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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
911

Studium pokročilých hořčíkových slitin s vysokou pevností pomocí in-situ metod / Study of advanced high strength magnesium alloys by in situ techniques

Fekete, Klaudia January 2019 (has links)
The aim of the present doctoral thesis was to reveal the active deformation mechanisms in novel high strength magnesium (Mg) alloys using advanced in-situ techniques with high time and space resolutions. The deformation behavior of two extruded Mg-LPSO alloys with a different volume fraction of the long-period stacking ordered (LPSO) phase was investigated in tension and compression at room temperature and in compression at 200 řC, 300 řC, and 350 řC. In order to support the results obtained by in-situ acoustic emission and synchrotron diffraction methods, detailed microstructure investigation was provided by transmission and scanning electron microscopy, particularly the backscattered electron imaging and electron backscatter diffraction technique were used. The results indicate that both temperature and the LPSO phase content significantly influence the plasticity of the magnesium matrix, particularly they affect the activation of extension twins and non-basal slip. Moreover, both parameters have a high impact on the formation of the deformation kinks in the LPSO phase. Keywords: Mg-LPSO alloys, deformation mechanisms, acoustic emission, synchrotron diffraction, in-situ methods.
912

Karyotypová evoluce u vybraných čeledí entelegynních pavouků / Karyotype evolution of selected families of entelegyne spiders

Kotz, Matěj January 2020 (has links)
The Araneoidea superfamily is a diverse clade of spiders with a great species diversity. The whole superfamily displays considerable conservativeness of observed karyotypes. Most likely ancestral karyotype in males is 24 acrocentric chromosomes with X1X2 sex determination system. The goal of this study is to explore the karyotype diversity of two araneoid families - Araneidae and Mimetidae. The majority of studied species exhibit the ancestral karyotype. In some species of the aformentioned families was observed sudden increase in chromosome numbers, up to 2n♂ = 52 in Araneidae and up to 2n♂ = 57 in Mimetidae. The latter number is the highest chromosome count observed in Entelegynae so far. Increase in 2n goes hand in hand with increase in sex chromosome numbers, leading up to X1X2X3X40 system in Araneidae and up to X1X2X3X4X5X6X70 in Mimetidae. I suggest polyploidy as a possible mechanism of the increase. To test this hypothesis, I measured the size of the genome using flow cytometry and used fluorescence in situ hybridization for the detection of 18S rRNA and 5S rRNA genes. For one species, probe for U2 snRNA gene was also optimized as part of this thesis. In many species studied, these techniques were used for the first time ever. In the case of the family Mimetidae, the largest genomes in...
913

Preparation and Characterization of Nanoscopic Solid State Hydrogen Storage Materials

