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<p>The class of meteorites called carbonaceous chondrites are examples of material from the solar system which have been relatively unchanged from the time of their initial formation. We investigate the carbonaceous chondrite subclasses CI, CM, CR, CV, and CO, which contain high levels of water and organic material, including amino acids. These subclasses span petrologic types 1 through 3, indicating the degree of internal chemistry undergone by the meteoritic parent body. The goal of this thesis is two-fold: to obtain a comprehensive view of amino acid abundances and relative frequencies in carbonaceous chondrites, and to recreate these patterns via thermodynamic computational models.</p> <p>We collate available amino acid abundance data for a variety of meteorites to identify patterns in total abundance and relative frequencies. We consider only a set of 20 proteinogenic alpha-amino acids created via a specific chemical pathway called Strecker synthesis. We plot abundances of individual amino acids for each subclass, as well as total abundances across all subclasses. We see a predominance in abundance and variety of amino acids in the CM and CR subclasses, which contain concentrations of amino acids greater by several orders of magnitude than other carbonaceous subclasses. These subclasses correspond to an aqueous alteration temperature range of 200 deg. C to 400 deg. C. Within the CM2 and CR2 meteorites, we identify trends in the relative frequencies of amino acids in preparation for computational modeling.</p> <p>Now having a baseline observed amino acid abundance plot, we recreate both the total amino acid abundance pattern as well as the relative frequency of amino acids within the CM2 chondrite subclass using computational models. We use thermodynamic theory of Gibbs free energies to calculate the output of amino acids in a meteoritic parent body assuming chemical equilibrium and some set of initial concentrations of organic material. Our model recreates abundance patterns in the temperature range 200 deg. C to 400 deg. C, ~10⁵ parts-per billion (ppb), and the temperature range 400 deg. C to 500 deg. C, ~10² ppb. Our model does not fit well between temperatures of 150 deg. C to 200 deg. C. Our current model assumes a uniform composition of initial chemical reactants; likely an inhomogeneous composition would be a more accurate physical representation of a parent body. In addition, we match relative frequencies to observed frequencies for each amino acid in the CM2 subclass to well within an order of magnitude.</p> / Master of Science (MSc)

Remediation of contaminated groundwater remains a high-priority national goal in the United States. Water is essential to life, and new sources of water are needed for an expanding population. Groundwater remediation remains a significant technical challenge despite decades of research into this field. New approaches are needed to address the most severely-polluted aquifers, and cost-effective solutions are required to meet remediation objectives that protect human health and the environment. Source reduction combined with Monitored Natural Attenuation (MNA) is a remediation strategy whereby the source of contamination is aggressively treated or removed and the residual groundwater plume depletes due to natural processes in the subsurface. The USEPA requires long-term performance monitoring of groundwater at MNA sites over the remediation timeframe, which often takes decades to complete. Presently, computational tools are lacking to adequately integrate source remediation with economic models. Furthermore, no framework has been developed to highlight the tradeoff between the degree of remediation versus the level of benefit within a cost structure. Using the Natural Attenuation Software (NAS) package developed at Virginia Tech, a set of formulae have been developed for calculating the TOR for petroleum-contaminated aquifers (specifically tracking benzene and MTBE) through statistical techniques. With the knowledge of source area residual saturation, groundwater velocity, and contaminant plume source length, the time to remediate a site contaminated with either benzene or MTBE can be determined across a range of regulatory maximum contaminant levels. After developing formulae for TOR, an integrated and interactive decision tool for framing the decision analysis component of the remediation problem was developed. While MNA can be a stand-alone groundwater remediation technology, significant benefits may be realized by layering a more traditional source zone remedial technique with MNA. Excavation and soil vapor extraction when applied to the front end of a remedial action plan can decrease the amount of time to remediation and while generally more expensive than an MNA-only approach, may accrue long-term economic advantages that would otherwise be foregone. The value of these research components can be realized within the engineering and science communities, as well as through government, business and industry, and communities where groundwater contamination and remediation are of issue. Together, these tools constitute the Sâ ªEâ ªEâ ªPâ ªAGE paradigm, founded upon the concept of sound science for an environmental engineering, effectual economics, and public policy agenda. The TOR formulation simplifies the inputs necessary to determine the number of years that an MNA strategy will require before project closure and thus reduces the specialized skills and training required to perform a numerical analysis that for one set of conditions could require many hours of simulation time. The economic decision tool, that utilizes a life cycle model to evaluate a set of feasible alternatives, highlights the tradeoffs between time and economics can be realized over the lifetime of the remedial project. / Ph. D.

