TY  - THES
A1  - Yuan, Jiayin
T1  - Poly(Ionic Liquid)s
BT  - innovative polyelectrolytes for materials applications
Y1  - 2015
ER  - 
TY  - THES
A1  - Yang, Haojin
T1  - Deep representation learning for multimedia data analysis
Y1  - 2019
ER  - 
TY  - THES
A1  - Vogel, Heike
T1  - Genetics of obesity and type 2 diabetes
N2  - By using mouse outcross populations in combination with bioinformatic approaches, it was possible to identify and characterize novel genes regulating body weight, fat mass and β-cell function, which all contribute to the pathogenesis of obesity and T2D. In detail, the presented studies identified 1. Ifi202b/IFI16 as adipogenic gene involved in adipocyte commitment, maintenance of white adipocyte identity, fat cell size and the inflammatory state of adipose tissue. 2. Pla2g4a/PLA2G4A as gene linked to increased body weight and fat mass with a higher expression in adipose tissue of obese mice and pigs as well as in obese human subjects. 3. Ifgga2/IRGM as novel regulator of lipophagy protecting from excess hepatic lipid accumulation. 4. Nidd/DBA as a diabetogenic locus containing Kti12, Osbpl9, Ttc39a and Calr4 with differential expression in pancreatic islets and/or genetic variants. 5. miR-31 to be higher expressed in adipose tissue of obese and diabetic mice and humans targeting PPARy and GLUT4 and thereby involved in adipogenesis and insulin signaling. 6. Gjb4 as novel gene triggering the development of T2D by reducing insulin secretion, inducing apoptosis and inhibiting proliferation. The performed studies confirmed the complexity and strong genetic heritability character of obesity and T2D. A high number of genetic variations, each with a small effect, are collectively influencing the degree and severity of the disease. The use of mouse outcross populations is a valid tool for disease gene identification; however, to facilitate and accelerate the process of gene identification the combination of mouse cross data with advanced sequencing resources and the publicly available data sets are essential. The main goal for future studies should be the translation of these novel molecular discoveries to useful treatment therapies. More recently, several classes of novel unimolecular combination therapeutics have emerged with superior efficacy than currently prescribed options and pose the potential to reverse obesity and T2D (Finan et al., 2015). The glucagon-like peptide-1 (GLP-1)- estrogen conjugate, which targets estrogen into cells expressing GLP-1 receptors, was shown to improve energy, glucose and lipid metabolism as well as to reduce food reward (Finan et al., 2012; Schwenk et al., 2014; Vogel et al., 2016). Another possibility is the development of miRNA-based therapeutics to prevent obesity and T2D, such as miRNA mimetics, anti-miRNA oligonucleotides and exosomes loaded with miRNAs (Ji and Guo, 2019; Gottmann et al., 2020). As already described, genome-wide association studies for polygenic obesity and T2D traits in humans have also led to the identification of numerous gene variants with modest effect, most of them having an unknown function (Yazdi et al., 2015). These discoveries resulted in novel animal models and have illuminated new biologic pathways. Therefore, the integration of mouse-human genetic approaches and the utilization of the synergistic effects have the potential to lead to the identification of more genes responsible for common Mendelian forms of obesity and T2D, as well as gene × gene and gene × environment interactions (Yazdi et al., 2015; Ingelsson and McCarthy, 2018). This combination may help to unravel the missing heritability of obesity and T2D, to identify novel drug targets and to design more efficient and personalized obesity prevention and management programs.
Y1  - 2021
CY  - Potsdam
ER  - 
TY  - THES
A1  - Thonicke, Kirsten
T1  - The influence of disturbance, climate extremes and land-use change on vegetation dynamics
Y1  - 2019
ER  - 
TY  - THES
A1  - Stroncik, Nicole A.