Surrey, Alexander 30 September 2016 (has links)
Die Speicherung von Wasserstoff in Form von Hydriden im festen Aggregatzustand hat den Vorteil einer hohen volumetrischen und gravimetrischen Wasserstoffspeicherdichte, die sowohl für die stationäre als auch die mobile Anwendung nötig ist. Um die Anforderungen dieser Anwendungen erfüllen zu können, müssen die Speichereigenschaften dieser Materialien weiter verbessert werden. Als zentrales Konzept dieser Dissertation wird die Nanostrukturierung verfolgt, die eine vielversprechende Strategie zur Modifizierung der thermodynamischen und kinetischen Eigenschaften von Hydriden darstellt. Die Transmissionselektronenmikroskopie (TEM) stellt dabei eine unverzichtbare Untersuchungsmethode solch nanoskopischer Materialien dar. Als problematisch erweist sich dabei die durch Radiolyse hervorgerufene Zersetzung der meisten Hydride bei der Beleuchtung mit dem abbildenden Elektronenstrahl. Im ersten Teil dieser Arbeit wird eine Methodik entwickelt um dieses Phänomen quantitativ mit Hilfe von Valenzelektronenenergieverlustspektroskopie zu untersuchen. Hierzu kommt kugelgemahlenes MgH2 als Modellsystem zum Einsatz. Die Dehydrierung kann quantitativ durch die inelastische Streuung der hochenergetischen Elektronen am MgH2-Plasmon erklärt werden. Eine Lösung dieses grundlegenden Problems wird theoretisch an Hand von Multislice TEM-Kontrastsimulationen untersucht. Hierbei wird ein TEM Experiment unter Wasserstoff bei Umgebungsdruck anstatt unter Vakuum simuliert, was mit Hilfe eines speziellen TEM Halters, in dem das Gas durch elektronentransparente Fenster eingeschlossen ist, realisiert werden kann. Im zweiten Teil wird der Einfluss des Nanoconfinements (Nanoeinschließung), einer speziellen Form der Nanostrukturierung, des komplexen Hydrids LiBH4 auf dessen Wasserstoffspeichereigenschaften untersucht, wofür eine neuartige nanoporöse aerogel-ähnliche Kohlenstoff-Gerüststruktur zum Einsatz kommt. Diese wird durch Salt Templating synthetisiert - einer simplen und nachhaltigen Methode zur Herstellung nanoporöser kohlenstoffbasierter Materialien mit großen Porenvolumina. Es wird gezeigt, dass durch das Nanoconfinement die Wasserstoffdesorptionstemperatur, die für makroskopisches LiBH4 bei über 400 °C liegt, auf 310 °C sinkt und die Desorption bereits bei 200 °C einsetzt. Eine teilweise Rehydrierung ist unter moderaten Bedingungen (100 bar und 300 °C) möglich, wobei die Reversibilität durch eine partielle Oxidation des amorphen Bor gehemmt ist. Im Gegensatz zu Beobachtungen einer aktuellen Veröffentlichung von in hoch geordnetem, nanoporösen Kohlenstoff eingebetteten LiBH4 deuten die in-situ TEM-Heizexperimente der vorliegenden Arbeit darauf hin, dass beide Reaktionsprodukte (B und LiH) in den Poren des aerogel-ähnlichen Kohlenstoffs verbleiben.:List of Figures vi 1. Introduction 1 2. Fundamentals 5 2.1. Solid state hydrogen storage 5 2.2. Thermodynamics 7 2.3. Magnesiumhydride, MgH2 9 2.4. Lithiumborohydride, LiBH4 10 2.5. Nanoconfinement 12 2.5.1. Nanoconfinement of MgH2 13 2.5.2. Nanoconfinement of LiBH4 15 2.6. Radiation damage of hydrides in the TEM 17 3. Theoretical and Experimental Methods 19 3.1. Ball milling 19 3.2. X-ray diffraction analysis 19 3.3. Thermal Characterization 20 3.3.1. Differential Scanning Calorimetry 20 3.3.2. Coupled Thermogravimetry and Mass Spectroscopy 21 3.4. Melt infiltration of LiBH4 21 3.5. Solid State Nuclear Magnetic Resonance 21 3.6. Transmission Electron Microscopy 23 3.6.1. In-situ TEM Heating 25 3.6.2. Environmental TEM 26 3.6.3. Electron Energy Loss Spectroscopy 28 3.6.4. Multislice Simulations 33 4. Electron Beam induced Dehydrogenation of MgH2 38 4.1. Microscopic Model of Hydrogen Release 38 4.2. Determination of Characteristic Electron Doses 39 4.3. Beam Damage Mechanism 42 4.4. Thickness Dependence of the Electron Dose 43 4.5. Conclusions for the Electron Beam Induced Dehydrogenation 47 4.6. Multislice Simulations for ETEM Studies 47 4.6.1. Methods of the Multislice Simulations 48 4.6.2. Results and Discussion of the Multislice Simulations 50 4.6.3. Conclusions of the Multislice Simulations 54 5. Nanoconfinement of LiBH4 in Aerogel-Like Carbon 56 5.1. Nanoporous Carbon Scaffolds 56 5.2. DSC Analysis of Melt Infiltration 58 5.3. XRD Analysis 59 5.4. Thermogravimetry and Mass Spectrometry Analysis 60 5.4.1. Hydrogen