På senare år har efterfrågan på stålmaterial av låg vikt ökat, speciellt inom transportsektorn. Genom att addera Al till stål sänks densiteten vilket gör att FeAl-legeringar är ett lovande material för fordonskonstruktion. Vätskekorrosionsegenskaper undersöktes av 3D – printade FeAl prover som innehöll 0 – 10 vikt% Al och 0,1 vikt% Zr för att bestämma hur korrosionsegenskaperna förändrades med avseende på Al – innehållet. Korrosionsresistansen var i stor utsträckning beroende av huruvida en passiv film av Al2O3 bildades på ytan eller ej. Korrosionshastigheten bestämdes genom EIS – och PDP – analyser utförda i 3,5 vikt% NaCl-lösning samt genom viktförlusttester i 1 M HCl respektive 0,5 M H2SO4. Vidare karaktäriserades proverna genom XRF, XRD, EDS, SEM och optisk mikroskopi vilket bland annat visade på att samtliga prover var enfassystem samt att den kemiska sammansättningen var enligt förväntan. Vidare indikerade optisk mikroskopi och SEM att ett högre Al – innehåll resulterar i att proverna blir mer porösa. Elektrokemiska tester antyder att ett Al – innehåll om 10 vikt% förbättrade korrosionsresistansen. Detta antyder möjligen, men kan inte definitivt fastslås från de utförda experimenten, att det krävs 10 vikt% Al för att en passiv film som täcker hela materialytan ska bildas. Korrosionshastigheten var 7 – 10 gånger högre vid viktförlusttest jämfört med elektrokemiska test. Detta förklaras genom att den skyddande passiva filmen bröts ned under de sura förhållanden som viktförlusttesten utfördes i medan den passiva Al2O3 filmen kunde bestå i de pH – neutrala förhållanden som elektrokemiska test utfördes vid. Detta speglar att bildandet och stabiliteten av Al2O3-filmen är vitalt för att sänka korrosionshastigheten. / In recent years the demand for lightweight ferritic steels has increased, particularly for transport applications. The addition of Al lowers the density, hence making FeAl alloys promising materials for such constructions. Aqueous corrosion properties of 3D – printed FeAl samples ranging from 0 – 10 wt% Al and containing 0.1 wt% Zr were investigated to determine how the Al content affects the corrosion resistance. The corrosion rate was found to greatly depend on the formation and stability of a protective passive film of Al2O3 forming on the material surface. A corrosion rate was obtained via EIS and PDP in 3.5 wt% NaCl as well as via weight loss testing in 1 M HCl and 0.5 M H2SO4. Additionally, XRF, XRD, EDS, SEM and optical microscopy tests were carried out to characterize the samples. XRF and EDS confirmed that the elemental composition of the samples was as expected and XRD indicated that all samples were single phase systems. Furthermore, optical microscopy and SEM indicated that higher Al content makes the samples more porous. Electrochemical testing indicated that addition of 10 wt% Al greatly improves the corrosion properties suggesting that it may require 10 wt% Al to form a passive film that covers the whole surface, although this cannot be said for certain from these experiments. Moreover, the corrosion rate was 7 – 70 times lower during electrochemical testing compared to weight loss testing, in which the passive film breaks down due to the acidic conditions. This emphasizes that the stability of the Al2O3 film is vital for slowing down the corrosion rate of FeAl alloys.

As microfabrication techniques stepped into the millimeter and sub-sub-millimeter scale world, a large amount of microelectronics has been developed and even commercialized. Microbatteries are considered as the important components to continuously power microelectronics without interruption. Over past few decades, a great deal of research have been devoted into the development of microbatteries with high energy density, long cycling life and minimum footprint area. These researches mainly focus on the fabrication procedure, which contributes to reducing the footprint area. However, the battery chemistry investigation and optimization are always ignored, which have great impact on the microbatteries performances. How to take the battery chemistry into account when shrinking the size of microbatteries is a huge challenge. To take up the challenge, applying the energy-dense materials into the three-dimensional microstructures could be a direct strategy. Among different three-dimensional microstrucutres, Swiss-roll microtube was proven as an effective way to improve the energy density without influencing the electrochemical kinetics. As for the material choice, the Zn-MnO2 aqueous system with high theoretical capacity and safe working environment is a good candidate for microbatteries. More importantly, fabrication and modification of both the electrode and electrolyte is compatible with standard microfabrication process in the atmosphere. Based on this, Zn anode is modified by a photolithgraphable electrolyte with small-molecular stabilizer, while the MnO2 cathode is modified by the zincophilic binder. Then the Swiss-roll three-dimensional structure is elaborately designed through the strain-engineering rolled-up technology to accommodate the energy-dense and highly reversible materials. As the results, the gap between bulky and microscale batteries is successfully bridged.

