TY - THES A1 - Schneider, Helen T1 - Reactive eutectic media based on ammonium formate for the valorization of bio-sourced materials T1 - Reaktive eutektische Medien auf Basis von Ammoniumformiat zur Aufwertung von biobasierten Substanzen N2 - In the last several decades eutectic mixtures of different compositions were successfully used as solvents for vast amount of chemical processes, and only relatively recently they were discovered to be widely spread in nature. As such they are discussed as a third liquid media of the living cell, that is composed of common cell metabolites. Such media may also incorporate water as a eutectic component in order to regulate properties such as enzyme activity or viscosity. Taking inspiration form such sophisticated use of eutectic mixtures, this thesis will explore the use of reactive eutectic media (REM) for organic synthesis. Such unconventional media are characterized by the reactivity of their components, which means that mixture may assume the role of the solvent as well as the reactant itself. The thesis focuses on novel REM based on ammonium formate and investigates their potential for the valorization of bio-sourced materials. The use of REM allows the performance of a number of solvent-free reactions, which entails the benefits of a superior atom and energy economy, higher yields and faster rates compared to reactions in solution. This is evident for the Maillard reaction between ammonium formate and various monosaccharides for the synthesis of substituted pyrazines as well as for a Leuckart type reaction between ammonium formate and levulinic acid for the synthesis of 5-methyl-2-pyrrolidone. Furthermore, reaction of ammonium formate with citric acid for the synthesis of yet undiscovered fluorophores, shows that synthesis in REM can open up unexpected reaction pathways. Another focus of the thesis is the study of water as a third component in the REM. As a result, the concept of two different dilution regimes (tertiary REM and in REM in solvent) appears useful for understanding the influence of water. It is shown that small amounts of water can be of great benefit for the reaction, by reducing viscosity and at the same time increasing reaction yields. REM based on ammonium formate and organic acids are employed for lignocellulosic biomass treatment. The thesis thereby introduces an alternative approach towards lignocellulosic biomass fractionation that promises a considerable process intensification by the simultaneous generation of cellulose and lignin as well as the production of value-added chemicals from REM components. The thesis investigates the generated cellulose and the pathway to nanocellulose generation and also includes the structural analysis of extracted lignin. Finally, the thesis investigates the potential of microwave heating to run chemical reactions in REM and describes the synergy between these two approaches. Microwave heating for chemical reactions and the use of eutectic mixtures as alternative reaction media are two research fields that are often described in the scope of green chemistry. The thesis will therefore also contain a closer inspection of this terminology and its greater goal of sustainability. N2 - Ein eutektisches System beschreibt eine homogene Mischung verschiedener Substanzen, welche bei einer einzigen Temperatur schmilzt und dabei einen Schmelzpunkt aufweist der unterhalb der Schmelzpunkte der einzelnen Komponenten liegt. Solche Gemische können aus simplen organischen Substanzen gebildet werden und haben deshalb in den letzten Jahrzehnten große Aufmerksamkeit als neuartige Lösungsmittel erhalten. Mittlerweile wird ihr Nutzung für eine Vielzahl chemischer Prozesse erforscht. Zudem wurde Entdeckt das solche Gemische auch in der Natur Verbreitung finden. In diesem Zuge werden sie z.B. als drittes flüssiges Medium der lebenden Zelle diskutiert, welches durch eutektische Gemische von gewöhnlichen Zellmetaboliten gebildet wird. Sie können dabei auch Wasser als eutektische Komponente enthalten, um Eigenschaften wie Enzymaktivität oder Viskosität zu regulieren. Inspiriert durch