A new family of perovskite titanates with formulae La4+nSr8-nTi12-nMnnO38 and La4Sr8Ti12-nMnnO38-δ have been investigated as potential fuel electrode materials for SOFCs. The series La4+nSr8-nTi12-nMnnO38 present layered domains within their structure. As such layers appear to have a large negative effect over the electrochemical properties only a few compounds have been characterised. The series La4Sr8Ti12-nMnnO38-δ present a rhombohedral (R-3c) unit cell at room temperature which becomes cubic when increasing the temperature up to 900°C both in air and in reducing conditions. The primitive volume correlates with the oxygen content for the reduced samples. TGA and magnetic studies have revealed that the Mn present is mainly as Mn⁺³. Preliminary HRTEM investigations have revealed that some crystallographic shears distributed randomly within a perovskite matrix remain in the structure, which implies that the oxygen overstoichiometry is compatible with rhombohedral distortions in the oxygen sublattice. Mn substitution does not have a large impact on the bulk conductivity of the phases studied, which remains close to the values observed in other related titanates, although the grain boundary contributions are largely improved. Relatively low polarisation resistances were observed under both hydrogen and methane conditions for the lowest n compounds of the series. The anodic overpotential for n=1 was fairly low to those reported in the literature for other materials and especially for titanate-based anodes, i.e. a value of 55mV at 0.5A/cm2, at 950°C, under wet hydrogen was obtained. Additionally, a value 72mV was obtained in the same conditions under methane. These values indicate that the use of Mn as dopant for perovskite-related titanates enhanced electrochemical performance of these anodes, especially at high temperatures.

This thesis details the development of manganese(III) acetate-mediated oxidative radical cyclisation methodology. In particular, the use of radicals to form complex, highly sterically congested and strained carbo- and heterocycles in a stereocontrolled manner is described. Chapter 1 gives a summary of the literature regarding three key areas relevant to this work. Radical reaction mechanisms are introduced, including the use of transition metals and lanthanides in C-centred radical cyclisations. The formation of highly sterically congested vicinal all-carbon quaternary stereocentres is also discussed. Finally, the use of radical cyclisation methodology for the synthesis of complex cyclic structures and applications in natural product total synthesis is examined. Chapter 2 gives an account of the manganese(III) acetate-mediated cyclisation of 5-pentenyl malonates bearing a terminal aryl group. The effects of the aryl group are tested with a range of electronically varied substituents. The formation of bi- and tricyclic cyclopentane-lactones bearing adjacent quaternary-quaternary-tertiary stereocentres is demonstrated. Chapter 3 demonstrates the synthesis of highly strained tricyclic bis-lactones. The metal complexes manganese(III) acetate and cerium(IV) ammonium nitrate are shown to give complementary stereoselectivity across a range of cyclisation substrates. Possible synthetic applications of tricyclic bis-lactones are also investigated. Chapter 4 details an asymmetric formal synthesis of the proteasome inhibitor salinosporamide A. An oxidative radical cyclisation forms the key heterocycle in Danishefsky’s synthesis of this biologically important molecule, and showcases the use of the radical chemistry in natural product synthesis. Full experimental details, selected NMR spectra, and X-ray crystallographic data are also provided.

This thesis presents three investigations of the magnetic and electronic proper- ties of manganese oxide materials. The investigations are performed using a variety of neutron scattering and x-ray scattering techniques. The electronic ground-state of Pr(Sr_0.1 Ca_0.9)₂ Mn₂O₇ an antiferromagnet with CE-type ordering, is determined using neutron spectroscopy, as opposed to the more usual approach of using diffraction. The Zener polaron model of the elec- tronic ground state of the CE-type magnetic phase is shown to be unsuitable for this material. The ground-state is shown to agree well with the electronic ground state proposed by Goodenough in the 1950’s, but without significant Mn^3+/Mn^4+ disproportionation. The distribution of the magnetisation density within the unit cell of the CE-type antiferromagnet La_0.5Sr_1.5MnO₄ is determined from a polarised neutron diffraction experiment by analysing the results with the maximum entropy method. The majority of the magnetisation density is found to be located at the Mn site. The investigation shows tentative evidence of a small magnetic moment on the in-plane O site. However, a larger moment is observed at both the La/Sr site and the out-of-plane O site. The magnetic structure of the magnetoelectric multiferroic DyMn₂O₅ is inves- tigated using resonant magnetic x-ray scattering. The magnetic structure is shown to be similar to other members of the RMn₂O₅ series of multiferroics, but with the key difference that the magnetic moments are closely aligned parallel with the crystallographic b-axis, in contrast to the usual observation of the moments being close to parallel with the a-axis. This study also shows evidence that the electrical polarisation has a significant contribution from the valence electrons of the O ions, agreeing with previous work.

