Halogenated heterocycles are common in pharmaceutical and natural products and there is a need to develop a better understanding of processes used to synthesize them. Although the halogenation of simple aromatic molecules is well understood, the mechanisms behind the halogenation of aromatic heterocycles have been more problematic to elucidate because multiple pathways are possible. Recently, new, radical-based mechanisms have been proposed for heterocycle halogenation. In this study, we examine and test the viability of possible nucleophilic substitution, SN2@X, mechanisms in the halogenation of anions derived from the deprotonation of aromatic heterocycles. All the experiments were done in a modified Thermo LCQ Plus equipped with ESI. The modifications allow a neutral reagent to be added to the helium buffer gas in the 3D ion trap. In this system, it is possible to monitor ion/molecule reactions over time periods up to 10 seconds. A variety of aromatic heterocyclic nucleophiles were chosen based on their inclusion of nitrogen and or sulfur as the heteroatoms. In addition to this, the halogenating molecules chosen included traditional halobenzenes and a new class of perfluorinated alkyl iodides. It was found that, experimentally, the SN2@X path is the likely mechanism in the halogenation of deprotonated heterocycles. With computational modeling, we have additional support for this substitution mechanism. From this original study, two more studies were developed to look at the competing nucleophilic aromatic substitution reaction, SNAr. In the first of these studies, the focus was to look at how electron withdrawing substituents about an aromatic ring affect the ratio of SN2@X verses SNAr. As nucleophiles, 2-thiophenide and 5-thiazolide were used. The neutral reagents focus on trifluorobromobenzene derivatives along with pentafluorobromo- and -iodobenzene, and a two trifluoroiodobenzenes. What was found was that the ratio of the reactions depends on where the fluorines, or electron withdrawing substituents are in relation to the bromine or iodine on the ring. If the fluorines are in a close location to stabilize the resulting ionic product, SN2@X proceeds easily. However, the fluorines directly adjacent to the bromine or iodine also provide steric hinderance in the SNAr reaction. In the final project, arylation and benzylation of bromopyridines was examined. The nucleophiles used were benzyl and phenyl anions as well as 5-thiazolide, and the neutral reagents were bromopyridines, with fluorines used as an electron withdrawing groups to help stabilize the transition state. In these experiments, steric hinderance highly affected the results between the phenyl and benzyl nucleophiles. With benzylic anions, the nucleophile is able to reach the aromatic ring with less steric interference and therefore can proceed with an SNAr reaction. In addition to this, with mono and difluorinated pyridine substrates, the nitrogen in the ring activated the ring yielding nucleophilic aromatic substitution losing fluoride rather than bromide in many cases.

Graphitic carbon nitride (g-C3N4) heterojunction composites with the semiconducting metal oxides, CeO2, ZnO and TiO2 are prepared in situ by co-calcination of the precursor materials or by a solvothermal method. The structural, morphological and the optical properties of the prepared materials are studied using various microscopy and spectroscopy techniques. The synthesized composite materials, CeO2/g-C3N4, ZnO/g-C3N4 and TiO2/g-C3N4 are more efficient in the photocatalytic degradation of the water pollutants indigo carmine (IC) and atrazine than the pure metal oxide, g-C3N4, or their physical mixtures. The CeO2/g-C3N4 and ZnO/g-C3N4 composites also exhibit improved degradation efficiencies of atrazine as compared to the individual metal oxide or g-C3N4 materials. The improved photocatalytic activity of the composites are attributed to the effective electron-hole charge separation within composite heterojunction, resulting from the well matched energy levels of the metal oxide and g-C3N4. This strategy could be helpful for the synthesis of other metal oxide and g-C3N4 composites for photocatalytic applications.