Desorption Properties of Nanoconfined LiBH4 60 5.4.2. Rehydrogenation of Nanoconfined LiBH4 63 5.5. In-situ STEM Analysis 63 5.6. Solid State 11B NMR 67 6. Conclusions 69 A. Appendix 71 A.1. Derivation of the Fourier-Log Deconvolution 71 A.2. Derivation of Equation 4.2 73 Bibliography 75 / Storing hydrogen in solid hydrides has the advantage of high volumetric and gravimetric hydrogen densities, which are needed for both stationary and mobile applications. However, the hydrogen storage properties of these materials must be further improved in order to meet the requirements of these applications. Nanostructuring, which represents one of the central approaches of this thesis, is a promising strategy to tailor the thermodynamic and kinetic properties of hydrides. Transmission electron microscopy (TEM) is an indispensable tool for the structural characterization of such nanosized materials, however, most hydrides degrade fast upon irradiation with the imaging electron beam due to radiolysis. In the first part of this work, a methodology is developed to quantitatively investigate this phenomenon using valence electron energy loss spectroscopy on ball milled MgH2 as a model system. The dehydrogenation can be quantitatively explained by the inelastic scattering of the incident high energy electrons by the MgH2 plasmon. A solution to this fundamental problem is theoretically studied by virtue of multislice TEM contrast simulations of a windowed environmental TEM experiment, which allows for performing the TEM analysis in hydrogen at ambient pressure rather than vacuum. In the second part, the effect of the nanoconfinement of the complex hydride LiBH4 on its hydrogen storage properties is investigated. For this, a novel nanoporous aerogel-like carbon scaffold is used, which is synthesized by salt templating - a facile and sustainable technique for the production of nanoporous carbon-based materials with large pore volumes. It is shown that the hydrogen desorption temperature, which is above 400 °C for bulk LiBH4, is reduced to 310 °C upon this nanoconfinement with an onset temperature as low as 200 °C. Partial rehydrogenation can be achieved under moderate conditions (100 bar and 300 °C), whereby the reversibility is hindered by the partial oxidation of amorphous boron. In contrast to recent reports on LiBH4 nanoconfined in highly ordered nanoporous carbon, in-situ heating in the TEM indicates that both decomposition products (B and LiH) remain within the pores of the aerogel-like carbon.:List of Figures vi 1. Introduction 1 2. Fundamentals 5 2.1. Solid state hydrogen storage 5 2.2. Thermodynamics 7 2.3. Magnesiumhydride, MgH2 9 2.4. Lithiumborohydride, LiBH4 10 2.5. Nanoconfinement 12 2.5.1. Nanoconfinement of MgH2 13 2.5.2. Nanoconfinement of LiBH4 15 2.6. Radiation damage of hydrides in the TEM 17 3. Theoretical and Experimental Methods 19 3.1. Ball milling 19 3.2. X-ray diffraction analysis 19 3.3. Thermal Characterization 20 3.3.1. Differential Scanning Calorimetry 20 3.3.2. Coupled Thermogravimetry and Mass Spectroscopy 21 3.4. Melt infiltration of LiBH4 21 3.5. Solid State Nuclear Magnetic Resonance 21 3.6. Transmission Electron Microscopy 23 3.6.1. In-situ TEM Heating 25 3.6.2. Environmental TEM 26 3.6.3. Electron Energy Loss Spectroscopy 28 3.6.4. Multislice Simulations 33 4. Electron Beam induced Dehydrogenation of MgH2 38 4.1. Microscopic Model of Hydrogen Release 38 4.2. Determination of Characteristic Electron Doses 39 4.3. Beam Damage Mechanism 42 4.4. Thickness Dependence of the Electron Dose 43 4.5. Conclusions for the Electron Beam Induced Dehydrogenation 47 4.6. Multislice Simulations for ETEM Studies 47 4.6.1. Methods of the Multislice Simulations 48 4.6.2. Results and Discussion of the Multislice Simulations 50 4.6.3. Conclusions of the Multislice Simulations 54 5. Nanoconfinement of LiBH4 in Aerogel-Like Carbon 56 5.1. Nanoporous Carbon Scaffolds 56 5.2. DSC Analysis of Melt Infiltration 58 5.3. XRD Analysis 59 5.4. Thermogravimetry and Mass Spectrometry Analysis 60 5.4.1. Hydrogen Desorption Properties of Nanoconfined LiBH4 60 5.4.2. Rehydrogenation of Nanoconfined LiBH4 63 5.5. In-situ STEM Analysis 63 5.6. Solid State 11B NMR 67 6. Conclusions 69 A. Appendix 71 A.1. Derivation of the Fourier-Log Deconvolution 71 A.2. Derivation of Equation 4.2 73 Bibliography 75
914