T1  - Volatiles as tracers for mantle processes and magma formation and evolution
N2  - The geochemical composition of oceanic basalts provides us with a window into the distribution of geochemical elements within the Earth’s mantle in space and time. In conjunction with a throughout knowledge on how the different elements behave e.g. during melt formation and evolution or on their partition behaviour between e.g. minerals and melts this information has been transformed into various models on how oceanic crust is formed along plume influenced or normal mid-ocean ridge segments, how oceanic crust evolves in response to seawater, on subduction recycling of oceanic crust and so forth. The work presented in this habilitation was aimed at refining existing models, putting further constraints on some of the major open questions in this field of research while at the same time trying to increase our knowledge on the behaviour of noble gases as a tracer for melt formation and evolution processes. In the line of this work the author and her co-workers were able to answer one of the major questions concerning the formation of oceanic crust along plume-influenced ridges – in which physical state does the plume material enter the ridge? Based on submarine volcanic glass He, Ne and Ar data, the author and her co-workers have shown that the interaction of mantle plumes with mid-ocean ridges occurs in the physical form of melts. In addition, the author and her co-workers have also put further constraints on one of the major questions concerning the formation of oceanic crust along normal mid-ocean ridges – namely how is the mid-ocean ridge system effectively cooled to form the lower oceanic crust? Based on Ne and Ar data in combination with Cl/K ratios of basaltic glass from the Mid-Atlantic ridge and estimates of crystallisation pressures they have shown, that seawater penetration reaches lower crustal levels close to the Moho, indicating that hydrothermal circulation might be an effective cooling mechanism even for the deep parts of the oceanic crust. Considering subduction recycling, the heterogeneity of the Earth’s mantle and mantle dynamic processes the key question is on which temporal and spatial scales is the Earth’s mantle geochemically heterogeneous? In the line of this work the author along with her co-workers have shown based on Cl/K ratios in conjunction with the Sr, Nd, and Pb isotopes of the OIBs representing the type localities for the different mantle endmembers that the quantity of Cl recycled into the mantle via subduction is not uniform and that neither the HIMU nor the EM1 and EM2 mantle components can be considered as distinct mantle endmembers. In addition, we have shown, based on He, Ne and Ar isotope and trace-element data from the Foundation hotspot that the near ridge seamounts of the Foundation seamount chain formed by the Foundation hotspot erupt lavas with a trace-element signature clearly characteristic of oceanic gabbro which indicates the existence of recycled, virtually unchanged lower oceanic crust in the plume source. This is a clear sign of the inefficiency of the stirring mechanism existing at mantle depth. Similar features are seen in other near-axis hotspot magmas around the world. Based on He, Sr, Nd, Pb and O isotopes and trace elements in primitive mafic dykes from the Etendeka flood basalts, NW Namibia the author along with her co-workers have shown that deep, less degassed mantle material carried up by a mantle plume contributed significantly to the flood basalt magmatism. The Etendeka flood basalts are part of the South Atlantic LIP, which is associated with the breakup of Gondwana, the formation of the Paraná-Etendeka flood basalts and the Walvis Ridge - Tristan da Cunha hotspot track. Thus reinforcing the lately often-challenged concept of mantle plumes and the role of mantle plumes in the formation of large igneous provinces. Studying the behaviour of noble gases during melt formation and evolution the author along with her co-workers has shown that He can be considerable more susceptible to changes during melt formation and evolution resulting not only in a complete decoupling of He isotopes from e.g. Ne or Pb isotopes but also in a complete loss of the primary mantle isotope signal. They have also shown that this decoupling occurs mainly during the melt formation processes requiring He to be more compatible during mantle melting than Ne. In addition, the author along with her co workers were able to show that incorporation of atmospheric noble gases into igneous rocks is in general a two-step process: (1) magma contamination by assimilation of altered oceanic crust results in the entrainment of air-equilibrated seawater noble gases; (2) atmospheric noble gases are adsorbed onto grain surfaces during sample preparation. This implies, considering the ubiquitous presence of the contamination signal, that magma contamination by assimilation of a seawater-sourced component is an integral part of mid-ocean ridge basalt evolution.
KW  - noble gases
KW  - mantle formation
KW  - mantle evolution
KW  - ocean-crust formation
KW  - plume-ridge interaction
KW  - contamination processes
KW  - magmatic processes
KW  - continental break-up
Y1  - 2019
ER  - 
TY  - THES
A1  - Schwanghart, Wolfgang
T1  - Digital elevation model analysis in geomorphology and natural hazards research
BT  - from algorithms to applications
Y1  - 2022
ER  - 
TY  - THES
A1  - Schleicher, Anja Maria
T1  - The significance of clay minerals in active fault zones
N2  - Die vorliegende Habilitationsschrift umfasst Forschungsergebnisse aus Studien, die sich mit Fluid-Gesteins-Wechselwirkungen und Deformationsprozessen in aktiven Störungszonen befassen, wobei der Einfluss der Tonminerale auf das geochemische und hydromechanische Verhalten dieser Störungen im Vordergrund steht. Kernproben (core) und Bohrklein (cuttings) aus vier verschiedenen Bohrprojekten an der San Andreas Störung (USA), der Nankai Trough Subduktionszone und der Japan Trench Subduktionszone (Japan), sowie der Alpine Störung in Neuseeland wurden untersucht. Die von ICDP (International Continental Scientific Drilling Program) und IODP (International Ocean Discovery Program) unterstützten Projekte verfolgen alle das Ziel, das Verhalten von Erdbeben besser zu verstehen.