The subject of this thesis relates to the design of new polymer electrolytes for battery and fuel cell applications. Classical Molecular Dynamics (MD) modelling studies are reported of the nano-structure and the local structure and dynamics for two types of polymer electrolyte host: poly(ethylene oxide) (PEO) for lithium batteries and perfluorosulfonic acid (PFSA) for polymer-based fuel cells. Both polymers have been modified by side-chain substitution, and the effect of this on charge-carrier transport has been investigated. The PEO system contains a 89-343 EO-unit backbone with 3-15 EO-unit side-chains, separated by 5-50 EO backbone units, for LiPF6 salt concentrations corresponding to Li:EO ratios of 1:10 and 1:30; the PFSA systems correspond to commercial Nafion®, Hyflon® (Dow®) and Aciplex® fuel-cell membranes, where the major differences again lie in the side-chain lengths. The PEO mobility is clearly enhanced by the introduction of side-chains, but is decreased on insertion of Li salts; mobilities differ by a factor of 2-3. At the higher Li concentration, many short side-chains (3-5 EO-units) give the highest ion mobility, while the mobility was greatest for side-chain lengths of 7-9 EO units at the lower concentration. A picture emerges of optimal Li+-ion mobility correlating with an optimal number of Li+ ions in the vicinity of mobile polymer segments, yet not involved in significant cross-linkages within the polymer host. Mobility in the PFSA-systems is promoted by higher water content. The influence of different side-chain lengths on local structure was minor, with Hyflon® displaying a somewhat lower degree of phase separation than Nafion®. Furthermore, the velocities of the water molecules and hydronium ions increase steadily from the polymer backbone/water interface towards the centre of the proton-conducting water channels. Because of its shorter side-chain length, the number of hydronium ions in the water channels is ~50% higher in Hyflon® than in Nafion® beyond the sulphonate end-groups; their hydronium-ion velocities are also ~10% higher. MD simulation has thus been shown to be a valuable tool to achieve better understanding of how to promote charge-carrier transport in polymer electrolyte hosts. Side-chains are shown to play a fundamental rôle in promoting local dynamics and influencing the nano-structure of these materials.

Natural gas, primarily methane (CH4), is produced in substantial amounts in ultramafic-hosted hydrothermal systems. These systems could also generate oil (heavier hydrocarbons) and the first building blocks of life (prebiotic molecules). In the presence of iron bearing minerals, serpentinisation reactions generate H2. Subsequently, CH4 could be synthesised by Fischer-Tropsch Type (FTT) reaction (4H2 + CO2 → CH4 + 2H2O) which is an abiotic process. This has lead to the idea of abiotic formation of larger organic molecules. Both thermodynamics and laboratory work support this idea, yet field data have been lacking. This study focuses on determining the organic content of fluids from ultramafic-hosted hydrothermal systems from the Mid-Atlantic Ridge (MAR) and the origin of the compounds. Fluids were collected from the Lost City, Rainbow, Ashadze and Logatchev vent fields during the EXOMAR (2005), SERPENTINE (2007), MoMARDREAMnaut (2007) and MOMAR08-Leg2 (2008) cruises conducted by IFREMER, France. A SBSE-TD-GC-MS technique was developed and used to extract, concentrate, separate and identify compounds in the fluids. Hydrothermally derived compounds appeared to consist mainly of hydrocarbons and O-bearing molecules. In addition, some amino acids were detected in the fluids by ULPC-ESI-QToF-MS but their origin will need to be determined. The organic content of the Rainbow fluids did not show intra field variability unlike differences could be noted over the years. In order to address the question of the source of the molecules, compound specific carbon isotopic analyses were carried out and completed with a bacterial (Pyrococcus abyssi) hydrothermal degradation experiment. The δ13C data fall in the range of -40 to -30‰ (vs. V-PDB), but individual δ13C values preclude the identification of a biogenic or abiogenic origin of the compounds. The degradation experiment, however, suggests an abiogenic origin of a portion of saturated hydrocarbons whereas carboxylic acids would be biogenic, and aromatic compounds would be thermogenic. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Submitted. Paper 3: Submitted. Paper 4: Submitted. / MoMARnet

Pyridazines are a heterocyclic aromatic compound containing a characteristic N-N bond that are utilized in many fields, including medicine and electronics. It is this latter field that Dr. Snyder's research group is focused upon. Organometallic compounds are a better conducting material than the current inorganic compounds used in electronics due to better conductance of electricity, lower production cost, and the ability to be formed into thin films. With this in mind, Dr. Snyder's research group has set out to synthesize organometallic compounds for this purpose. Following procedures set forth by Snyder etc, and altered to form an off-metal route, we have successfully synthesized a library of fulvenes, Thalium Cp salts, 5,6 fused pyridazines, and pyridazial complexes. Thalium Cp salts were converted to Rhenium and Magnenese complexes through transmetalation. We have had success with the off-metal route at both higher yields and greater purity than the previous published on-metal route. These compounds have been fully characterized by 1H NMR, 13C NMR, IR, and Elemental Analysis. In addition, progress has been initiated to form Bromo Thiophene complexes following procedures set forth in Snyder, etc and modified for the off-metal route. However only fulvenes, pyridazine, and Thalium Cp salts have been synthesized and characterized by 1H NMR and 13C NMR.