Novel thermal and electron-beam approaches for the fabrication of boron-rich nanowires

Gonzalez Martinez, Ignacio Guillermo 01 November 2016 (has links)
Pursuing the development and implementation of novel synthesis techniques to produce nanostructures with an interesting set of properties is a goal that advances the frontiers of nanotechnology. Also of fundamental importance is to revisit well-established synthesis techniques employing a new set of materials as precursors, substrates and catalysts. Fundamental breakthroughs in the field of nanotechnology can be achieved by developing new synthesis procedures as well as by adapting known procedures to new materials. This thesis focuses on both kinds of experiments. A variant of chemical vapor deposition (CVD) has been used to produce Al5BO9 nanowires out of sapphire wafers without the need of a catalyst material. The novelty of the work relies on the formation mechanism of the Al5BO9 nanowires. Essentially, the process can be described as a large-scale topological transformation taking place on the substrate’s surface as its chemical composition changes due to the arrival of precursor molecules. Dense mats of Al5BO9 nanowires cover large areas of the substrate that were previously relatively flat. The process is enhanced by a high temperature and the presence of pre-existing superficial defects (cracks, terraces, etc.) on the substrates. Al5BO9 nanowires as well as B/BOX nanowires and BOX nanotubes were also produced via a novel in-situ electron beam-induced synthesis technique. The process was carried out at room temperature and inside a transmission electron microscope. Au nanoparticles were used as catalyst for the case of B/BOX nanowires and BOX nanotubes, while the Al5BO9 nanowires were synthesized without the need of a catalyst material. The formation and growth of the nanostructures is solely driven by the electron beam. The growth mechanism of the B/BOX nanowires and BOX nanotubes relies on interplay between electrostatic charging of the precursor material (to produce and transport feedstock material) and electron stimulated desorption of oxygen which is able to activate the catalytic properties of the Au nanoparticles. For the case Al5BO9 nanowires a nucleation process based on massive atomic rearrangement in the precursor is instigated by the e-beam, afterwards, the length of some of the nanowires can be extended by a mechanism analogous to that of the growth of the B/BOX nanowires.
915

Molekulárně cytogenetická diagnostika marker chromozomů / Molecular-cytogenetic diagnostics of marker chromosomes

Tesner, Pavel January 2018 (has links)
Supernumerary marker chromosomes (sSMCs) are a relatively rare cytogenetic phenomenon. Their laboratory examination is often difficult, and the clinical interpretation is even more challenging. The main reason is that most sSMC carriers have no clinical manifestations. The chromosome origin and exact range of the aberration are very important, as well as the fact that sSMCs are often found in mosaics that can strongly influence both the phenotype and the interpretation of result. Prenatal sSMC finding is one of the most challenging situations in both clinical and laboratory genetics. This work deals with the investigation process of sSMC carriers using molecular cytogenetic techniques, especially fluorescence in situ hybridization (FISH). We investigated a total of 67 families collected both prospectively and retrospectively, and we found 70 unique sSMCs in a total of 74 individuals. Six cases were familial and in three cases two sSMCs were found in one individual. According to the initial karyotype finding, the cases were divided into two groups, sSMCs supernumerary to a normal karyotype (group A) and sSMCT s supernumerary to the Turner karyotype (group B). The chromosomal origin was successfully determined in 88,6 % sSMCs. In group A the most common findings were sSMCs derived from chromosome 15,...
916