In Kapitel 1 werden in einer kurzen Einleitung die allgemeinen thematischen Grundlagen und Ziele der Arbeit beschrieben. Kapitel 2 umfasst den Stand der Forschung, eine kurze Beschreibung der einzelnen Bohrprojekte und Standorte, sowie eine Zusammenfassung der wichtigsten Messmethoden. Kapitel 3 beinhaltet insgesamt zehn wissenschaftliche Arbeiten, die alle in einem methodisch-thematischen Zusammenhang stehen. Die Manuskripte wurden in den Jahren 2006-2015 veröffentlicht, wobei weitere Arbeiten aus diesem Themenbereich im Literaturverzeichnis vermerkt sind. Sie gehen auf unterschiedliche Fragestellungen um die Bildung und das Verhalten von Tonmineralen in aktiven Störungszonen ein. Insgesamt sechs Publikationen beinhalten Daten und Forschungsergebnisse, die im Rahmen des SAFOD Projektes, USA (San Andreas Fault Observatory at Depth) erstellt wurden. Hier wurde vor allem auf die Fluid-Gesteins-Wechselwirkungsprozesse im Störungsgestein und die daraus resultierende Bildung von Tonmineralen eingegangen. Drei weitere Arbeiten wurden im Rahmen des NanTroSEIZE Projektes, Japan (Nankai Trough Seismogenic Zone Experiment) und des JFAST Projektes, Japan (Japan Trench Fast Drilling Project) erstellt. Hier steht vor allem das Verhalten von quellfähigen Tonmineralen auf sich ändernde Umgebungsbedingungen (z.B. Temperatur und Feuchtigkeit) im Mittelpunkt. Die zehnte hier vorgestellte Veröffentlichung betrifft Analysen rund um das DFDP Projekt (Deep Fault Drilling Project) in Neuseeland, wobei hier die Deformation von Tonmineralen und das hydro-mechanische Verhalten der Störungszone im Vordergrund stehen. In neun Veröffentlichungen war ich als Erstautor für die Vorbereitung des Projektes, das Erstellen der Daten und die Fertigstellung der Manuskripte zuständig. In einer Publikation war ich als Mitautorin für die elektronenmikroskopischen Analysen und deren Interpretation verantwortlich. 
Die wichtigsten Ergebnisse der in Kapitel 3 vorgelegten Arbeiten werden in Kapitel 4 unter Berücksichtigung neuer Publikationen diskutiert. Nach der Beschreibung der Thesen in Kapitel 5 werden in Kapitel 6 „Outlook“ die Highlights zukünftiger Forschungspläne am GFZ näher beschrieben. Die Habilitationsschrift endet mit dem Anhang, in welchem unter anderem das Laborequipment genauer beschrieben wird, sowie die Publikationen, Konferenzbeiträge und Lehrbeiträge aufgelistet sind.
N2  - The habilitation thesis presented here includes results from several studies dealing with fluid-rock interactions and rock deformation processes in active fault zones. The focus in all of these studies is on the influence of clay minerals on the geochemical and the hydro-mechanical behavior of the fault rocks. The research was conducted on rock cores and cuttings from four scientific drilling projects at the San Andreas Fault (USA), the Nankai Trough subduction zone and the Japan Trench subduction zone (Japan), as well as the Alpine Fault in New Zealand. These ICDP (International Continental Scientific Drilling Program) and IODP (International Ocean Discovery Program) funded projects were all conducted with the aim to monitor and better understand earthquakes. 