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Manganese and iron homeostasis play an important role in oxidative stress protection in a variety of organisms. However, the transport and role of these metals in the periodontal pathogen Porphyromonas gingivalis were not well understood. Analysis of the genome of P. gingivalis W83 revealed the presence of two genes encoding homologs of ferrous iron transport protein, FeoB1 and FeoB2. The goal of this study was to determine the role of these two putative transporters in metal transport, their contributions to resistance to oxygen radicals and intracellular survival as well as the regulation and genetic organization of these two loci. Isogenic mutant strains deficient in FeoB1 and FeoB2, respectively, were generated and used in this study. The transport ability for manganese and iron was assessed and compared in feoB1, feoB2 mutant and wild type strains using 55Fe2+ and 54Mn2+. We demonstrated that feoB2 encodes a major manganese transporter, while FeoB1 functions as a major ferrous iron transporter. The roles of P. gingivalis FeoB1 and FeoB2 in oxidative stress defense and intracellular survival in host cells were determined using an oxidative stress survival assay and an in vitro infection assay, respectively. The feoB2 mutant exhibited reduced survival after exposure to H2O2 and to atmospheric oxygen and inside the host cells compared to the wild-type strain and its revertant, while the feoB1 mutant survived as well as the wild type strain under oxidative stress and possessed better capability to adhere to and survive in the host cells. Our results demonstrate that FeoB2 is required for protection of the bacterium from oxidative stress and for intracellular survival of P. gingivalis in host cells. However, FeoB1 is dispensable for both processes. Quantitative RT-PCR analysis revealed that expression of feoB2 in P. gingivalis is induced by oxidative stress. However, expression of feoB1 increased 2-fold upon exposure to lower growth temperature. Both observed inductions were specific and not detected under other stress conditions. We have also showed in this study that feoB2 is the second gene transcribed in an operon that is composed of a total of five genes and feoB1 is only co-transcribed with one downstream gene encoding a hypothetical protein. Notably, we also identified tandem repeats with potential to form stable stem-loop RNA secondary structure within the feoB2 and feoB1 transcripts.To our knowledge, this study has demonstrated the first connection among metal homeostasis, oxidative stress resistance and response to host cells in the periodontal pathogen, P. gingivalis.

Title: Cross-bridged cyclams as manganese(II) chelators Autor: Bc. Luděk Míka Department: Department of Inorganic Chemistry, Faculty of Science Supervisor: doc. RNDr. Jan Kotek, Ph.D. Supervisor's e-mail address: modrej@natur.cuni.cz Abstract: The aim of this project was to synthesize a new kind of Mn(II) complexes with ligands derived from cross-bridged cyclam. These complexes may be potentially used as contrast agents in magnetic resonance imaging. Six macrobicyclic ligands with various pendant arm were synthesized, three complexes were sucesfully prepared. Electrochemical properties of prepared manganese(II) complexes with synthesized ligands were studied using cyclic voltammetry. Relaxivity of prepared complexes was determined by 1 H NMR spectroscopy. Keywords: cross-bridged cyclam, phosphonate, phosphinate, pendant arms, manganese

