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Herein, the particle size distributions (PSDs) and shape analysis of in vivo bioproduced particles from aqueous Au3+ and Eu3+ solutions by the cyanobacterium Anabaena sp. are examined in detail at the nanoscale. Generally, biosynthesis is affected by numerous parameters. Therefore, it is challenging to find the key set points for generating tailored nanoparticles (NPs). PSDs and shape analysis of the Au and Eu-NPs were performed with ImageJ using high-resolution transmission electron microscopy (HR-TEM) images. As the HR-TEM image analysis reflects only a fraction of the detected NPs within the cells, additional PSDs of the complete cell were performed to determine the NP count and to evaluate the different accuracies. Furthermore, local PSDs were carried out at five randomly selected locations within a single cell to identify local hotspots or agglomerations. The PSDs show that particle size depends mainly on contact time, while the particle shape is hardly affected. The particles formed are distributed quite evenly within the cells. HR-PSDs for Au-NPs show an average equivalent circular diameter (ECD) of 8.4 nm (24 h) and 7.2 nm (51 h). In contrast, Eu-NPs preferably exhibit an average ECD of 10.6 nm (10 h) and 12.3 nm (244 h). Au-NPs are classified predominantly as “very round” with an average reciprocal aspect ratio (RAR) of ~0.9 and a Feret major axis ratio (FMR) of ~1.17. Eu-NPs mainly belong to the “rounded” class with a smaller RAR of ~0.6 and a FMR of ~1.3. These results show that an increase in contact time is not accompanied by an average particle growth for Au-NPs, but by a doubling of the particle number. Anabaena sp. is capable of biosorbing and bioreducing dissolved Au3+ and Eu3+ ions from aqueous solutions, generating nano-sized Au and Eu particles, respectively. Therefore, it is a low-cost, non-toxic and effective candidate for a rapid recovery of these sought-after metals via the bioproduction of NPs with defined sizes and shapes, providing a high potential for scale-up.
This thesis explores and examines the effectiveness and efficacy of traditional machine learning (ML), advanced neural networks (NN) and state-of-the-art deep learning (DL) models for identifying mental distress indicators from the social media discourses based on Reddit and Twitter as they are immensely used by teenagers. Different NLP vectorization techniques like TF-IDF, Word2Vec, GloVe, and BERT embeddings are employed with ML models such as Decision Tree (DT), Random Forest (RF), Logistic Regression (LR) and Support Vector Machine (SVM) followed by NN models such as Convolutional Neural Network (CNN), Recurrent Neural Network (RNN) and Long Short-Term Memory (LSTM) to methodically analyse their impact as feature representation of models. DL models such as BERT, DistilBERT, MentalRoBERTa and MentalBERT are end-to-end fine tuned for classification task. This thesis also compares different text preprocessing techniques such as tokenization, stopword removal and lemmatization to assess their impact on model performance. Systematic experiments with different configuration of vectorization and preprocessing techniques in accordance with different model types and categories have been implemented to find the most effective configurations and to gauge the strengths, limitations, and capability to detect and interpret the mental distress indicators from the text. The results analysis reveals that MentalBERT DL model significantly outperformed all other model types and categories due to its specific pretraining on mental data as well as rigorous end-to-end fine tuning gave it an edge for detecting nuanced linguistic mental distress indicators from the complex contextual textual corpus. This insights from the results acknowledges the ML and NLP technologies high potential for developing complex AI systems for its intervention in the domain of mental health analysis. This thesis lays the foundation and directs the future work demonstrating the need for collaborative approach of different domain experts as well as to explore next generational large language models to develop robust and clinically approved mental health AI systems.
Coat color and pattern are a distinguished feature in mammalian carnivores, shaped by climatic cycles and habitat type. It can be expressed in various ways, such as gradients, polymorphisms, and rare color variants. Although natural selection explains much of the phenotypic variation found in the wild, genetic drift and heterozygote deficiency, as prominent in small and fragmented populations, may also affect phenotypic variability through the fixation of recessive alleles. The aim of this study was to test whether rare color variants in the wild could relate to a deficiency of heterozygotes, resulting from habitat fragmentation and small population size. We present an overview of all rare color variants in the order Carnivora, and compiled demographic and genetic data of the populations where they did and did not occur, to test for significant correlations. We also tested how phylogeny and body weight influenced the presence of color variants with phylogenetic generalized linear mixed models (PGLMMs). We found 40 color-variable species and 59 rare color variants. In 17 variable phenotypic populations for which genetic diversity was available, the average AR was 4.18, HO = 0.59, and HE= 0.66, and FIS= 0.086. We found that variable populations displayed a significant reduction in heterozygosity and allelic richness compared to non-variable populations across species. We also found a significant negative correlation between population size and inbreeding coefficients. Therefore, it is possible that small effective size had phenotypic consequences on the extant populations. The high frequency of the rare color variants (averaging 20%) also implies that genetic drift is locally overruling natural selection in small effective populations. As such, rare color variants could be added to the list of phenotypic consequences of inbreeding in the wild.