In Situ Ptychography of Heterogeneous Catalysts using Hard X-Rays: High Resolution Imaging at Ambient Pressure and Elevated Temperature

Baier, Sina, Damsgaard, Christian D., Scholz, Maria, Benzi, Federico, Rochet, Amélie, Hoppe, Robert, Scherer, Torsten, Shi, Junjie, Wittstock, Arne, Weinhausen, Britta, Wagner, Jakob B., Schroer, Christian G., Grunwaldt, Jan-Dierk 03 June 2020 (has links)
A new closed cell is presented for in situ X-ray ptychography which allows studies under gas flow and at elevated temperature. In order to gain complementary information by transmission and scanning electron microscopy, the cell makes use of a Protochips E-chipTM which contains a small, thin electron transparent window and allows heating. Two gold-based systems, 50 nm gold particles and nanoporous gold as a relevant catalyst sample, were used for studying the feasibility of the cell. Measurements showing a resolution around 40 nm have been achieved under a flow of synthetic air and during heating up to temperatures of 933 K. An elevated temperature exhibited little influence on image quality and resolution. With this study, the potential of in situ hard X-ray ptychography for investigating annealing processes of real catalyst samples is demonstrated. Furthermore, the possibility to use the same sample holder for ex situ electron microscopy before and after the in situ study underlines the unique possibilities available with this combination of electron microscopy and X-ray microscopy on the same sample.
917

In Situ and Ex Situ Hydrogenation Studies of Zintl Phases Containing Tetrelides or Gallium

