foram submetidas ao fracionamento químico de fósforo e espectroscopia de alta resolução da borda de absorção (XANES - X-ray absorption near edge structure). Observou-se que, de maneira geral, os teores de fósforo no solo foram sempre mais altos nas áreas cultivadas, principalmente na camada superficial, em comparação aos da área com vegetação nativa, o que reflete o impacto das adubações fosfatadas. A aplicação superficial do fertilizante fosfatado gerou nítidos gradientes de P no perfil do solo, principalmente para as frações lábeis e moderadamente lábeis, sendo essas frações as que sofreram maior influência do fertilizante quando comparadas às frações de menor disponibilidade. Considerando-se os mesmos extratores, os teores das frações orgânicas foram maiores em comparação às correspondentes frações inorgânicas. As formas de fósforo nos solos estudados foram predominantemente associadas ao alumínio e ao ferro, com destaque para o nutriente associado ao alumínio, sendo que, com o ferro, a associação ocorreu predominantemente por meio de fenômenos de adsorção em detrimento de fenômenos de precipitação. / There is no doubt that the successful exploitation of the Cerrado was only possible due to the research that developed specific correction and fertilization technologies to this particular environment. Due to the characteristics of soils in the region, part of applied phosphorus (P) is retained by the soil in plant unavailable forms, resulting in accumulation of significant amounts of nutrient in the soil. Despite not being a relatively new issue and the large number of research performed on this topic, the assessment of the soil P availability still raise important questions. In addition to studies in which the efficiency of various extractants have been tested, such as Mehlich-1 and anion exchange resin, other techniques are being used for this purpose. Studies for evaluating the P distribution (dynamic) in different soil fractions and the changes in this fractions due to the management applied to crops and also the time of cultivation have been conducted with increasing intensity. Studies have also been carried out in order to identify the forms of P accumulation in soils. For this purpose, modern spectroscopic techniques such as spectroscopy based on synchrotron light source, have been used as a powerful tool, assisting in the identification of P compounds presents in the soil. The aims of this study were to evaluate the changes in available, fractions and forms of P in soils of Cerrado with different times under no-till cultivation system. Composite soil samples were collected in four areas under 5, 8, 12 and 18 years of no-till cultivation since the areas were opened, and also in a area under native vegetation. The soil in the area was classified as Typic Hapludox and the areas were cultivated alternating crops of soybeans, corn and cotton. Available P was extracted by Mehlich - 1 and anion exchange resin. The samples were subjected to Hedley´s chemical fractionation of P and X- ray absorption near edge structure (XANES). It was observed that, in general, the levels of P in the soil were always higher in cultivated areas, mainly in the topsoil, when compared to the area under native vegetation, which reflects the impact of phosphate fertilization. Surface application of phosphate fertilizer produced sharp gradients of P in the soil profile, especially for both labile and moderately labile fractions, and these fractions suffered the greatest influence of fertilizer compared to fractions of lower availability. Considering the same extractants, the organic P fractions contents were higher compared to the corresponding inorganic fractions. Forms of phosphorus in soils were predominantly associated with aluminum (Al) and iron (Fe), especially P associated with Al, and with Fe the association occurred predominantly through adsorption phenomenon rather than precipitation reactions.

Linear covalently closed (LCC) DNA minivectors serve to be superior to conventional circular covalently closed (CCC) plasmid DNA (pDNA) vectors due to enhancements to both transfection efficiency and safety. Specifically, LCC DNA minivectors have a heightened safety profile as insertional mutagenesis is inhibited by covalently closed terminal ends conferring double-strand breaks that cause chromosomal disruption and cell death in the low frequency event of chromosomal integration. The development of a one-step, E. coli based in vivo LCC DNA minivector production system enables facile and efficient production of LCC DNA minivectors referred to as DNA ministrings. This novel in vivo system demonstrates high versatility, generating DNA ministrings catered to numerous potential applications in gene therapy and vaccine development. In the present study, numerous aspects pertaining to the generation of gene therapeutics with LCC DNA ministrings have been explored with relevance to both industry and clinical settings. Through systematic assessment of induction duration, cultivation strategy, and genetic/chemical modifications, the novel in vivo system was optimized to produce high yields of DNA ministrings at ~90% production efficiency. Purification of LCC DNA ministrings using anion exchange membrane chromatography demonstrated rapid, scalable purification of DNA vectors as well as its potential in the separation of different DNA isoforms. The application of a hydrogel-based strong Q-anion exchange membrane, with manipulations to salt gradient, constituted effective separation of parental supercoiled CCC precursor pDNA and LCC DNA. The resulting DNA ministrings were employed for the generation of 16-3-16 gemini surfactant based synthetic vectors and comparative analysis, through physical characterization and in vitro transfection assays, was conducted between DNA ministring derived and CCC pDNA derived lipoplexes. Differences in DNA topology were observed to induce differences in particle size and DNA protection/encapsulation upon lipoplex formation. Lastly, the in vivo DNA minivector production system successfully generated gagV3(BCE) LCC DNA ministrings for downstream development of a HIV DNA-VLP (Virus-like particle) vaccine, thus highlighting the capacity of such system to produce DNA ministrings with numerous potential applications.