Chapter 1 contains a short introduction to the topic with basic principles and objectives regarding the research approach. Chapter 2 describes the state of the art in clay mineral and fault zone science, gives a short description of the individual drilling projects and their locations on which the research was based, and summarizes the most important analytical methods used. Chapter 3 comprises ten peer-reviewed publications that are connected thematically and methodologically. The papers were published in the years 2006-2015, and additional related publications including myself as co-author are given in the literature list. The ten publications address different questions concerning the formation of clay minerals and processes of fluid-rock interaction in active fault zones. Six papers contain results from the SAFOD drilling project, USA (San Andreas Fault Observatory at Depth), with the main focus on fluid-rock interaction processes in fault rocks and the formation and location of clay minerals. Three publications report on research from the NanTroSEIZE drilling project (Nankai Trough Seismogenic Zone Experiment) and the JFAST drilling project (Japan Trench Fast Drilling Project). Both projects are situated in Japan. Here, the swelling behavior of smectite clay minerals in relation to changing environmental conditions (e.g. temperature and/or humidity) was investigated. The last publication included here concerns a study from the DFDP project (Deep Fault Drilling Project) in New Zealand, where I investigated the deformation of clay minerals on the context of the hydro-mechanical behavior of the fault zone rocks. I was first author in nine of the publications and in charge of the project preparation, measurements and data analyses, and the completion of the manuscript. As co-author on the other publication I was responsible for electronmicroscopy analyses (SEM and TEM) and their interpretation. 
The key results from the publications in Chapter 3 are discussed in Chapter 4 with additional considerations from more recent papers. Following the major theses in Chapter 5, Chapter 6 highlights a future research project in clay mineralogy research at the GFZ. An appendix includes more detailed descriptions of the laboratory equipment and lists of all publications, conference contributions and teaching courses and modules.
KW  - fault zone
KW  - Störungszone
KW  - clay mineral
KW  - fluid-rock interaction
KW  - Tonminerale
KW  - Fluid-Gesteins Wechselwirkung
Y1  - 2019
ER  - 
TY  - THES
A1  - Scheffler, Christiane
T1  - Studies on plasticity within the universal pattern of growth and developmet of children and adolescents
N2  - The anatomically modern human Homo sapiens sapiens is distinguished by a high adaptability in physiology, physique and behaviour in short term changing environmental conditions. Since our environmental factors are constantly changing because of anthropogenic influences, the question arises as to how far we have an impact on the human phenotype in the very sensitive growth phase in children and adolescents. Growth and development of all children and adolescents follow a universal and typical pattern. This pattern has evolved as the result of trade-offs in the 6-7 million years of human evolution. This typically human growth pattern differs from that of other long-living social primate species. It can be divided into different biological age stages, with specific biological, cognitive and socio-cultural signs. Phenotypic plasticity is the ability of an organism to react to an internal or external environmental input with a change in the form, state, and movement rate of activity (West-Eberhard 2003). The plasticity becomes visible and measurable particularly when, in addition to the normal variability of the phenotypic characteristics within a population, the manifestation of this plasticity changes within a relatively short time. The focus of the present work is the comparison of age-specific dimensional changes. The basic of the presented studies are more than 75,000 anthropometric data-sets of children and adolescence from 1980 up today and historical data of height available in scientific literature. Due to reduced daily physical activity, today's 6-18 year-olds have lower values of pelvic and elbow breadths. The observed increase in body height can be explained by hierarchies in social networks of human societies, contrary to earlier explanations (influence of nutrition, good living conditions and genetics). A shift towards a more feminine fat distribution pattern in boys and girls is parallel to the increase in chemicals in our environment that can affect the hormone system. Changing environmental conditions can have selective effects over generations so that that genotype becomes increasingly prevalent whose individuals have a higher progeny rate than other individuals in this population. Those then form the phenotype which allows optimum adaptation to the changes of the environmental conditions. Due to the slow patterns of succession and the low progeny rate (Hawkes et al. 1998), fast visible in the phenotype due to changes in the genotype of a population are unlikely to occur in the case of Homo sapiens sapiens within short time. In the data sets on which the presented investigations are based, such changes appear virtually impossible. The study periods cover 5-30 to max.100 years (based on data from the body height from historical data sets).