Auer, Henry 01 October 2018 (has links)
Die Hydrierung von Zintl-Phasen führt zur Bildung von Einlagerungshydriden, die ausschließlich von Kationen koordiniert sind, zu polyanionischen Hydriden, bei denen Wasserstoff kovalent an das stärker elektronegative Element bindet, oder zu einer Kombination von beiden Motiven. Es wurde eine Reihe neuer Verbindungen dargestellt und mittels Laborröntgen-, Synchrotron- und Neutronenpulverbeugung strukturell charakterisiert. Die meisten Beispiele werden durch die Hydrierung von Zintl-Phasen im CrB- oder FeB-Strukturtyp erhalten. Die beiden Typen sind strukturell eng verwandt. Sie sind durch das Auftreten von polyanionischen Zickzackketten gekennzeichnet. Die Einlagerungshydride LnTtH (Ln = La, Nd, Tt = Si, Ge, Sn) sind Oxidationsprodukte der formal metallischen Zintl-Phasen LnTt = Ln3+ Tt2- e- . Wasserstoff besetzt dabei Ln-Tetraederlücken. Die Produkte treten als gefüllter FeB- (P -Phase, LaGeH-Strukturtyp) oder als gefüllter CrB-Strukturtyp (C -Phase, NiZrH-Strukturtyp) auf. Die Hydrierung der elektronenpräzisen Zintl-Phasen AeTt (Ae = Sr, Ba, Tt = Ge, Sn, CrB-Strukturtyp) führt zu wasserstoffarmen (AeTtHy , y < 1) und wasserstoffreichen (AeTtHy , 1 < y ≤ 2) Phasen. Erstere weisen partiell gefüllte Ae4-Lücken auf. In Phasen mit kleinem y (< 0.4) wird der Wasserstoff statistisch über die Lücken verteilt (α-Phasen). Etwas höhere Gehalte führen zu partieller (β-SrGeHy , 0.47 < y < 0.75) oder vollständiger (β-BaGeH0.5 ) Ordnung. Die wasserstoffreichen Phasen AeTtHy , 1 < y ≤ 2 (γ-Phasen), zeigen sowohl die Strukturmotive von Einlagerungs- als auch von polyanionischen Hydriden. SrSiH1.6 und BaSiH1.9 als literaturbekannte Verbindungen wurden das erste mal strukturell charakterisiert. Die homologe Reihe konnte um SrGeH1.2 , BaGeH1.6 und BaSnH1.3 erweitert werden. Die Ae4 -Tetraeder sind in diesen Phasen vollständig mit Hydridionen besetzt. Zusätzlicher Wasserstoff bindet kovalent an die Polyanionen. Außerdem verknüpfen sich die Zickzackketten z. T. senkrecht zur Kettenrichtung. Es wurden insgesamt drei Strukturtypen differenziert, die alle strukturell eng verwandt sind. Das führt zu Problemen bei der Strukturbestimmung aus Pulverdaten. Der kovalente Charakter der Bindung wurde durch Festkörperkernresonanzspektroskopie und Dichtefunktionaltheorierechnungen charakterisiert. Typische Tetrel-Wasserstoff-Bindungslängen sind 155(2) pm (Si-H), 163(2) pm (Ge-H) und 186(1) pm (Sn-H). In situ -Neutron, Röntgen- und Synchrotronpulverbeugung wurden angewandt um Reaktionsabläufe aufzuklären. Beim Heizen unter Wasserstoffdruck treten im AeTt-H2 -System (Ae = Sr, Ba, Tt = Ge, Sn) verschiedene reversible Reaktionen zwischen den γ-, β- und α-Phasen auf, bevor ein irreversibler Zersetzungsschritt in die binären Hydride AeH2 und die Tt-reichen Zintl-Phasen AeTt2 beobachtet wird. Ein In situ Beugungsexperiment der Reaktion von NdGa mit Wasserstoff zeigt direkt die Bildung von NdGaH1+x (isostrukturell zu γ-AeTtHy ), das eine Zusammensetzung von mindestens x = 0.17 bis 0.80 aufweist. Die Ga-H Abstände sind lang (ca. 200 pm) und darum keine klassischen 2-Elektronen-2-Zentrenbindungen. In situ Beugung an den Reaktionen von KSi und CsSi mit Wasserstoff konnte gezeigt werden, dass die Hydride KSiH3 und CsSiH3 in einem Schritt gebildet werden. Diese Phasen weisen SiH3--Anionien auf, die isoelektronisch zu PH3 sind. Weiteres Heizen unter Wasserstoffdruck führt zur Zersetzung in KH und K8Si46 oder zur Rückbildung von CsSi. Außerdem wurde eine Reihe weiterer Verbindungen auf die Reaktivität gegenüber Wasserstoff untersucht. Die Phasen AeTt2 , AGe und ASixGe1-x (A = K, Rb, Cs) bilden keine Hydride unter den untersuchten Bedingungen (mindestens 5 MPa H2, 700 K). Die Gallide CaGa, Sr8Ga7 und Ba8Ga7 weisen Reaktivität gegenüber Wasserstoff auf. Diese Beispiele zersetzen sich in binäres Hydrid und die galliumreichen Phasen Ca3Ga8, SrGa4 und BaGa4 . In situ Laborröntgenbeugung der Reaktion von CaGa mit Wasserstoff führt zur Bildung