P. chrysosporium est un champignon saprophyte capable de dégrader de nombreux xénobiotiques, ce qui le rend particulièrement intéressant pour des applications en bioremédiation. Plusieurs publications mettent en avant l'importance de la maîtrise de l'homéostasie métallique dans la production de certaines enzymes lignolytiques. La présence de manganèse est en effet nécessaire à la production des manganèses peroxydases, alors qu'à l'inverse une carence permettra la production de lignines peroxydases. Cependant, la caractérisation de transporteurs impliqués dans le contrôle de l'homéostasie métallique n'a fait l'objet de recherches poussées que chez le champignon modèle S. cerevisiae. L'analyse des transporteurs putatifs de manganèse de 26 espèces fongiques représentant 20 ordres fongiques a permis de constituer un répertoire de 281 transporteurs de manganèse. L'analyse phylogénétique a permis de mettre en évidence que des processus de duplication, mais également de délétion, avaient eu lieu en particulier chez S. cerevisiae. Cependant ce dernier ne possède pas de transporteurs de manganèse appartenant à la famille des Cation Diffusion Facilitator. Dans le génome de P. chrysosporium, onze transporteurs de manganèse appartenant à différentes familles de gènes ont été identifiés. Le niveau d'expression de ces différents gènes a été étudié notamment en condition lignolytique. Ces transporteurs ont également été clonés afin de vérifier leurs fonctions par complémentation en système hétérologue. Cette étude a permis de mettre en évidence les transporteurs de manganèse putatifs de nombreux organismes fongiques, ainsi que l'absence d'une famille de transporteurs impliquée dans les mouvements de manganèse chez S. cerevisiae / P. chrysosporium is a saprophytic fungus able to degrade many xenobiotics which makes it particularly attractive for applications in bioremediation. Several publications highlight the importance of metal homeostasis in the production of lignolytics enzymes. Indeed the presence of manganese is required for the production of manganese peroxidase. Conversely, deficiency allows the production of lignins peroxidases. Characterization of transporters involved in the control of manganese homeostasis has been only researched in the model S. cerevisiae. Analysis of putative manganese transporters of 26 fungal species representing 20 orders of fungus was used to form a repertory of 281 transporters of manganese. Phylogenetic analysis allowed to highlight that duplication process, but also deletion, had occurred particularly in S. cerevisiae. However this one is devoid of transporters belonging to the manganese Cation Diffusion Facilitator. Eleven transporters belonging to gene families in which manganese transporters have been found were identified in the P. chrysosporium?s genome. Expression level of these genes was examined particularly in ligninolytic condition. Transporters have also been cloned in order to verify their functions by complementation in heterologous system. This study allowed to identify putative manganese transporters of numerous fungal organisms and the lack of a transporters family involved in the manganese transport in S. cerevisiae

Master of Science / Department of Agronomy / Dorivar Ruiz Diaz / The limitation of an essential nutrient for plant growth can affect crop yield. Research has been focused mainly on macronutrients, nevertheless micronutrients are equally important. This thesis is divided into three studies, which had the purpose of assessing frequent questions that producers have about micronutrient fertilizers and their effect on several crops in Kansas. The objective of the first study was to summarize and analyze results from studies since 1962 until 2015 to verify responses to zinc (Zn) and sulfur (S) fertilization in corn (Zea mays), sorghum (Sorghum bicolor (L.) Moench), wheat (Triticum aestivum) and soybean (Glycine max (L.) Merr). The treatments evaluated consisted of fertilizer Zn or S application versus their respective unfertilized treatments. Zinc fertilization significantly increased corn yield; no significant response was found for sorghum, wheat and soybean. Sulfur fertilization did not increase yields on corn and wheat. The objectives of the second study were: (i) to evaluate soybean response to S and micronutrients boron (B), copper (Cu), manganese (Mn), and Zn fertilizer application and to assess soil test and soybean seed and tissue nutrient concentration with fertilization. Treatments consisted of an unfertilized control, micronutrient fertilizer as individual nutrient for B, Cu, Mn, S and Zn applied broadcast pre-plant, in addition to a blend of these nutrients using two different placements (broadcast and band). Secondary and micronutrient fertilization showed no significant effect on soybean yield at any of the ten locations. Zinc fertilization showed significant effects on soybean tissue and seed Zn concentration. The objective of the third study was to evaluate soybean tissue nutrient response to micronutrient fertilizers in field strips with high variability in soil properties in the area evaluated. The study consisted of two strips (with and without fertilizer) and replicated three times. The treatment with fertilizer included a blend of Cu, Mn and Zn at a rate of 11.2 kg ha⁻¹ and B at a rate of 2.8 kg ha⁻¹. Initial soil tests B, Cu, Mn and Zn were not good indicators of soybean tissue response. Within-field variability of soybean Zn and B tissue content were affected by soil pH and organic matter; and these factors may be used to help explain field variability in plant availability. The micronutrient blend treatment showed higher tissue Zn and B values compared to the control. When pH ranged from 5.5 to 7.6, B in soybean tissue was higher on the control than the micronutrient blend treatment. Copper concentration in soybean tissue did not show significant difference between treatments at any location, regardless of pH and organic matter levels.

