This thesis is a part of grant assignment and focuses on the effect and properties of input material, limestone, on reactivity and speed of decarbonation. The aim of this thesis is to find the effect of chemical composition, petrography, genesis and diagenesis, porosity and microstructure of limestones on reactivity and speed and profile of decarbonation. The experimental part of thesis describes analysis of chosen limestone samples regarding porosity, reactivity by Bischof-Uhde method and process of decarbonation of calcite in term of crystallinity of product.

Chemoselektive Peptidfragmentverknüpfungsmethoden sind ein zentrales Element der chemischen Peptid- und Proteinsynthese. Auf der Suche nach einem „universellen Werkzeug für die Peptidligation“ wurde in den vergangenen zwei Jahrzenten eine Vielzahl unterschiedlicher Hilfsmolekülen (Auxiliare) entwickelt. Trotz des enormen Forschungaufwandes blieben bisher verfügbare Nα-Auxiliare jedoch in ihrer Anwendung auf glycinhaltige Ligationsstellen beschränkt. Im Fall der häufig verwendeten säurelabilen Nα-Auxiliare müssen zudem starke Säuren oder Supersäuren eingesetzt werden, um das Hilfsmolekül nach der Peptidligation zu entfernen. Dabei wurde häufig die Spaltung der zuvor aufgebauten Amidbindung als unerwünschte Nebenreaktion beobachtet. In der vorliegenden Arbeit wurde die Synthese von acht Nα-Auxiliaren erarbeitet und deren Anwendung in der erweiterten nativen chemischen Ligation untersucht. Dabei konnten sechs Hilfsmoleküle identifiziert werden, welche die Auxiliar-Abspaltung unter mild-basischen Bedingungen ermöglichten. Von besonderer Bedeutung war das 2-Mercapto-2-phenethyl-Grundgerüst, welches im Gegensatz zu bisher beschriebenen Nα-Auxiliaren erstmals den Zugang zu sterisch anspruchsvollen Verknüpfungstellen, jenseits von Glycin, gestattete. Der Nutzen des Auxiliars wurde in die chemische Totalsynthese zweier antimikrobieller Peptide demonstriert. Durch die Verwendung eines 13C-markierten Hilfsmoleküls konnte der Mechanismus der radikalischen Auxiliar-Abspaltungsreaktion in NMR-Experimenten detailliert untersucht werden. Zusätzlich wurde das 2-Mercapto-2-phenethyl-Auxiliar in einer neuen Methode der chemischen Proteinsynthese eingesetzt, welche die gewünschten Proteine ohne eine einzige HPLC-Reinigung in reiner Form lieferte. Im letzen Teil der Arbeit wurde mit dem 2-Selenol-2-phenethyl-Grundgerüst erstmals die Anwendung eines Selenol-funktionalisierten Nα-Auxiliars beschrieben. Das Hilfsmolekül ermöglichte besonders schnelle Verknüpfungsreaktionen und konnte zudem rasch mit hoher Selektivität entfernt werden. / Chemoselective ligation methods are an essential element of chemical peptide and protein synthesis. The search of a „universal tool for peptide ligation“ led to a range of different ligation auxiliaries over the last two decades. Despite the intense research in this field established Nα-auxiliaries remained limited to glycine-containing ligation sites. Furthermore, the application of frequently used acid-labile Nα-auxiliaries requires strong acids or superacids to remove the auxiliary after the ligation reaction. Under these harsh acidic conditions the cleavage of the established amide bond has been observed as an undesired side-reaction. This work describes the synthesis of eight Nα-auxiliaries and their application in extended native chemical ligation. Six helping molecules were identified enabling auxiliary cleavage under mild-basic conditions. Perhaps most important and in contrast to previously reported Nα-auxiliaries, the 2-mercapto-2-phenethyl group facilitated access to sterically demanding ligation sites, beyond glycine. The synthetic utility of the auxiliary was demonstrated by the chemical total synthesis of two antimicrobial peptides. The application of a 13C-labelled scaffold allowed a detailled study oft the radical auxiliary cleavage reaction by NMR-spectroscopy. Additionally, the 2-mercapto-2-phenethyl auxiliary was utilised for a novel method of chemical protein synthesis, which delivered the desired proteins without a single HPLC-purification in high purity. Finally, a selenol-functionalized Nα-auxiliary is described for the first time by introducing the 2-selenol-2-phenethyl mojety. This scaffold enabled execptionally rapid peptide ligations and is readily removed with high selectivity.

Two and three-phase flow processes involving gas, liquid and solid, are common in nature and industry, and include some of the most complex and poorly-understood transport problems. In this research hydrodynamics, heat and mass transfer processes in complex two and three-phase flows were investigated. The interfacial surface area concentration in a short vertical column subject to the through flow of fiber-liquid-gas slurry was experimentally measured using the gas absorption technique. The experimental data were statistically analyzed for parametric effects, and were empirically correlated. The absorption of a gaseous species by a slurry droplet with internal circulation and containing reactive micro-particles was simulated, and parametrically studied. The micro-particles were found to enhance the absorption rate. The absorption rate was sensitive to droplet recirculation, and shrinkage of particles with time resulted in declining absorption rates. The transport of soot particles, suspended in laminar hot gas flowing in a tube, was modeled and parametrically studied. Due to coupled thermal radiation and thermophoresis, a radially-nonuniform temperature profile develops, leading to sharp, non-uniform radial soot-concentration profiles. The assumption of monodisperse particles leads to over-prediction of thermophoresis. The transport and removal of particles suspended in bubbles rising in a stagnant liquid pool were modeled based on a Eulerian – Monte Carlo method. The bubble hydrodynamics were treated in Eulerian frame, using the Volume-of-Fluid (VOF) technique, while particle equations of motion were numerically solved in Lagrangian frame. The bubbles undergo shape change, and have complex internal circulation, all of which influence the particle removal. Model predictions were also compared with experimental data. Using a resemblance between two-phase flow in microchannels, and in large channels at microgravity, a simple Weber number-based two-phase flow regime map was developed for microchannels. Based on the available air-water experimental data, a criterion for the prediction of conditions that lead to flow regime transition out of the stratified-wavy flow pattern in horizontal annular channels was proposed. The thermocapillary effects on liquid-vapor interface shape during heterogeneous bubble ebullition in microchannels were analytically studied.