The elimination of natural organic matter (NOM) is an important aim of water treatment in demineralisation plants of power stations. NOM is regarded as corrosion risk factor in the steam water cycle because of its potential to decompose into low-molecular-weight (LMW) acids and carbon dioxide. Further, the removal of NOM is also one of the main objectives in the drinking water production, since it can cause i) colour, taste and odour problems, ii) formation of carcinogen halogenated disinfection by-products (DBPs) after disinfection with chlorine and iii) bacterial growth in the water distribution system. In earlier studies, it was found that anion exchange is a successful method to remove NOM fractions. However, NOM fractions with low charge density (LMW neutrals and hydrophobic organic carbon (HOC)) and/or large molecular size (biopolymers and particulate organic carbon (POC)) could not be removed in some cases in satisfying quantities. The aim of the present work was to investigate the uptake performance of different anion exchange resins (AERs) in regard to problematic NOM fractions. The AERs differ especially in their functional groups (tertiary versus quaternary amines) and matrix material (polystyrene versus polyacrylic resins). The use of different AERs provides an option to identify possible interactions between adsorbate (NOM fractions) and adsorber (AERs) as well as the mechanism which determine the removal efficiency. The NOM fraction adsorption onto AERs was studied in equilibrium and fixed-bed experiments with three types of starch with different molecular size distributions (model substances for biopolymer fraction) as well as 2-naphthol (model substance for the LMW neutral fraction) at acidic pH (relevant for water in demineralisation plants of power stations) and neutral pH (covering most raw waters). Furthermore, the NOM fraction uptake from “real” acidic and neutral water samples, obtained from a demineralisation plant of a power station, was estimated for different AERs. Results were discussed in terms of size-exclusion, anion exchange and hydrophilic/hydrophobic repulsion. In case that size-exclusion influences the NOM uptake onto AERs, it was found that the smaller the size of the NOM molecules and the higher the water content of the AERs, the more effective the uptake is. Thus, for the removal of biopolymers and POC, polyacrylic resins with high water content could be a good choice. Contrary, polystyrene AERs are the most effective resins in the removal of NOM fractions, if no size-exclusion occurs. They seem to be able to uptake more hydrophilic NOM fractions by polar/ionic interactions between acids/acidic components and tertiary/quaternary amines as well as to remove more hydrophobic NOM fractions by π-π stacking and/or hydrophobic interactions on the polystyrene matrix. Further, it was found that the higher the total volume (anion exchange) capacity of an AER, the higher its NOM removal by polar/ionic interactions can be. At acidic pH, weak/medium base AERs have higher total volume (anion exchange) capacities than strong base AERs, whereas, at neutral pH, strong base AERs have the highest ones. In view of these results, the application of polyacrylic AERs with high water content can be recommended to remove NOM components with large molecular size in demineralisation and drinking water plants. If there is a higher amount of smaller NOM fractions, especially LMW neutrals, than polystyrene weak/medium base AERs should be favoured in demineralisation plants and polystyrene strong base AERs in drinking water treatment plants. From the engineering point of view, breakthrough curve (BTC) prediction models are important for the design of fixed-bed filter. Therefore, two different BTC model approaches were tested in the present study to describe the single-solute adsorption onto AERs: i) the homogenous surface diffusion model (HSDM) with linear driving force (LDF) approach for surface diffusion, known from activated carbon adsorption, and ii) the Glueckauf/Helfferich formulae as an extension of the height equivalent to a theoretical plate (HETP) model, initially used to describe ion exchange processes. It was found that the Glueckauf/Helfferich approach is not only a suitable tool for the fast calculation of BTCs for ionic components, but it can also successfully be applied, after considering the