einer neuen, kristallinen Phase. Bildung und Zersetzung laufen in einem sehr schmalen Temperaturfenster ab. Die neue Phase konnte noch nicht charakterisiert werden. / The hydrogenation of Zintl phases leads to interstitial hydrides that are coordinated exclusively by cations, polyanionic hydrides that exhibit a covalent bond to the more electronegative element, or a combination of both motifs. A series of new compounds is prepared and structurally characterised by laboratory X-ray, synchrotron and neutron powder diffraction. Most examples can be derived via hydrogenation of CrB- or FeB-type Zintl phases. These structure types are closely related and characterised by polyanionic zigzag chains. The interstitial hydrides LnTtH (Ln = La, Nd, Tt = Si, Ge, Sn) are oxidation products of the formally metallic Zintl phases LnTt = Ln3+ Tt2- e- . Hydrogen occupies tetrahedral Ln4-voids. The products occur as a filled FeB-type phase (P-phase, LaGeH-structure type) or a filled CrB-type phase (C-phase, ZrNiH-structure type). The hydrogenation of electron-precise Zintl phases AeTt (Ae = Sr, Ba, Tt = Ge, Sn, CrB-structure type) leads to hydrogen-poor (AeTtHy , y < 1) and hydrogen-rich phases (AeTtHy , 1 < y ≤ 2). The first show partially hydrogen-filled Ae4-voids. For low contents y < 0.4, hydrogen is statistically distributed over the voids (α-phases). Slightly increased hydrogen contents lead to partial (β-SrGeHy , 0.47 ≤ y ≤ 0.75) or full ordering (β-BaGeH0.5 ). The hydrogen-rich phases AeTtHy, 1 < y ≤ 2 (γ-phases), combine interstitial and polyanionic hydride motifs. The literature-known phases SrSiH1.6 and BaSiH1.9 could be structurally characterised for the first time. The homologue series was extended to SrGeH1.2, BaGeH1.6 and BaSnH1.3 . Tetrahedral Ae4-voids are totally filled with hydride anions. The additional hydrogen binds to the polyanions. Furthermore, some of the zigzag chains are interconnected perpendicular to the chain direction. Three different structure types exhibiting a close structural relationship were identified. This leads to difficulties in structure determination from powder diffraction. The covalent character of the bond is characterised by solid-state nuclear magnetic resonance and density functional theory calculations. Typical tetrel-hydrogen bond lengths are 155(2) pm (Si-H), 163(2) pm (Ge-H) and 186(1) pm (Sn-H). In situ neutron, X-ray and synchrotron powder diffraction were used to elucidate reaction schemes. The AeTt-H2 systems (Ae = Sr, Ba, Tt = Ge, Sn) show several reversible reaction steps between γ-, β- and α-phases upon heating under hydrogen pressure. Finally, an irreversible decomposition into the binary hydrides AeH2 and Tt-rich Zintl phases AeTt2 occurs. In situ diffraction of the reaction of NdGa with hydrogen leads directly to NdGaH1+x (isostructural to γ-AeTtHy ) which shows a large compositional range from at least x = 0.17 to 0.80. Ga-H distances are long (about 200 pm) and, thus, not classical 2-electron-2-center bonds. In situ diffraction of the reactions of KSi and CsSi with hydrogen show a one step formation of the corresponding hydrides KSiH3 and CsSiH3 . They exhibit SiH3--anions which are isoelectronic to PH3 . Further heating under hydrogen pressure leads to decomposition into KH and K8Si46 or reformation of CsSi, respectively. Finally, further compounds were tested for reactivity towards hydrogen. The phases AeTt2 (Ae = Ca, Sr, Ba, Tt = Si, Ge), AGe and ASixGe1-x (A = K, Rb, Cs) do not form corresponding hydrides under the investigated conditions (at least 5 MPa H2, 700 K). The gallides CaGa, Sr8Ga7 and Ba8Ga7 show reactivity towards hydrogen. They decompose into binary hydride and the gallium-rich phases Ca3 Ga8 , SrGa4 or BaGa4. Furthermore, laboratory in situ diffraction of the reaction of CaGa with hydrogen indicates the formation of a new, crystalline phase. Formation and decomposition occur in a relative small temperature window. The new phase could not be characterised, yet.
918