N2  - Der anatomisch moderne Mensch Homo sapiens sapiens zeichnet sich durch eine hohe Anpassungsfähigkeit von Physiologie, Körperbau und Verhalten an sich kurzfristig ändernde Umweltbedingungen aus. Daraus ergibt sich die Frage inwieweit anthropogene Umweltbedingungen die sehr sensible Wachstumsphase von Kindern und Jugendlichen beeinflussen können. Das universelle und für den Menschen typische Wachstums- und Entwicklungsmuster mit unterschiedlichen biologisch, kognitiv und soziokulturell abgrenzbaren Entwicklungsstadien, welches sich in 6-7 Millionen Jahren menschlicher Evolution herausgebildet hat, unterscheidet sich von dem anderer langlebender sozialer Primaten. Phänotypische Plastizität ist die Fähigkeit eines Organismus sich in Form, Zustand, Aktivitätsrate oder Verhalten an unterschiedliche Umweltbedingungen anzupassen (West-Eberhard 2003). Beim Menschen wird diese Plastizität u.a. sichtbar, wenn sich anthropometrisch bestimmbare Merkmale im Vergleich von Populationen in relativ kurzer Zeit ändern. Der Schwerpunkt der vorliegenden Arbeit ist es, altersspezifische Änderung von Körpermaßen (Skelettbreiten, Körperendhöhe und Fettverteilungsmuster) aufeinanderfolgender Populationen in Abhängigkeit von neuen Umweltparametern zu vergleichen. Dem liegen ca. 75 000 anthropo-metrische Datensätzen von Kindern und Jugendlichen seit 1980 bis heute und historische Datensätze aus der Literatur zugrunde. Aufgrund verringerter alltäglicher Bewegung haben heutige 6-18-Jährige geringere Werte der Becken- und der Ellenbogenbreiten. Die beobachtete Zunahme der Körperhöhe lässt sich entgegen früherer Erklärungen (Einfluss von Ernährung, guter Lebensbedingungen und Genetik) durch Hierarchien in sozialen Netzwerken menschlicher Gesellschaften erklären. Eine Verschiebung zu einem eher weiblichen Fettverteilungsmuster bei Jungen und Mädchen findet sich parallel zur Zunahme von Chemikalien in unserer Umwelt, die das Hormonsystem beeinflussen können. Die beschriebene Plastizität des Phänotyps findet im Rahmen des genetisch manifestierten Wachstumsmusters bei Kindern und Jugendlichen statt. Epigenetische Einflüsse können nicht ausgeschlossen werden, sind aber an Körpermaßdaten per se nicht bestimmbar. Die Veränderung der analysierten Körpermaße unterstreicht, dass der Phänotyp des Menschen sich an veränderte Umweltbedingungen sehr plastisch anpassen kann. Wegen der langsamen Generationenfolge und Entwicklung des Menschen sind derartige eigentlich kurzfristige Veränderungen nur über einen Zeitraum von mindestens 5-30 Jahren zu beobachten.
KW  - plasticity
KW  - skeletal breadth measurement
KW  - Fat Patterning
KW  - secular trend
KW  - body height
Y1  - 2018
ER  - 
TY  - THES
A1  - Schaefer, Laura
T1  - Oszillation und Adaptation als Mechanismen neuromuskulärer Steuer- und Regelprozesse
Y1  - 2021
ER  - 
TY  - THES
A1  - Savatieiev, Oleksandr
T1  - Carbon nitride semiconductors: properties and application as photocatalysts in organic synthesis
N2  - 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.
N2  - Graphitische Kohlenstoffnitride (g-CNs) werden durch g-CN vom Melonen-Typ, Poly(heptazinimide) (PHIs), g-CN auf Triazinbasis und Poly(triazinimid) mit interkaliertem LiCl (PTI/Li+Cl-) repräsentiert. Diese Materialien bestehen aus sp2-hybridisierten Kohlenstoff- und Stickstoffatomen; das C:N-Verhältnis liegt nahe bei 3:4; das Grundgerüst ist 1,3,5-Triazin oder Tri-s-Triazin; die Grundgerüste sind kovalent über sp2-hybridisierte Stickstoffatome oder NH-Moleküle miteinander verbunden; die Schichten werden über schwache van-der-Waals-Kräfte wie in Graphit zu einem Stapel zusammengefügt. Aufgrund der mittleren Bandlücke (~2,7 eV) werden g-CNs, wie z. B. g-CN vom Melonen-Typ und PHIs, durch Photonen mit einer Wellenlänge ≤ 460 nm angeregt. Seit 2009 werden g-CNs aktiv als Photokatalysatoren für die Entwicklung von Wasserstoff und Sauerstoff - zwei Halbreaktionen der vollständigen Wasserspaltung - untersucht, indem entsprechende Opferstoffe eingesetzt werden. Gleichzeitig ist die Anwendung von g-CNs als Photokatalysatoren in der organischen Synthese auf wenige Reaktionen beschränkt geblieben. Die kumulative Habilitation fasst die Forschungsarbeiten zusammen, die von der Gruppe "Innovative heterogene Photokatalyse" zwischen 2017 und 2023 auf dem Gebiet der organischen Photokatalyse mit Kohlenstoffnitrid durchgeführt wurden, die von Dr. Oleksandr Savatieiev geleitet wird.