diesen raffinierten Einsatz eutektischer Gemische untersucht diese Arbeit die Verwendung reaktiver eutektischer Medien (REM) für die chemische Anwendung. Solche unkonventionellen Medien zeichnen sich durch die Reaktivität ihrer Komponenten aus, was bedeutet, dass das Gemisch sowohl die Rolle des Lösungsmittels als auch des Reaktanten selbst übernehmen kann. Die Arbeit konzentriert sich auf neuartige REM auf Basis von Ammoniumformiat und untersucht deren Potenzial für die Nutzung von bio-basierten Substanzen. Die Verwendung von REM ermöglicht die Durchführung einer Reihe lösungsmittelfreier Reaktionen, was im Vergleich zu Reaktionen in Lösung die Vorteile einer besseren Atomökonomie, höhere Ausbeuten und schnellere Reaktionsgeschwindigkeiten mit sich bringt. Dies zeigt sich an der Maillard-Reaktion zwischen Ammoniumformiat und verschiedenen Monosacchariden zur Synthese substituierter Pyrazine sowie an der Leuckart-Reaktion zwischen Ammoniumformiat und Lävulinsäure zur Synthese von 5-Methyl-2-pyrrolidon. Darüber hinaus zeigt die Reaktion von Ammoniumformiat mit Zitronensäure zur Synthese noch unentdeckter Fluorophore, dass die Synthese in REM bisher unerschlossene Reaktionswege eröffnen kann. Ein weiterer Schwerpunkt der Arbeit ist die Untersuchung von Wasser als dritte Komponente im REM. Daher erscheint das Konzept zweier unterschiedlicher Verdünnungsregime (tertiäres REM und REM im Lösungsmittel) nützlich für das Verständnis des Einflusses von Wasser. Es zeigt sich, dass kleine Mengen Wasser von großem Nutzen für die Reaktion sein können, indem sie die Viskosität senken und gleichzeitig die Reaktionsausbeuten erhöhen. Für den Aufschluss von Lignocellulose werden REM auf Basis von Ammoniumformiat und organischen Säuren eingesetzt. Die Arbeit stellt damit einen neuen Ansatz für das Konzept der Bioraffinerie vor, der eine erhebliche Prozessintensivierung durch die gleichzeitige Erzeugung von Cellulose, Lignin sowie die Herstellung von Chemikalien aus REM-Komponenten verspricht. Die Arbeit untersucht die erzeugte Cellulose, sowie die Bedingungen zur Erzeugung von Nanocellulose und umfasst die Strukturanalyse von extrahiertem Lignin. Abschließend untersucht die Arbeit das Potenzial der Mikrowellenenergie zum Erhitzen chemischer Reaktionen in REM und beschreibt die Synergie zwischen diesen beiden Ansätzen. Mikrowellentechnologie für chemische Reaktionen und die Verwendung eutektischer Gemische als alternative Reaktionsmedien sind zwei Forschungsfelder, die häufig im Rahmen der Grünen Chemie beschrieben werden. Die Arbeit beinhaltet daher auch eine genauere Betrachtung dieser Terminologie und ihres übergeordneten Ziels der Nachhaltigkeit. KW - solvent-free reactions KW - deep eutectic solvents KW - microwave synthesis KW - green chemistry KW - biorefinery KW - deoxyfructosazine KW - citrazinic acid KW - Bioraffinerie KW - Citrazinsäure KW - stark eutektisches Lösungsmittel KW - Deoxyfructosazin KW - Grüne Chemie KW - Mikrowellensynthese KW - lösungsmittelfreie Synthese Y1 - 2023 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-613024 ER - TY - THES A1 - Herrero Alonso, Yohana T1 - Properties of high-redshift galaxies in different environments T1 - Eigenschaften von Galaxien mit hoher Rotverschiebung in verschiedenen Umgebungen N2 - The Lyman-𝛼 (Ly𝛼) line commonly assists in the detection of high-redshift galaxies, the so-called Lyman-alpha emitters (LAEs). LAEs are useful tools to study the baryonic matter distribution of the high-redshift universe. Exploring their spatial distribution not only reveals the large-scale structure of the universe at early epochs, but it also provides an insight into the early formation and evolution of the galaxies we observe today. Because dark matter halos (DMHs) serve as sites of galaxy formation, the LAE distribution also traces that of the underlying dark matter. However, the details of this relation and their co-evolution over time remain unclear. Moreover, theoretical studies predict that the spatial distribution of LAEs also impacts their own circumgalactic medium (CGM) by influencing their extended Ly𝛼 gaseous halos (LAHs), whose origin is still under investigation. In this thesis, I make several contributions to improve the knowledge on these fields using samples of LAEs observed with the Multi Unit Spectroscopic Explorer (MUSE) at redshifts of 3 < 𝑧 < 6. N2 - Die Lyman-𝛼 (Ly𝛼)-Linie erleichtert die Detektion von Galaxien bei hoher Rotverschiebung, sogenannten den Lyman-Alpha-Emittern (LAEs). Die Erforschung ihrer Verteilung enthüllt nicht nur die großräumige Struktur des Universums in frühen Epochen, sondern bietet auch einen Einblick in die Entstehung und Entwicklung der Galaxien, die wir heute beobachten. Da Halos aus Dunkler Materie (DMHs) als Orte der Galaxienentstehung dienen, spiegelt die LAE-Verteilung auch die der zugrunde liegenden Dunklen Materie wider. Darüber hinaus sagen theoretische Studien voraus, dass die Verteilung von LAEs auch Auswirkungen auf ihr eigenes zirkumgalaktisches Medium (CGM) hat, indem sie ihre ausgedehnten gasförmigen Ly𝛼-Halos (LAHs) beeinflusst. In dieser Dissertation leiste ich mehrere Beiträge zur Verbesserung des Wissens über diese Felder anhand von Stichproben von LAEs, die mit dem Multi Unit Spectroscopic Explorer (MUSE) bei Rotverschiebungen von 3 < 𝑧 < 6 beobachtet wurden. KW - high-redshift KW - Lyman-alpha emitters KW - clustering KW - large-scale structure KW - Lyman-Alpha-Emitter KW - Clustering KW - hoher Rotverschiebung KW - großräumige Struktur des Universums Y1 - 2023 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-613288 ER - TY - JOUR A1 - Stone, Kate A1 - Nicenboim, Bruno A1 - Vasishth, Shravan A1 - Rösler, Frank T1 - Understanding the effects of constraint and predictability in ERP JF - Neurobiology of language N2 - Intuitively, strongly constraining contexts should lead to stronger probabilistic representations of sentences in memory. Encountering unexpected words could therefore be expected to trigger costlier shifts in these representations than expected words. However, psycholinguistic measures commonly used to study probabilistic processing, such as the N400 event-related potential (ERP) component, are sensitive to word predictability but not to contextual constraint. Some research suggests that constraint-related processing cost may be measurable via an ERP positivity following the N400, known as the anterior post-N400 positivity (PNP). The PNP is argued to reflect update of a sentence representation and to be distinct from the posterior P600, which reflects conflict detection and reanalysis. However, constraint-related PNP findings are inconsistent. We sought to conceptually replicate Federmeier et al. (2007) and Kuperberg et al. (2020), who observed that the PNP, but not the N400 or the P600, was affected by constraint at unexpected but plausible words. Using a pre-registered design and statistical approach maximising power, we demonstrated a dissociated effect of predictability and constraint: strong evidence for predictability but not constraint in the N400 window, and strong evidence for constraint but not predictability in the later window. However, the constraint effect was consistent with a P600 and not a PNP, suggesting increased conflict between a strong representation and unexpected input rather than greater update of the representation. We conclude that either a simple strong/weak constraint design is not always sufficient to elicit the PNP, or that previous PNP constraint findings could be an artifact of smaller sample size. KW - N400 KW - anterior PNP KW - posterior P600 KW - probabilistic processing KW - constraint KW - predictability KW - entropy Y1 - 2022 U6 - https://doi.org/10.1162/nol_a_00094 SN - 2641-4368 VL - 4 IS - 2 SP - 221 EP - 256 PB - MIT Press CY - Cambridge, MA, USA ER - TY - JOUR A1 - Quarmby, Andrew James A1 - Mönnig, Jamal A1 - Mugele, Hendrik A1 - Henschke, Jakob A1 - Kim, MyoungHwee A1 - Cassel, Michael A1 - Engel, Tilman T1 - Biomechanics and lower limb function are altered in athletes and runners with achilles tendinopathy compared with healthy controls: A systematic review JF - Frontiers in Sports and Active Living N2 - Achilles tendinopathy (AT) is a debilitating