The production of isolated metallic nanoparticles with multifunctionalized properties, such as size and shape, is crucial for biomedical, photocatalytic, and energy storage or remediation applications. This study investigates the initial particle formations of gold nanoparticles (AuNPs) bioproduced in the cyanobacteria Anabaena sp. using high-resolution transmission electron microscopy images for digital image analysis. The developed method enabled the discovery of cerium nanoparticles (CeNPs), which were biosynthesized in the cyanobacteria Calothrix desertica. The particle size distributions for AuNPs and CeNPs were analyzed. After 10 h, the average equivalent circular diameter for AuNPs was 4.8 nm, while for CeNPs, it was approximately 5.2 nm after 25 h. The initial shape of AuNPs was sub-round to round, while the shape of CeNPs was more roundish due to their amorphous structure and formation restricted to heterocysts. The local PSDs indicate that the maturation of AuNPs begins in the middle of vegetative cells and near the cell membrane, compared to the other regions of the cell.
Well-being is essential for all people. Therefore, important factors influencing people’s well-being must be investigated. Well-being is multifaceted and defined as, for example, psychological, emotional, mental, physical, or social well-being. Here, we focus on psychological well-being. The study aimed to analyze different aspects of connectedness as potential predictors of psychological well-being. For this purpose, we conducted a study examining the psychological well-being of 184 participants (130 women, 54 men, age: M = 31.39, SD = 15.24) as well as their connectedness with oneself (self-love), with others (prosocialness), with nature (nature connectedness), and with the transcendent (spirituality). First, significant positive correlations appeared between psychological well-being and self-love, nature connectedness, and spirituality. Furthermore, correlations between the four aspects of connectedness were significant, except for the relationship between self-love and prosocialness. A regression analysis revealed that self-love and nature connectedness positively predicted participants’ psychological well-being, while spirituality and prosocialness did not explain any incremental variance. The strong relationship between self-love and well-being was partly mediated by nature connectedness. Hence, self love, understood as a positive attitude of self-kindness, should be considered in more detail to enhance psychological well-being. Besides this, a more vital connectedness to the surrounding nature could benefit people’s well-being.
The title compound, [Fe(C5H5)(C21H24NO2)], which is produced by the oxidation of 1-(4-tert-butylphenyl)-2-ethyl-3-ferrocenylpyrrole, crystallizes as a racemic mixture in the centrosymmetric space group P21/n. The central heterocyclic pyrrole ring system subtends dihedral angles of 13.7 (2)° with respect to the attached cyclopentadienyl ring and of 43.6 (7)° with the major component of the disordered phenyl group bound to the N atom. The 4-tert-butylphenyl group, as well as the non-substituted Cp ring are disordered with s.o.f. values of 0.589 (16) and 0.411 (16), respectively. In the crystal, molecules with the same absolute configuration are linked into infinite chains along the b-axis direction by O—H···O hydrogen bonds between the hydroxy substituent and the carbonyl O atom of the adjacent molecule.
This work addresses the challenge of calibrating multiple solid-state LIDAR systems. The study focuses on three different solid-state LIDAR sensors that implement different hardware designs, leading to distinct scanning patterns for each system. Consequently, detecting corresponding points between the point clouds generated by these LIDAR systems—as required for calibration—is a complex task. To overcome this challenge, this paper proposes a method that involves several steps. First, the measurement data are preprocessed to enhance its quality. Next, features are extracted from the acquired point clouds using the Fast Point Feature Histogram method, which categorizes important characteristics of the data. Finally, the extrinsic parameters are computed using the Fast Global Registration technique. The best set of parameters for the pipeline and the calibration success are evaluated using the normalized root mean square error. In a static real-world indoor scenario, a minimum root mean square error of 7 cm was achieved. Importantly, the paper demonstrates that the presented approach is suitable for online use, indicating its potential for real-time applications. By effectively calibrating the solid-state LIDAR systems and establishing point correspondences, this research contributes to the advancement of multi-LIDAR fusion and facilitates accurate perception and mapping in various fields such as autonomous driving, robotics, and environmental monitoring.