Denna studie har som syfte att studera vilka tankar förskolebarn i åldern mellan 5-6 år har om energiprocesser kopplat till människokroppen. Metoden var en kvalitativ semistrukturerad intervjustudie som genomfördes på en förskola samt i en förskoleklass. Teoretiska utgångspunkten var social konstruktivism. Intervjuerna kompletterades med en docka som blev ett kommunikativt redskap. Resultatet av studien visar att de flesta barn relatera mat som en viktig energikälla. Barnens tankar om vart de får sin energi ifrån ligger i vardagsspråket, där barnen använder energi begreppet som att känner sig utvilad och har ork för att kunna leka. Den skiljer sig till den naturvetenskapliga betydelsen av energi där vi får vår energi genom cellandningen. Barns tankar om hur de får sin energi skiljer sig och sammanfattas i fem olika kategorier. Kategorierna är: genom mat, genom rörelse, genom vila, genom vätska och genom syre. / The purpose of this study is to investigate how preschool children between the age of 5 and 6 years reflect about energy processes connected to the body. The study was conducted with semi structured interviews with a preschool class and a preschool. The theoretical framework for the study is social constructivism. The study was conducted with communicative tools (a doll). The result of the study is most children relate food as an important source of energy. Children ́s perceptions about where they got the energy from, lies in the form of informal language, where they use the word energy when they feel alert and have strength to play. It differs from the science ́s descriptions of energy, that we obtain energy through cellular respiration. Children ́s perceptions about where they got the energy from are divided into five categories. The categories are: through food, through motion, through rest, through fluid and through oxygen.

The main objective of this study was the formulation of food-grade water-in-oil (W/O) nano-dispersions based mainly on medium or long-chain triglycerides. Two types of dispersions were formulated and structurally compared, namely emulsions and microemulsions. The systems were used as matrices for encapsulating targeted bioactive molecules with specific characteristics such as antioxidants or peptides. The structural characterization of the formulated systems was investigated using techniques such as Electron Paramagnetic Resonance (EPR) spectroscopy, Dynamic Light Scattering (DLS), Cryogenic Transmission Electron Microscopy (Cryo-TEM) and Small Angle Xray Scattering (SAXS). The existence of swollen inverse micelles was revealed for the case of microemulsions whereas larger droplets still at the nano-scale were observed for the case of emulsions. Structural differences in the presence of the bioactive molecules or induced by the alteration of components were also observed. In order to study the efficacy of the formulations, the proposed loaded systems were assessed either using EPR spectroscopy or Well Diffusion Assay (WDA) depending on the bioactive molecule. It was found that the encapsulated molecules retained their claimed characteristics when encapsulated to the proposed matrices. Finally, some of the formulated dispersions were investigated for their behavior under gastrointestinal (GI) conditions. A two-step digestion model using recombinant Dog Gastric Lipase (rDGL) and Porcine Pancreatic Lipase (PPL) was proposed to simulate lipid hydrolysis in humans. The studies revealed significant decrease of the rDGL specific activity in the presence of the microemulsion while in the presence of lower percent of surfactants (case of emulsion) no alterations were observed.