Freundlich model for the mass balance, for the rapid prediction of BTCs for single-solute organic molecules. For competitive BTC predictions, the ideal adsorbed solution theory (IAST) within the LDF model was applied. All calculated BTCs fit the experimental data in a good manner. Thus, the investigated BTC models can be applied for estimating the breakthrough bed volumes of different AERs to avoid leakage of NOM in the drinking or demineralised water caused by overloading. / Die Entfernung von natürlichen organischen Substanzen (NOM) ist ein wichtiges Ziel für die Herstellung von Reinstwasser im Kraftwerksbetrieb, da diese sich im Wasser/Dampf-Kreislauf zu niedermolekularen Säuren und Kohlenstoffdioxid zersetzen können und so ein potentielles Korrosionsrisiko darstellen. Außerdem ist die Elimination von natürlichen organischen Substanzen einer der Schwerpunkte in der Trinkwasseraufbereitung, da NOM im Trinkwasser folgende Konsequenzen verursachen können i) Farb-, Geschmacks- und Geruchsprobleme, ii) Bildung von kanzerogen halogenierten Desinfektionsnebenprodukten nach der Desinfektion mit Chlor und iii) Bakterienwachstum im Wasserverteilungssystem. In früheren Untersuchungen wurde festgestellt, dass Anionenaustauscherharze (AERs) die NOM-Fraktionen in der Regel erfolgreich aufnehmen können. Nur NOM-Fraktionen mit geringer Ladungsdichte (niedermolekulare Neutralstoffe und hydrophober organischer Kohlenstoff) und/oder großer Molekülgröße (Biopolymere und partikulärer organischer Kohlenstoff) können unter bestimmten Bedingungen nicht in zufriedenstellender Menge entfernt werden. Ziel dieser Arbeit war es, das Aufnahmeverhalten unterschiedlicher AERs hinsichtlich problematischer NOM-Fraktionen zu untersuchen. Die AERs unterscheiden sich vor allem in ihren funktionellen Gruppen (tertiäre versus quaternäre Amine) und ihrer Matrix (Polystyren- versus Polyacryl-Harze). Die Verwendung unterschiedlicher AERs erlaubt es, mögliche Wechselwirkungen zwischen Adsorbat (NOM-Fraktionen) und Adsorber (AERs) und die Mechanismen, die die NOM-Aufnahme entscheidend bestimmen, zu identifizieren. Die Entfernung von NOM-Fraktionen durch AERs wurde in Gleichgewichts- und Festbett-versuchen mittels dreier Stärketypen mit unterschiedlicher Molekülgrößenverteilung (Modellsubstanzen für die Biopolymere) und 2-Naphthol (Modellsubstanz für die Neutralstoffe) unter sauren pH-Bedingungen (relevant für die Herstellung von Reinstwasser im Kraftwerksbetrieb) und neutralen pH-Bedingungen (bedeutsam für die meisten Rohwässer) untersucht. Außerdem sollte das Adsorptionsverhalten von AERs bezüglich verschiedener NOM-Fraktionen unter Einsatz von „real“ neutralen und sauren Wasserproben aus einer Wasseraufbereitungsanlage eines Kraftwerksbetriebes eingeschätzt werden. In dieser Arbeit konnte gezeigt werden, dass falls Größenausschluss die NOM-Aufnahme von AERs beeinflusst, dann ist die Adsorption der NOM-Fraktionen umso größer, je kleiner die NOM-Moleküle sind und je höher der Wassergehalt der AERs ist. Daher kann für die Entfernung von größeren Biopolymeren, der Einsatz von AERs mit Polyacryl-Matrix und hohem Wassergehalt die beste Option sein. AERs mit Polystyren-Matrix besitzen die höchste Aufnahmekapazität für NOM-Fraktionen, falls kein Größenausschluss auftritt. Es scheint für sie möglich zu sein, sowohl hydrophile NOM-Fraktionen durch polare/ionische Wechselwirkungen zwischen NOM Säuren/sauren Komponenten und tertiären/quaternären Aminen aufzunehmen als auch hydrophobe NOM-Fraktionen durch π-π Anziehungen und/oder hydrophobe Interaktionen an die Polystyren-Matrix zu binden. Weiterhin konnte gezeigt werden, dass je höher die Gesamtvolumenkapazität eines AERs, desto größer ist die NOM-Entfernung auf Grund von polaren/ionischen Wechselwirkungen. Es gilt, dass schwach/mittel basische AERs im Vergleich zu stark basischen AERs höhere Gesamtvolumenkapazitäten unter sauren pH-Bedingungen besitzen und stark basische AERs die höchsten Gesamtvolumenkapazitäten unter neutralen pH-Bedingungen aufweisen. Auf Grund dieser Ergebnisse ist es möglich, die Verwendung von AERs mit Polyacryl-Matrix und hohem Wassergehalt für die Entfernung von NOM-Fraktionen mit großer Molekülgröße in Reinst- und Trinkwasseraufbereitungsanlagen zu empfehlen. Falls es einen höheren Anteil von kleineren NOM-Fraktionen, im Besonderen Neutralstoffen, gibt, sollte die Verwendung von schwach/mittel