The modification of anode materials is important to enhance the power generation of MFCs (microbial fuel cells). A novel and cost-effective modified anode that is fabricated by dispersing manganese dioxide (MnO2) and HNTs (Halloysite nanotubes) on carbon cloth to improve the MFCs' power production was reported. The results show that the MnO2/HNT anodes acquire more bacteria and provide greater kinetic activity and power density compared to the unmodified anode. Among all modified anodes, 75 wt% MnO2/HNT exhibits the highest electrochemical performance. The maximum power density is 767.3 mWm(-2), which 21.6 higher than the unmodified anode (631 mW/m(2)). Besides, CE (Coulombic efficiency) was improved 20.7, indicating that more chemical energy transformed to electricity. XRD (X-Ray powder diffraction) and FTIR (Fourier transform infrared spectroscopy) are used to characterize the structure and functional groups of the anode. CV (cyclic voltammetry) scans and SEM (scanning electron microscope) images demonstrate that the measured power density is associated with the attachment of bacteria, the microorganism morphology differed between the modified and the original anode. These findings demonstrate that MnO2/FINT nanocomposites can alter the characteristics of carbon cloth anodes to effectively modify the anode for practical MFC applications. (C) 2016 Elsevier Ltd. All rights reserved.

Student Number : 9904952F - MSc Dissertation - School of Chemical and Metallurgical Engineering - Faculty of Engineering and the Built Environment / This dissertation is a study of the effect of manganese, nitrogen and molybdenum on the corrosion behaviour of a low nickel, austenitic stainless steel. The trademarked steel, HerculesTM, has a composition of 10 wt% Mn, 0.05 wt% C, 2 wt% Ni, 0.25 wt% N and 16.5 wt% Cr. Eighteen alloys with a HerculesTM base composition were made with varying manganese, molybdenum and nitrogen contents, to establish the effect of these elements on the corrosion behaviour of the steel, and to determine a composition that would ensure increased corrosion resistance in very corrosive applications. The manganese was varied in three levels (5, 10 and 15 wt%), the molybdenum in three levels (0.5, 1 and 2 wt%) while the nitrogen was varied only in two levels (0.15 and 0.3 wt%). The dissertation details the manufacturing and electrochemical corrosion testing of these alloys. Preliminary tests were done on 50g buttons, and full-scale tests on 5 kg ingots. The buttons had a composition that was not on target, this was however rectified in the making of the ingots. Potentiodynamic tests were done in a 5 wt% sulphuric acid solution and the corrosion rate (mm/y) was determined directly from the scans. From the corrosion test results, it was clear that an increase in manganese decreases the corrosion rate, since the 5 wt% Mn alloys had the highest corrosion rate, whereas the 15 wt% Mn alloys, the lowest. The addition of molybdenum at 5 wt% Mn decreased the corrosion rate such that a trend of decreasing corrosion rate with increasing molybdenum was observed. At 10 and 15 wt% Mn molybdenum again decreased the corrosion rate significantly, but the corrosion rate value remained more or less constant irrespective of the increasing molybdenum content. At nitrogen levels lower than those of HerculesTM (less than 0.25 wt%) there was no change in corrosion rate as nitrogen was increased to levels closer to 0.25 wt%. For nitrogen levels higher than 0.25 wt%, corrosion rates decreased as nitrogen levels were increased further from 0.25 wt% but only at Mo contents lower than 1.5 wt%. The HerculesTM composition was developed for its mechanical properties. Microstructural analyses revealed that the 5 wt% Mn alloys were not fully austenitic and since the 15 wt% Mn alloys behave similarly to the 10 wt% Mn alloys, it was concluded that 10 wt% Mn was optimum for HerculesTM. All the alloys tested had a much lower corrosion rate than HerculesTM. Any addition of molybdenum thus improved the corrosion rate of this alloy. An alloy with a HerculesTM base composition, 10 wt% Mn, 0.15 wt% N and a minimum addition of 0.5 wt% Mo would be a more corrosion resistant version of HerculesTM. Pitting tests were done on the 10 wt% Mn ingots in a 3.56 wt% sodium chloride solution. The results showed that an increase in molybdenum increased the pitting resistance of the ingots. Immersion tests in a 5 wt% sulphuric acid solution at room temeperature on the 10 wt% Mn ingots confirmed that the ingots corroded by means of general corrosion.