The recent developments and improvements of instrumental methods for the analyses of the environmental contaminants, especially the persistent organic pollutants (POPs), have made it possible to detect and quantify these at very low concentrations in environmental and biotic matrices. The main objective of this thesis is to demonstrate the capability of the atmospheric pressure chemical ionization technique (APCI), using gas chromatography coupled to tandem mass spectrometry for the determination of a wide range of environmental contaminants, including the POPs regulated by Stockholm Convention, such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), but also the derivates of PBDEs and novel brominated flame retardants (NBFRs). The APCI was operated in charge transfer condition, preferably producing molecular ions. Multiple reaction monitoring (MRM) experiments were optimized by adjusting cone voltage, collision energy and dwell time. Optimization of source parameters, such as gas flows and temperatures was also performed. Low concentration standards were analyzed, achieving a visible chromatographic peak for 2 fg 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) demonstrating the excellent sensitivity of the system. Adequate linearity and repeatability were observed for all the studied compounds. The performance of APCI methods was validated against the conventional methods using gas chromatography coupled to high resolution mass spectrometry for chlorinated compounds in a wide range of matrices including environmental, air, human and food matrices. The GC-APCI-MS/MS method was successfully applied to a set of 75 human serum samples to study the circulating levels of POPs in epidemiologic studies. Moreover the method was utilized to establish temporal trends of POPs in osprey eggs samples collected during the past five decades.

Incineration is a mainstream strategy for solid waste management in Sweden and all over the world. Improved knowledge and understanding about the distribution of trace elements (in ashes) during incineration, and how trace element partitioning respond to the changes in waste composition, are important in terms of combustion process optimization and plant efficiency. Moreover, determination of chemical association of trace elements in ashes are vital for avoiding environmental concerns and to promote possible reuse. In this study, partitioning of trace elements in ashes during incineration as function of input waste fuel and incineration technology was investigated. Further, chemical association of trace elements in resulting ashes was studied. An evaluation was also performed about feasibility of metal extraction from sulfidic mining waste and flotation tailings. Moreover, green liquor dreg (GLD) was tested with respect to stabilization of metals within the sulfidic mining waste. Findings showed that the total input of trace elements and chlorine affects the partitioning and increasing chlorine in the input waste caused increase in transfer of trace elements to fly ash especially for lead and zinc. Vaporization, condensation on fly ash particles and adsorption mechanisms play an important role for metal distribution. Firing mixed waste, especially biofuel mix, in grate or fluidized (CFB) boilers caused increased transfer into fly ash for almost all trace elements particularly lead and zinc. Possible reasons might be either an increased input concentration of respective element in the waste fuel, or a change in volatilization behavior due to the addition of certain waste fractions. Chemical association study for fly ashes indicated that overall, Cd, Pb, Zn, Cu and Sb are presenting major risk in most of the fly ashes, while in bottom ashes, most of elements are associated with stable fraction. Further, fuel type affects the association of elements in ashes. Chemical leaching of mining waste materials showed that sulfuric acid (under different conditions) is the best reagent to recover zinc and copper from sulfidic mining waste and also copper from flotation tailings. GLD indicates potential for metal stabilization in mining waste by reducing the metal mobility. Extraction methods could be applied to treat mining waste in order to meet the regulatory level at a specific mining site.Similarly stabilization/solidification  methods might be applied after leaching for recovery of metals.