g-CN-Photokatalysatoren aktivieren Moleküle, d. h. sie erzeugen ihre reaktiveren Zwischenprodukte mit offener Schale über drei Modi: i) photoinduzierter Elektronentransfer (PET); ii) protonengekoppelter Elektronentransfer im angeregten Zustand (ES-PCET) oder direkter Wasserstoffatomtransfer (dHAT); iii) Energietransfer (EnT). Der Bereich der Reaktionen, die über oxidativen PET ablaufen, d. h. die Ein-Elektronen-Oxidation eines Substrats zum entsprechenden Radikalkation, wird durch die Synthese von Sulfonylchloriden aus S-Acetylthiophenolen dargestellt. Der Bereich der Reaktionen, die über reduktive PET ablaufen, d. h. Reduktion eines Substrats mit einem Elektron zum entsprechenden radikalischen Anion, wird durch die Synthese von γ,γ-Dichloroketonen aus Enonen und Chloroform repräsentiert.
Aufgrund der zahlreichen sp2-hybridisierten Stickstoffatome in der Struktur der g-CN-Materialien können sie X-H-Bindungen in organischen Molekülen spalten und temporäre Wasserstoffatome speichern. Der ES-PCET- oder dHAT-Modus der Aktivierung organischer Moleküle zu den entsprechenden Radikalen wird bei Substraten mit relativ sauren X-H-Bindungen und solchen, die sich durch eine niedrige Bindungsdissoziationsenergie auszeichnen, wie z. B. die C-H-Bindung neben den Heteroelementen, durchgeführt. Andererseits reduziert reduktiv gequenchtes g-CN, das ein Wasserstoffatom trägt, eine Carbonylverbindung über PCET zum Ketylradikal, was im Vergleich zum Elektronentransfer der thermodynamisch günstigere Weg ist. Der Umfang dieser Reaktionen wird durch die Cyclodimerisierung von α,β-ungesättigten Ketonen zu Cyclopentanolen dargestellt.
Der angeregte Zustand von g-CN zeigt eine komplexe Dynamik mit der anfänglichen Bildung eines angeregten Singulett-Zustands, der beim Übergang zwischen den Systemen einen angeregten Triplett-Zustand erzeugt, der durch eine Lebensdauer von > 2 μs gekennzeichnet ist. Aufgrund der langen Lebensdauer aktivieren g-CN organische Moleküle über EnT. So sensibilisiert g-CN beispielsweise Singulett-Sauerstoff, der das wichtigste Zwischenprodukt bei der Dehydrierung von Aldoximen zu Nitriloxiden ist. Das transiente Nitriloxid unterliegt einer [3+2]-Cycloaddition zu Nitrilen und ergibt Oxadiazole-1,2,4.
PET, ES-PCET und EnT sind grundlegende Phänomene, die über die organische Photokatalyse hinaus Anwendung finden. Hybridkomposit wird durch die Kombination von leitfähigen Polymeren wie Poly(3,4-ethylendioxythiophen)polystyrolsulfonat (PEDOT:PSS) mit Kaliumpoly(heptazinimid) (K-PHI) gebildet. Nach PET modulierte K-PHI die Population der Polaronen und damit die Leitfähigkeit von PEDOT:PSS. Der Ausgangszustand von PEDOT:PSS wird wiederhergestellt, wenn das Material O2 ausgesetzt wird. K-PHI:PEDOT:PSS kann für die O2-Sensorik verwendet werden.
In Gegenwart von Elektronendonatoren, wie tertiären Aminen und Alkoholen, und bei Lichteinstrahlung wird K-PHI photogeladen - das g-CN-Material sammelt Elektronen und ladungsausgleichende Kationen an. Dieser photogeladene Zustand ist unter anaeroben Bedingungen wochenlang stabil, gleichzeitig ist er aber ein starkes Reduktionsmittel. Diese Eigenschaft ermöglicht die zeitliche Entkopplung von Lichtsammlung und Energiespeicherung in Form von Elektron-Protonen-Paaren von der Nutzung in der organischen Synthese. Der photogeladene Zustand von K-PHI reduziert Nitrobenzol zu Anilin und ermöglicht die Dimerisierung von α,β-ungesättigten Ketonen zu Hexadienonen im Dunkeln.
KW  - carbon nitride
KW  - photocatalysis
KW  - photochemistry
KW  - photocharging
KW  - organic synthesis
Y1  - 2023
ER  -