Iron-mediated oxidative cyclisation provides an efficient approach to pyrano[3,2-a]carbazole alkaloids. Thus, improved routes to girinimbine and murrayacine as well as the first total syntheses of O-methylmurrayamine A and 7-methoxymurrayacine are reported. Asymmetric epoxidation of girinimbine led to (−)-trans-dihydroxygirinimbine and the assignment of its absolute configuration. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Le fer est l'un des rares métaux qui ne soit pas produit industriellement par électrolyse. Pour aider au développement d'un tel procédé pour l'acier, l'électrolyse des oxydes de fer en milieu sodique est examinée, selon deux approches. La première démarche consiste en l'étude expérimentale du mécanisme réactionnel. L'électrochimie des ions indique qu'il est possible de produire du métal par électrodéposition en milieu alcalin. Parallèlement, l'étude de la réduction d'une particule d'oxyde hématite révèle qu'elle subit, lors de sa conversion en fer métallique, une transformation macroscopique en phase solide. Les analyses démontrent la formation de magnétite comme intermédiaire réactionnel. La seconde démarche est dédiée à la production du fer métallique, par électrolyse d'une suspension de particules d'oxyde dans diverses configurations de cellules. L'incidence des paramètres de procédé a été établie et permet de proposer des éléments de conception d'une cellule industrielle / Iron is one of the few metals which is not industrially produced by electrolysis. The electrowinning of iron metal from its oxides in alkaline solution has been studied to develop such an ironmaking route. Two approaches have been adopted. The first one concerns the evaluation of the reaction mechanism. The study of iron ions electrochemistry in alkaline media shows that the electrodeposition of iron metal is possible. The study of a single iron oxide particle reduction reveals that a reaction of the hematite solid phase is possible. The analysis of a partially converted particle proves that magnetite is formed as an intermediate. The second field of study is dedicated to the production of iron metal in various electrochemical cells, using a suspension electrolysis process. The influence of the key operating parameters is established to assess the possible scale-up. All these elements are gathered to propose the main features of an industrial cell dedicated to the reaction

Parce qu'ils présentent des propriétés remarquables par rapport à leurs équivalents massifs, les nanomatériaux occupent une place de plus en plus importante dans l'industrie et en médecine. Leur essor rapide a généré de nombreuses craintes dans l'opinion publique notamment au regard de certaines méconnaissances liées à leur toxicité. Notre projet vise l'utilisation du séléniure de cadmium (CdSe) comme matériau modèle afin d'établir une corrélation entre la structure chimique des nanoparticules, leur réactivité de surface, leur (photo)stabilité et leur toxicité. Des quantum dots (QDs) CdSe et alliages CdSe(S) ont été préparés en milieu aqueux à 100°C ou par voie hydrothermale de manière à ne différer que par leur structure chimique de coeur (alliage ternaire vs semi-conducteur binaire) alors que d'autres paramètres comme la taille, la charge ou la nature du ligand de surface, ont été maintenus constants. Des études de cytotoxicité menées sur Escherichia coli ont montré que la libération de Cd2+ jouait un rôle important dans la toxicité pour les deux QDs. Nos résultats ont également mis en évidence que les QDs CdSe(S) alliés étaient plus stables et moins toxiques que les QDs CdSe. Sans négliger l'importance de la libération d'ion Cd2+ par les nanoparticules, une corrélation entre la stabilité et la production d'espèces réactives de l?oxygène (EROs) a montré que la toxicité était en partie dépendante de la photostabilité des QDs. Notre étude met en perspective une relation entre la réactivité, la stabilité du coeur des nanoparticules, et la toxicité photo-induite / Due to their unique properties compared to their bulk counterparts, nanomaterials have gained considerable attention, especially in industry and medicine. Their fast development has generated many public concerns, especially because of a lack of knowledge regarding their toxicity. Our project aims to use cadmium selenide (CdSe) as a model material in order to initiate a research aiming at establishing a correlation between the nanoparticles chemical structure, their surface reactivity, their stability and their toxicity. CdSe and alloyed CdSe(S) quantum dots (QDs) were prepared in aqueous phase either at 100°C or under hydrothermal conditions in order to differ solely by their core chemical structure (ternary alloy vs binary semiconductor), while other parameters such as the size, the surface charge or the surface ligand, have been kept constant. Cytotoxicity studies carried out on Escherichia coli have shown that release of Cd2+ played a key role in the toxicity for both QDs. However, alloyed CdSe(S) QDs were also found more stable and less toxic than CdSe nanocrystals. Without disregarding the importance of Cd2+ ions release by the nanoparticles, a correlation between the stability and the production of reactive oxygen species (ROS) showed that toxicity was dependent on QDs photostability. Our study highlights a relationship between the core reactivity, stability and the photo-induced toxicity QD nanoparticles