injury in athletes, especially for those engaged in repetitive stretch-shortening cycle activities. Clinical risk factors are numerous, but it has been suggested that altered biomechanics might be associated with AT. No systematic review has been conducted investigating these biomechanical alterations in specifically athletic populations. Therefore, the aim of this systematic review was to compare the lower-limb biomechanics of athletes with AT to athletically matched asymptomatic controls. Databases were searched for relevant studies investigating biomechanics during gait activities and other motor tasks such as hopping, isolated strength tasks, and reflex responses. Inclusion criteria for studies were an AT diagnosis in at least one group, cross-sectional or prospective data, at least one outcome comparing biomechanical data between an AT and healthy group, and athletic populations. Studies were excluded if patients had Achilles tendon rupture/surgery, participants reported injuries other than AT, and when only within-subject data was available.. Effect sizes (Cohen's d) with 95% confidence intervals were calculated for relevant outcomes. The initial search yielded 4,442 studies. After screening, twenty studies (775 total participants) were synthesised, reporting on a wide range of biomechanical outcomes. Females were under-represented and patients in the AT group were three years older on average. Biomechanical alterations were identified in some studies during running, hopping, jumping, strength tasks and reflex activity. Equally, several biomechanical variables studied were not associated with AT in included studies, indicating a conflicting picture. Kinematics in AT patients appeared to be altered in the lower limb, potentially indicating a pattern of “medial collapse”. Muscular activity of the calf and hips was different between groups, whereby AT patients exhibited greater calf electromyographic amplitudes despite lower plantar flexor strength. Overall, dynamic maximal strength of the plantar flexors, and isometric strength of the hips might be reduced in the AT group. This systematic review reports on several biomechanical alterations in athletes with AT. With further research, these factors could potentially form treatment targets for clinicians, although clinical approaches should take other contributing health factors into account. The studies included were of low quality, and currently no solid conclusions can be drawn. KW - achilles tendinopathy KW - biomechanics KW - neuromuscular KW - kinetics KW - electromyography KW - athletes KW - runners KW - kinematics Y1 - 2023 U6 - https://doi.org/10.3389/fspor.2022.1012471 SN - 2624-9367 PB - Frontiers CY - Lausanne, Schweiz ER - TY - JOUR A1 - Heissel, Andreas A1 - Pietrek, Anou F. A1 - Kangas, Maria A1 - Van der Kaap-Deeder, Jolene A1 - Rapp, Michael A. T1 - The Mediating Role of Rumination in the Relation between Basic Psychological Need Frustration and Depressive Symptoms JF - Journal of Clinical Medicine N2 - Research within the framework of Basic Psychological Need Theory (BPNT) finds strong associations between basic need frustration and depressive symptoms. This study examined the role of rumination as an underlying mechanism in the association between basic psychological need frustration and depressive symptoms. A cross-sectional sample of N = 221 adults (55.2% female, mean age = 27.95, range = 18–62, SD = 10.51) completed measures assessing their level of basic psychological need frustration, rumination, and depressive symptoms. Correlational analyses and multiple mediation models were conducted. Brooding partially mediated the relation between need frustration and depressive symptoms. BPNT and Response Styles Theory are compatible and can further advance knowledge about depression vulnerabilities. KW - psychopathology KW - elf-determination theory KW - response styles theory KW - frustration KW - depressive disorder KW - emotional regulation KW - rumination Y1 - 2023 U6 - https://doi.org/10.3390/jcm12020395 SN - 2077-0383 VL - 12 SP - 1 EP - 10 PB - MDPI CY - Basel, Schweiz ET - 2 ER -