basischen AERs in Vollentsalzungsanlagen von Kraft-werksbetrieben und stark basischen AERs in Trinkwasseraufbereitungsanlagen bevorzugt werden. Vor allem im Hinblick auf technische Anwendungen ist es wichtig, Durchbruchskurven (BTC) vorausberechnen zu können. In der vorliegenden Arbeit wurden zwei Modellansätze für die Berechnung von BTCs für die Einkomponentenadsorption getestet: i) das homogene Oberflächendiffusionsmodell mit linearer Triebkraft (LDF), bekannt aus Untersuchungen zur Aufnahme von NOM an Aktivkohle, und ii) die Glueckauf/Helfferich-Formeln, primär verwendet für die Beschreibung von Ionenaustauschprozessen. Es konnte gezeigt werden, dass das Glueckauf/Helfferich-Verfahren nicht nur ein geeignetes Instrument für die schnelle Berechnung von BTCs für ionische Komponenten ist, sondern dass dieses, nach Berücksichtigung des Freundlich-Ansatzes in der Massenbilanz, auch erfolgreich angewendet werden kann, um BTCs für Einkomponentenadsorption von Organika zu berechnen. Für die Vorausberechnung von BTCs für Mehrkomponentensysteme wurde die Theorie der idealen adsorbierten Lösung im LDF-Modell genutzt. Die berechneten BTCs stimmen in guter Qualität mit den experimentell ermittelten BTCs überein. Die Ergebnisse verdeutlichen, dass die untersuchten BTC-Modelle eingesetzt werden können, um Durchbruchspunkte für die jeweiligen AERs zu bestimmen und damit die Gefahr des Schlupfes von NOM ins Trink- bzw. Reinstwasser zu minimieren.

Per- and polyfluoroalkyl substances (PFASs) is a group of man-made, highly persistent chemicals. Due to the specific surface-active attributes of these molecules, applications are numerous and feed an economically important industry. During the last decade, PFASs have been detected globally in the environment, living organisms and tap water. The combination of toxic properties and high bioaccumulative potential, together with the discovery that conventional water treatment methods do not remove PFAS, renders further research on purification methods highly needed.  Three techniques of purifying water from PFASs were examined. Nanofiltration technology (NF) is a membrane filtration technique, which produces a purified product (the permeate) by generating an effluent of high contaminant concentration (the reject water). To decontaminate the reject water, adsorption by granular activated carbon (GAC) or anion exchange (AE) have been proposed. The efficiency of these three technologies was studied at Bäcklösa drinking water treatment plant (DWTP) in Uppsala. A nanofiltration pilot with two 270NF membranes (Dow Filmtech™), connected in series, was used. A high removal efficiency (>90%) was found for all PFASs. Furthermore, it was confirmed that the concentration in the permeate water was a function of the concentration in the incoming raw water; increased PFAS raw water concentration resulted in increased PFAS permeate concentration. Size-exclusion and electrostatic repulsion were deemed important mechanisms. For the comparison of GAC (Filtrasorb 400®) and AE (Purolite® A-600), a column experiment was set up. The perfluoroalkane (-alkyl) sulfonic acids (PFSAs) and perfluorooctanesulfonamide (FOSA) had similar removal efficiencies using both GAC and AE, and the efficiency increased with increasing chain length. AE was found to have a higher average removal efficiency of perfluoroalkyl carboxylic acid (PFCAs) (62-95%) than GAC (49-81%). In conclusion, longer chain length PFASs were removed more effectively than shorter-chained, and the PFSAs and FOSA showed higher removal efficiency compared to the PFCAs. Furthermore, linear isomers were removed more effectively than branched for GAC and AE. In contrast, the opposite was found for the NF membrane, where branched isomers were better retained. / Per- och polyfluorerade alkylsubstanser (PFAS) är en grupp syntetiska, ytterst persistenta kemikalier. På grund av deras ytaktiva egenskaper är de lämpliga för användning i många produkter och tillverkningsprocesser, och är således viktiga för en ekonomiskt betydande industri. Under det senaste årtiondet har PFAS påträffats i miljön, levande organismer och kranvatten världen över.  