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Biopsychosoziale Aspekte der beruflichen Wiedereingliederung nach kardiologischer Rehabilitation
(2020)
Bischöfe im Frankenreich waren einflussreiche politische Akteure, die im Laufe des 9. Jahrhunderts ein gelehrtes Wissen vom eigenen Amt entwickelten. Spiegelungen dieses Wissens über das Wesen des Bischofsamtes finden sich in vielen Texten, die meisten stammen aus Westfranken. Offen ist bislang jedoch, welche Relevanz dieses Wissen und das bischöfliche Standesbewusstsein hatten – ist es als normativer Referenzrahmen von anderen politisch relevanten Ständen anerkannt? Wie entwickelt es sich über die Umbruchzeit des 10. Jahrhunderts in der post-karolingischen Zeit und beginnenden Kirchenreform? Diesen Fragen widmet sich das Buch durch eine Untersuchung von Bischofsabsetzungen in Westfranken im 9. und 10. Jahrhundert und durch eine Analyse des Bischofsbildes in monastischen wie bischöflichen Kreisen im 10. und frühen 11. Jahrhundert. So kann ein differenziertes Bild der Wahrnehmung des Bischofsamtes und der konkrete Umgang mit dem Wissen vom Bischofsamt in verschiedenen Kontexten gezeichnet werden.
Carbon nitride semiconductors: properties and application as photocatalysts in organic synthesis
(2023)
Graphitic carbon nitrides (g-CNs) are represented by melon-type g-CN, poly(heptazine imides) (PHIs), triazine-based g-CN and poly(triazine imide) with intercalated LiCl (PTI/Li+Cl‒). These materials are composed of sp2-hybridized carbon and nitrogen atoms; C:N ratio is close to 3:4; the building unit is 1,3,5-triazine or tri-s-triazine; the building units are interconnected covalently via sp2-hybridized nitrogen atoms or NH-moieties; the layers are assembled into a stack via weak van der Waals forces as in graphite. Due to medium band gap (~2.7 eV) g-CNs, such as melon-type g-CN and PHIs, are excited by photons with wavelength ≤ 460 nm. Since 2009 g-CNs have been actively studied as photocatalysts in evolution of hydrogen and oxygen – two half-reactions of full water splitting, by employing corresponding sacrificial agents. At the same time application of g-CNs as photocatalysts in organic synthesis has been remaining limited to few reactions only. Cumulative Habilitation summarizes research work conducted by the group ‘Innovative Heterogeneous Photocatalysis’ between 2017-2023 in the field of carbon nitride organic photocatalysis, which is led by Dr. Oleksandr Savatieiev.
g-CN photocatalysts activate molecules, i.e. generate their more reactive open-shell intermediates, via three modes: i) Photoinduced electron transfer (PET); ii) Excited state proton-coupled electron transfer (ES-PCET) or direct hydrogen atom transfer (dHAT); iii) Energy transfer (EnT). The scope of reactions that proceed via oxidative PET, i.e. one-electron oxidation of a substrate to the corresponding radical cation, are represented by synthesis of sulfonylchlorides from S-acetylthiophenols. The scope of reactions that proceed via reductive PET, i.e. one-electron reduction of a substrate to the corresponding radical anion, are represented by synthesis of γ,γ-dichloroketones from the enones and chloroform.
Due to abundance of sp2-hybridized nitrogen atoms in the structure of g-CN materials, they are able to cleave X-H bonds in organic molecules and store temporary hydrogen atom. ES-PCET or dHAT mode of organic molecules activation to the corresponding radicals is implemented for substrates featuring relatively acidic X-H bonds and those that are characterized by low bond dissociation energy, such as C-H bond next to the heteroelements. On the other hand, reductively quenched g-CN carrying hydrogen atom reduces a carbonyl compound to the ketyl radical via PCET that is thermodynamically more favorable pathway compared to the electron transfer. The scope of these reactions is represented by cyclodimerization of α,β-unsaturated ketones to cyclopentanoles.
g-CN excited state demonstrates complex dynamics with the initial formation of singlet excited state, which upon intersystem crossing produces triplet excited state that is characterized by the lifetime > 2 μs. Due to long lifetime, g-CN activate organic molecules via EnT. For example, g-CN sensitizes singlet oxygen, which is the key intermediate in the dehydrogenation of aldoximes to nitrileoxides. The transient nitrileoxide undergoes [3+2]-cycloaddition to nitriles and gives oxadiazoles-1,2,4.