Evolution de surface lors de la corrosion de magnésium : nouvelles approches analytiques pour comprendre les mécanismes de corrosion et de protection / Surface evolution of corroding magnesium : new analytical approaches to understand corrosion mechanisms and protection strategies

Maltseva, Alina 26 September 2018 (has links)
Les alliages légers (Al, Mg) sont aujourd’hui majoritairement utilisés dans les industries aéronautique, électronique, automobile. Toutefois, la faible résistance à la corrosion et à l’abrasion de ces alliages restreint leur développement à grande échelle. Les nouveaux concepts de protection contre la corrosion des alliages légers se basent non seulement sur un effet barrière par une couche épaisse d'oxyde (PEO) ou peindre, mais surtout sur une protection active à l’aide d’inhibiteurs de corrosion spécifiques. Ces inhibiteurs de corrosion pourraient être libérés "sur demande" et génèrent un phénomène ‘d’auto guérison’. L’utilisation des méthodes d’analyse in situ and ex situ modernes spectroscopiques pourraient permettre de mettre en lumière l’évolution de systèmes aussi complexe et aider à mieux définir les facteurs régulant ces processus. / Nowadays light alloys (Al, Mg) are widely used in a number of areas such as electronics, aeronautic, automotive and construction industries. However, the low corrosion and wear resistance of these alloys hinders application of Al and Mg alloys on a larger scale. The new concepts for corrosion protection of light alloys should include not only barrier protection by a thick oxide layer (PEO) or by paint but also an active protection by specific corrosion inhibitors which can be released “on request” and ensure so-called “self-healing”. Use of in situ and ex situ spectroscopic methods could bring a new view to the evolution of such a complicated system and help to define factors controlling these processes.
919

Dříve evoluční zatracenci, nyní tvůrci reprodukční strategie: původ a reprodukce samčí linie vodních skokanů Pelophylax esculentus / Earlier evolutionary dead-ends, now the creators of a reproductive strategy: the origin and reproduction of the all-male water frog lineage Pelophylax esculentus

Doležálková, Marie January 2017 (has links)
Asexual modes of reproduction are usually based on the principle of copying (cloning) DNA from the female and passing it on to the offspring. For most asexually reproducing vertebrates the progeny develop from an unreduced and often unfertilised egg. This is driven by the mechanisms of parthenogenetic and gynogenetic reproduction. While in the former the clonal germ cell develops spontaneously and separately, in the latter a sexual partner is needed to activate the cleavage of the ovum, although without the fusion of the sperm and egg. Therefore in both cases there is no fertilization and the clonal progeny consist solely of daughters, hence the majority of previous studies have only focused on asexual female lineages. However, on rare occasions asexual clonal males can arise when the right fertilization occurs. Whilst these offspring are usually infertile, fertile diploid asexual males have been discovered in just three genera of hybrid origin in vertebrates. One of these unique cases is the European water frog complex of the genus Pelophylax, whose distribution includes the Czech Republic. In areas around the upper Odra River populations of hybrid males were recently discovered who form stable all-male lineages, similar to those formed by asexual females. The results of this study show that males produce...
920

Identifikace klíčových regulátorů genové exprese v savčím oocytu a embryu / Identification of key regulators of gene expression in mammalian oocyte and embryo

Jansová, Denisa January 2017 (has links)
Mammalian oocyte is a highly differentiated cell which gives rise to an embryo after fertilization. Importantly, fully-grown oocytes become transcriptionally inactive at the end of the growth phase. During following stages of development, i. e. meiotic maturation of the oocyte and early embryonic development, only transcripts previously synthesized and stored are used. The tight correlation between mRNA distribution and subsequent protein localization and function provides a mechanism of spatial and temporal regulation of gene expression used by various cell types. However, not much is known about mRNA localization and translation in the mammalian oocyte and early embryo. The aim of my thesis was to determine the localization of transcripts and components of translational machinery in the mammalian oocyte and embryo and to uncover the mechanisms of spatiotemporal regulation of translation as a prerequisite for correct oocyte and embryo development. We have shown that nuclei of both mouse and human oocytes contain RNA molecules and RNA binding proteins. Following the nuclear envelope breakdown (NEBD), translational hot-spots occur in the area surrounding the nuclear region. We suppose that mRNAs previously retained in the nucleus are released to the cytoplasm during NEBD and their subsequent...

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