Kombinationen av toxiska egenskaper, en hög bioackumuleringspotential och upptäckten att konventionella reningsmetoder inte avlägsnar substanserna från vatten, gör att vidare forskning av reningsmetoder för PFAS är mycket angelägen. Tre reningsteknikers förmåga att rena vatten från PFAS undersöktes. Nanofiltrering (NF) är en membranfiltreringsteknik som utöver den renade produkten, permeatet, även framställer en biprodukt av hög föroreningsgrad, rententatet. För att rena rententatet har adsorption till granulärt aktivt kol (GAC) eller jonbytarmassa (AE) föreslagits. Teknikerna utvärderades på Bäcklösa Vattenverk i Uppsala.  Nanofiltreringen undersöktes i en pilotanläggning där två 270NF (Dow Filmtech™) membran var seriekopplade. En hög reningsgrad (>90%) konstaterades för alla typer av PFAS. Vidare visades PFAS-koncentrationen i permeatet vara en funktion av PFAS-koncentrationen i råvattnet; en ökad råvattenkoncentration gav en ökad permeatkoncentration. Storleksseparation och elektrostatisk repulsion befanns vara viktiga mekanismer som påverkade reningsgraden. För att undersöka de mekanismer som påverkar PFAS-adsorption jämfördes GAC (Filtrasorb 400®) och AE (Purolite® A-600) i ett kolonnexperiment. Reningsgraden för GAC och AE av perfluorerade sulfonsyror (PFSA) och perfluorooktan sulfonamider (FOSA) var lika hög och reningseffektiviteten ökade med ökande kolkedjelängd. AE återfanns ha en högre genomsnittlig reningsgrad av perfluorkarboxylsyror (PFCA) (62-95%) än GAC (49-81%). Sammanfattningsvis avlägsnades PFAS av längre kolkedjelängd mer effektivt än kortare kolkedjor, och PFAS med sulfonsyror och sulfonamider som funktionella grupper uppvisade en högre reningsgrad än karboxylsyrorna. Vidare renades linjära isomerer mer effektivt än grenade både genom GAC och AE. Däremot konstaterades det motsatta för NF-membranen, där grenade isomerer renades mer effektivt. / SafeDrink

Ce travail porte sur la synthèse et la caractérisation de membranes polymères échangeuses d'anions, destinées à la protection de l'électrode à air dans une batterie lithium-air (en vue d'une application pour véhicule électrique). Ces matériaux à architecture de réseaux interpénétrés de polymères (RIP) associent un réseau polyélectrolyte cationique hydrocarboné, la poly(épichlorohydrine) (PECH), à un réseau de polymère neutre qui peut être soit hydrocarboné, soit fluoré. Tout d'abord, la synthèse du réseau polyélectrolyte et son assemblage sur l'électrode à air ont été optimisés. Une première série de RIP associant ce réseau PECH à un réseau de poly(méthacrylate d'hydroxyéthyle) a été synthétisée. Une seconde série de matériaux combinant ce même réseau PECH à un réseau de polymère fluoré a été développée. L'ensemble de ces matériaux a été caractérisé, et pour chaque série de RIP, la méthode de synthèse et la composition ont été optimisées. Les membranes RIP présentent des propriétés améliorées par rapport au réseau simple de PECH. L'électrode à air protégée par ces nouvelles membranes échangeuses d'anions présente une stabilité améliorée dans les conditions de fonctionnement de la batterie lithium-air. Plus précisément, une durée de vie de 1000 h est obtenue lorsque l'électrode à air a été modifiée avec un RIP fluoré, soit une augmentation d'un facteur 20 de la durée de vie de l'électrode non modifiée. / This work focuses on the synthesis and characterization of polymer membranes to be used as anion exchange membranes for protection on an air electrode in a new lithium–air battery for electric vehicle. In these materials showing interpenetrating polymer networks (IPN) architecture, a hydrogenated cationic polyelectrolyte network, the poly(epichlorohydrin) (PECH), is associated with a neutral network, which can be either hydrogenated or fluorinated. First, the synthesis of the polyelectrolyte network and the membrane/electrode assembly were optimized. Second, a first IPN series associating the PECH network with a poly(hydroxyethyl methacrylate) network was synthesized. Third, the same PECH network was associated with a fluorinated polymer network. All the materials were characterized, and optimal synthesis methods as well as an optimal composition were determined for each association. The IPNs show improved properties compared with the single PECH network. The air electrode protected by these new anion exchange membranes shows improved stability in the working conditions of the lithium-air battery. Specifically, a lifetime of 1000 h was obtained when the electrode was modified with a fluorinated IPN, a 20-fold increase in the lifetime of the non-modified electrode.