There are multiple applications for polymers: our bodies are built of them, plastic bags and boxes used for storage are composed of them, as are the shells for electronics, TVs, computers, clothes etc. Many polymers are cheap, and easy to manufacture and process which make them suitable for disposable systems. The choice of polymer to construct an object will therefore highly influence the properties of the object itself. The focus of this thesis is the application of commonly used polymers to solve some challenges regarding integration of electrodes in electrokinetic devices and 3D printing. The first part of this thesis regards electrokinetic systems and the electrodes’ impact on the system. Electrokinetic systems require Faradaic (electrochemical) reactions at the electrodes to maintain an electric field in an electrolyte. The electrochemical reactions at the electrodes allow electron-to-ion transduction at the electrode-electrolyte interface, necessary to drive a current at the applied potential through the system, which thereby either cause flow (electroosmosis) or separation (electrophoresis). These electrochemical reactions at the electrodes, such as water electrolysis, are usually problematic in analytical systems and systems applied in biology. One solution to reduce the impact of water electrolysis is by replacing metal electrodes with electrochemically active polymers, e.g. poly(3,4-ethylenedioxythiophene) (PEDOT). Paper 1 demonstrates that PEDOT electrodes can replace platinum electrodes in a gel electrophoretic setup. Paper 2 reports an all-plastic, planar, flexible electroosmotic pump which continuously transports water from one side to the other using potentials as low as 0.3 V. This electroosmotic pump was further developed in paper 3, where it was made into a compact and modular setup, compatible with commercial microfluidic devices. We demonstrated that the pump could maintain an alternating flow for at least 96 h, with a sufficient flow of cell medium to keep cells alive for the same period of time. The second part of the thesis describes the use of 3D printers for manufacturing prototypes and the material requirements for 3D printing. Protruding and over-hanging structures are more challenging to print using a 3D printer and usually require supporting material during the printing process. In paper 4, we showed that polyethylene glycol (PEG), in combination with a carbonate-based plasticizer, functions well as a 3D printable sacrificial template material. PEG2000 with between 20 and 30 wt% dimethyl carbonate or propylene carbonate have good shear-thinning rheology, mechanical and chemical stability, and water solubility, which are advantageous for a supporting material used in 3D printing. The advances presented in this thesis have solved some of the challenges regarding electrokinetic systems and prototype manufacturing. Hopefully this will contribute to the development of robust, disposable, low-cost, and autonomous electrokinetic devices. / Polymera material finns överallt omkring oss; våra kroppar är uppbyggda av dem,plastpåsarna och burkarna vi förvarar vår mat av består av dem, våra kläder och andra tingsom finns i vår vardag är uppbyggda av olika typer av polymerer. En polymer är uppbyggd aven repetitiv sekvens av identiska grupper, de kan liknas vid en mönsterrapport vilken är denminsta del som man behöver repetera för att få mönstret. Beroende på hur rapporten ser ut såförändras utseendet av mönstret. Hos en polymer påverkar sammansättningen av denrepetitiva gruppen (rapporten) egenskaperna av materialet och polymerer kan vara allt frånhårda och robusta, till flexibla och elektriskt ledande. Arbetet som presenteras i den häravhandlingen berör hur funktionen av olika system påverkas av att man använder sig avpolymerer istället för konventionella material. Första delen av avhandlingen handlar om integrering av elektronik i system som innehållervätska. När vätskor, laddade partiklar, molekyler och joner rör på sig på grund av ett yttreelektriskt fält, så kallas detta för elektrokinetik. Detta kan användas för att pumpa vätska ikanaler som är mindre än 0.2 mm, genom så kallad elektroosmos, samtidigt kommermolekyler med olika laddning att börja