PET, ES-PCET and EnT are fundamental phenomena that are applied beyond organic photocatalysis. Hybrid composite is formed by combining conductive polymers, such as poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) with potassium poly(heptazine imide) (K-PHI). Upon PET, K-PHI modulated population of polarons and therefore conductivity of PEDOT:PSS. The initial state of PEDOT:PSS is recovered upon material exposure to O2. K-PHI:PEDOT:PSS may be applied in O2 sensing.
In the presence of electron donors, such as tertiary amines and alcohols, and irradiation with light, K-PHI undergoes photocharging – the g-CN material accumulates electrons and charge-compensating cations. Such photocharged state is stable under anaerobic conditions for weeks, but at the same time it is a strong reductant. This feature allows decoupling in time light harvesting and energy storage in the form of electron-proton couples from utilization in organic synthesis. The photocharged state of K-PHI reduces nitrobenzene to aniline, and enables dimerization of α,β-unsaturated ketones to hexadienones in dark.
This habilitation thesis includes seven case studies that examine climate variability during the past 3.5 million years from different temporal and spatial perspectives. The main geographical focus is on the climatic events of the of the African and Asian monsoonal system, the North Atlantic as well as the Arctic Ocean. The results of this study are based on marine and terrestrial climate archives obtained by sedimentological and geochemical methods, and subsequently analyzed by various statistical methods.
The results herein presented results provide a picture of the climatic background conditions of past cold and warm periods, the sensitivity of past climatic climate phases in relation to changes in the atmospheric carbon dioxide content, and the tight linkage between the low and high latitude climate system. Based on the results, it is concluded that a warm background climate state strongly influenced and/or partially reversed the linear relationships between individual climate processes that are valid today. Also, the driving force of the low latitudes for climate variability of the high latitudes is emphasized in the present work, which is contrary to the conventional view that the global climate change of the past 3.5 million years was predominantly controlled by the high latitude climate variability. Furthermore, it is found that on long geologic time scales (>1000 years to millions of years), solar irradiance variability due to changes in the Earth-Sun-Moon System may have increased the sensitivity of low and high latitudes to Influenced changes in atmospheric carbon dioxide.
Taken together, these findings provide new insights into the sensitivity of past climate phases and provide new background conditions for numerical models, that predict future climate change.
Die Arbeit stellt die Funktionsweise und den Erwerb der deutschen Groß- und Kleinschreibung auf theoretischer und empirischer Grundlage dar. Den Ausgangspunkt bildet eine textpragmatische Verallgemeinerung bisheriger graphematischer Ansätze, die zu einem übergreifenden Modell des Majuskelgebrauchs im Deutschen erweitert werden und dabei auch nicht-orthografische Teilbereiche einschließen (Versalsatz, Kapitälchen, Binnenmajuskel etc.).
Im empirischen Teil der Arbeit werden die orthografischen Leistungsdaten von ca. 5.700 Probanden verschiedener Altersklassen (4. Klasse bis Erwachsenenbildung) untersucht und zu einem allgemeinen Erwerbsmodell der Groß- und Kleinschreibung ausgebaut. Mit Hilfe neuronaler Netzwerksimulationen werden unterschiedliche Lernertypen unterschieden und Diskontinuitäten im Kompetenzerwerb nachgewiesen, die auf qualitative Strategiewechsel in der Ontogenese hindeuten. Den Abschluss bilden orthografiedidaktische und rechtschreibdiagnostische Reflexionen der Daten.