Introduction Oligonucleotides are short nucleic acid chains, usually 19-27mer long. They bind to their corresponding chain, making a specific inhibition possible. In pharmaceuticals, this can be used to inhibit the expression of a gene or protein of interest. Oligonucleotides are usually analyzed based on separation using both hydrophobic and ion-exchange properties. In this project, the possibility to use a mixed-mode column to separate these oligonucleotides and their impurities were explored. Method Liquid chromatography is used as the separation method and the method of detection is both mass spectrometry and UV. Three different columns are evaluated; C18, DNAPac RP, and mixed-mode RP/WAX. Results and discussion Different compositions of mobile phases and gradients are evaluated based on a literature study. Triethylamine, triethylammonium acetate, ammonium formate, hexafluoroisopropanol is used along with both methanol and acetonitrile. Phosphate buffer is evaluated on LC-UV. The results from the C18 column displays a good separation of the oligonucleotides, whilst the DNAPac RP is not as sufficient using the same mobile phases. The mixed-mode column provides good separation and selectivity using phosphate buffer and UV detection. Conclusion Mixed-mode column has the potential to be used for separation of oligonucleotides and one future focus would be to make the mobile phase compatible with mass spectrometry. Phosphate buffer and UV detection seems to be the go-to mobile phase using mixed-mode column even though MS is a more powerful tool for the characterization and identification of oligonucleotides. This provides a hint about the challenge in making the mobile phase MS compatible.

Avloppsreningsverk (ARV) utgör en viktig del som spridningsväg för utsläpp av organiska mikroföroreningar, som per- och polyfluorerade alkylsubstanser (PFAS) och läkemedelssubstanser, från samhället till den akvatiska miljön. Befintliga reningssteg vid ARV reducerar mikroföroreningar dåligt varav denna studie syftade till att jämföra reduktionseffektiviteten av 5 olika granulära aktiva kol (GAK) och en anjonbytare (AIX) för att välja ut det material som är mest lämpat för vidare undersökningar i pilotskala inför installation ett avancerat reningssteg i Kungsängsverkets ARV i Uppsala. GAK (Filtrasorb 400, Cyclecarb 401, Brennsorb 1240, Aquasorb 5000 och Aquasorb 2000) utvärderades för avskiljning av 13 PFAS-ämnen i ett inledande bägarförsök genom placering i avloppsvatten från Kungsängsverket i 8 h. Cyclecarb 401 var mest effektivt vid avskiljning av PFAS där reduktionsgraden för PFAS-11 (85 %) och PFOS (90 %) var 35 % och 40 % högre än för det minst effektiva GAK Brennsorb 1240. Cyclecarb 401, Brennsorb 1240 och AIX Purolite 694E undersöktes i ett andra bägarförsök enligt en liknande metod, men utvärderades med avseende på avskiljning av 12 PFAS och 18 läkemedelssubstanser över 48 h. Resultatet för PFAS var likvärdigt för GAK, men AIX visades nå samma reduktionsgrad av PFAS som Cyclecarb 401 och detta skedde snabbare. Efter 48 h var reduktionen med GAK högst för läkemedelssubstanser (91-99 %) och med AIX för PFAS (78 %). Samtliga adsorbenter tillfördes även till kolonner, där Purolite 694E även seriekopplades efter Cyclecarb 401, med ett kontinuerligt flöde av avloppsvatten motsvarande 5 min kontakttid (EBCT). Även om duplikatprover togs varje vecka genomfördes inom ramen för detta examensarbete analyser för de prover tagna en timme (12 bäddvolymer), 2 veckor (4000 bäddvolymer) och 7 veckor (14 000 bäddvolymer) efter start för 12 PFAS och 18 läkemedelssubstanser. Purolite 694E reducerade PFAS bäst, 40-50 % bättre än GAK, följt av negativt laddade läkemedelssubstanser och adsorptionen för dessa ämnen var bättre över tid än för GAK. Seriekoppling av AIX efter GAK förbättrade reduktionsgraden över tid för främst PFAS (30 % ökning vid 14 000 bäddvolymer). Även för läkemedelssubstanser med negativ laddning som adsorberades väl av AIX. Adsorptionen till