separera, så kallad elektrofores. Elektroosmos användsinom t.ex. analytisk kemi för injektion och transport av vätskor. Elektrofores används inombl.a. rättsvetenskap och molekylärbiologi för att separera makromolekyler, så som DNA ochproteiner, med avseende på deras storlek och laddning. I dessa system använder man sig oftastav metallelektroder. När en spänning läggs till ett par metallelektroder som är i kontakt med vatten kommer denhuvudsakliga reaktionen att vara spjälkning av vatten, så kallad vattenelektrolys. Spjälkningav vatten innebär att det bildas vät-och syrgas samt att pH börjar ändras. Gaserna som bildaskan bryta kopplingen mellan elektroderna och därmed stoppar strömmen, så som sker när mandrar ut sladden för t.ex. en elvisp. Förändringar i pH kan t.ex. påverka biologiska provernegativt, så som proteiners funktion och kan leda till celldöd, men kan också minska flödenaen elektroosmotisk pump kan generera. Det finns flera olika sätt hur man kan hanteravattenelektrolys i system med metallelektroder, så som användning av en pH-buffer. Arbetet iden här avhandlingen visar vad som händer om man ersätter metallelektroder med elektrisktledande plastelektroder. I detta fall har metallelektroderna ersatts av den elektriskt ledandepolymeren PEDOT vilket resulterar i att , där man istället för generera gas och pHviförändringar, så förflyttar man joner mellan elektroden och omgivande lösning. Ledandepolymerer är billiga och enkla att tillverka vilket gör dem lämpliga för engångssystem. förändringar, så förflyttar man joner mellan elektroden och omgivande lösning. Ledandepolymerer är billiga och enkla att tillverka vilket gör dem lämpliga för engångssystem.I den här avhandlingen visas följande exempel där metallelektroder ersatts av ledandeplastelektroder: Gelelektrofores (separation av proteiner i en gel), (se papper 1), tyg som kanpumpa vatten (plan elektroosmotisk pump, se papper 2) och en kompakt pump som inte ärstörre än ett kaffemått, som enkelt kan kopplas till befintliga sprutkopplingar och som kananvändas för att kontrollera flödet över t.ex. celler (se papper 3). Andra delen av avhandlingen handlar om 3D skrivare och hur materialval påverkarutskriften och designen. 3D skrivare är ett bra alternativ för att snabbt och billigt kunnaproducera prototyper och funktionella individanpassade objekt i varierande storlekar.3D skrivare kan beskrivas som en avancerad spritsmaskin där material läggs lager på lager föratt bygga upp det slutgiltiga objektet utifrån en datorgenererade 3D model. Detta förändrarhelt hur man designar objekt och vilka möjliga strukturer och material man kan använda sigav jämfört än då man till exempel använder sig av svarv eller fräs för tillverkning. Det finnsflera olika typer av 3D skrivare, t.ex. smältplastskrivare (den typ som man kan se i flertaletaffärer idag) och den variant som använts i den här avhandlingen, en sprutbaserad. Ensprutbaserad 3D skrivare kan hantera många olika typer av material så länge dessa kan fyllas ien spruta och tryckas ut genom en nål. Det färdiga resultat kan därmed bli mycket olikaberoende på vilka material som använts. Överhängande och utstickande strukturer kan vara komplicerade att skriva ut med en3D skrivare. Utskrift av dessa strukturer kan underlättas genom att man skriver ut en temporärstruktur i ett annat material, ett offermaterial. Offermaterialet fungerar som en mall eller stödtill det slutgiltiga objektet och tas bort (offras) när övriga delar av objektet är klara. I den häravhandlingen beskrivs hur ett offermaterial baserat på polyetylen glykol (PEG, vanligtförekommande i t.ex. schampo och läkemedel) och en mjukgörare kan anpassas för attfungera tillsammans med en sprutbaserad 3D skrivare (se papper 4) för att skriva ut strukturerfrån 0,2 mm och uppåt. Arbetet i den här avhandlingen visar användningen av den ledande polymeren PEDOT i ettelektroforessystem och en elektroosmotisk pump. Detta kan förhoppningsvis underlättautvecklingen av dessa system till att bli mindre, smidigare, snabbare och billigare. Den andradelen presenterar ett vattenlösligt, PEG-baserat material som kan användas som stöd till andramaterial i sprutbaserade 3D utskrifter för att underlätta tillverkningen av 3D utskrivna objekt.