AIX gynnades mest av substanser med negativa laddning. Adsorptionen till samtliga adsorbenter gynnades av PFAS med en sulfonatgrupp, en lägre syrakonstant, en högre fördelningskonstant mellan oktanol och vatten samt en längre kolkedja. En seriekoppling av AIX efter GAK är främst intressant för förbättrad avkiljning av diklofenak och PFOS vid Kungsängsverket, men även avskiljning av andra PFAS och negativt laddade läkemedelssubstanser kan förbättras. Andra ämnen adsorberades väl av GAK där Cyclecarb 401 i samtliga försök visats mest effektiv. De analyserade provpunkterna för kolonnförsöket var för få varav en kommande noggrannare undersökning över hela försökets genomförande kommer påvisa livslängderna för varje adsorbent vid EBCT 5 min. EBCT var kort varav efterföljande försök bör undersöka avskiljningens effektivitet för Kungsängsverket vid längre EBCT. / Waste water treatment plants (WWTPs) constitute an important role in releasing organic micropollutants, such as per- and polyfluoroalkyl substances (PFAS) and pharmaceuticals, from the society into the aquatic environment. Reduction of them in existing treatment methods in WWTPs is insufficient which is why the aim of this study was to examine the reduction efficiency for 5 granular activated carbons (GAC) and an anion exchange resin (AIX) and choose the adsorbent most suited for further studies in pilot scale before an advanced treatment step is built to Kungsängsverket WWTP in Uppsala.  GAC (Filtrasorb 400, Cyclecarb 401, Brennsorb 1240, Aquasorb 5000 and Aquasorb 2000) were evaluated for 13 PFAS compounds in an initial batch experiment using wastewater from Kungsängsverket during 8 h. Cyclecarb 401 had the highest removal efficiency for PFAS where the reduction grade for PFAS-11 (85 %) and PFOS (90 %) was 35 % and 40 % higher than for the least efficient GAC Brennsorb 1240. Cyclecarb 401, Brennsorb 1240 and the AIX Purolite 694E were evaluated in a second batch experiment through a similar method, analyzed for 12 PFAS and 18 pharmaceuticals over 48 h. The results for PFAS were similar for GAC, but AIX reached the same reduction grade for PFAS as Cyclecarb 401 which also happened faster. After 48 h reduction with GAC was best for pharmaceuticals (91-99 %) and with AIX for PFAS (78 %). Finally, these adsorbents were placed in individual columns, where Cyclecarb 401 was connected to an additional column with Purolite 694E, with a continuous flow of wastewater with an empty bed contact time (EBCT) of 5 min. Even though duplicate samples were taken each week analysis was performed for samples taken an hour (12 bed volumes), 2 weeks (4000 bed volumes) and 7 weeks after start (14 000 bed volumes) for 12 PFAS and 18 pharmaceuticals. Purolite 694E reduced PFAS the best, 40-50 % better than GAC, followed by negatively charged pharmaceuticals and adsorption for these compounds was better over time than with GAC. AIX after GAC increased reduction grade over time primarily for PFAS (30 % improvement after 14 000 bed volumes) but also for pharmaceuticals well adsorbed by AIX. Adsorption to AIX was mainly improved with a negative charge of the compound. Adsorption to adsorbents was favored for PFAS containing a sulfonate group, compounds with a lower acid dissociation constant, a higher octanol-water partition coefficient and a longer carbon chain. Implementation of AIX after GAC would be of interest for Kungsängsverket mainly due to the improved removal of diclofenac and PFOS, but also if removal of other PFAS and pharmaceuticals will become prioritized. Other compounds were removed by GAC well where Cyclecarb 401 was most effective in all experiments. The analyzed samples for the column experiment were too few which is why a more comprehensive study of all samples over the whole experiment period will be able to determine the life length of each adsorbent for EBCT 5 min. EBCT was short which is why further experiments need to examine the reduction efficiency for Kungsängsverket at a longer EBCT.