Focusing on the triangulation of detective fiction, masculinity studies and disability studies, "Investigating the Disabled Detective – Disabled Masculinity and Masculine Disability in Contemporary Detective Fiction" shows that disability challenges common ideals of (hegemonic) masculinity as represented in detective fiction. After a theoretical introduction to the relevant focal points of the three research fields, the dissertation demonstrates that even the archetypal detectives Dupin and Holmes undermine certain nineteenth-century masculine ideals with their peculiarities. Shifting to contemporary detective fiction and adopting a literary disability studies perspective, the dissertation investigates how male detectives with a form of neurodiversity or a physical impairment negotiate their masculine identity in light of their disability in private and professional contexts. It argues that the occupation as a detective supports the disabled investigator to achieve ‘masculine disability’. Inversing the term ‘disabled masculinity’, predominantly used in research, ‘masculine disability’ introduces a decisively gendered reading of neurodiversity and (acquired) physical impairment in contemporary detective fiction. The term implies that the disabled detective (re)negotiates his masculine identity by implementing the disability in his professional investigations and accepting it as an important, yet not defining, characteristic of his (gender) identity. By applying this approach to five novels from contemporary British and American detective fiction, the dissertation demonstrates that masculinity and disability do not negate each other, as commonly assumed. Instead, it emphasises that disability allows the detective, as much as the reader, to rethink masculinity.
X-ray computed tomography (XRT) is a three-dimensional (3D), non-destructive, and reproducible investigation method capable of visualizing and examining internal and external structures of components independent of the material and geometry. In this work, XRT with its unique abilities complements conventionally utilized examination methods for the investigation of microstructure weakening induced by hydrogen corrosion and furthermore provides a new approach to corrosion research. The motivation for this is the current inevitable transformation to hydrogen-based steel production. Refractories of the system Al2O3-SiO2 are significant as lining materials. Two exemplary material types A and B, which differ mainly in their Al2O3:SiO2 ratio, are examined here using XRT. Identical samples of the two materials are measured, analyzed, and then compared before and after hydrogen attack. In this context, hydrogen corrosion-induced porosity and its spatial distribution and morphology are investigated. The results show that sample B has an higher resistance to hydrogen-induced attack than sample A. Furthermore, the 3D-representation revealed a differential porosity increase within the microstructure.
Die aus nachwachsenden Rohstoffen hergestellten biologisch abbaubaren Polymere Polymilchsäure (polylactic acid, PLA) und Polyhydroxybuttersäure (polyhydroxybutyrate, PHB) wurden im Rahmen dieser Arbeit mit hydrierten amorphen Kohlenstoffschichten (amorphous hydrogenated carbon, a-C:H) bei unterschiedlichen Winkeleinstellungen mit verschiedenen Dicken beschichtet. Ähnlich wie herkömmliche Polymere haben Biopolymere oft ungeeignete Oberflächeneigenschaften für industrielle Zwecke, z.B. eine geringe Härte. Für manche Anwendungen ist es daher notwendig und vorteilhaft, die Oberflächeneigenschaften von Biopolymeren unter Beibehaltung der Haupteigenschaften des Trägermaterials zu modifizieren. Eine geeignete Oberflächenmodifikation ist das Aufbringen von dünnen a-C:H Schichten. Ihre Eigenschaften hängen wesentlich vom sp²- und sp³-Hybridisierungsverhältnis der Kohlenstoffatome und dem Gehalt an Wasserstoffatomen ab. Das sp²/sp³-Verhältnis sollte in der vorliegenden Arbeit durch Variation der Beschichtungsgeometrie gesteuert werden. Da Beschichtungen bei 0°, direkt vor der Plasmaquelle, einen höheren Anteil an sp³ und indirekt (180°) beschichtete ein höheren Anteil an sp² aufweisen, wird in dieser Arbeit gezeigt, dass es möglich ist, das sp²/sp³ -Verhältnis zu kontrollieren. Dazu werden die einzelnen Proben in den Winkeln 0, 30, 60, 90, 120, 150 und 180° vor der Plasmaquelle platziert und mit einer Dauer von 2.5, 5.0, 7.5 und 10.0 Minuten beschichtet. Für den Winkeln 0° ergaben sich die Schichtdicken von 25, 50, 75 und 100 nm. Die a-C:H Schichten wurden alle mit Radiofrequenzplasma-unterstützter chemischer Gasphasenabscheidung und Acetylen als C und H Quelle abgeschieden, nachdem sie 10 Minuten lang mit einem Sauerstoffplasma vorbehandelt worden waren. Nach dieser O₂-Behandlung und der a-C:H Abscheidung werden die Oberflächen mit makroskopischen und mikroskopischen Messmethoden untersucht und die Daten anschließend analysiert. Die Oberflächenmorphologie wird mit Hilfe der Rasterelektronenmikroskopie und der Rasterkraftmikroskopie erfasst. Auf diese Weise können auch Informationen über die Stabilität der Schicht und die Oberflächenrauhigkeit gesammelt werden. Mit Kontaktwinkelmessungen (contact angle, CA) wird nicht nur die Benetzbarkeit, sondern auch die Kontaktwinkelhysterese durch Auf- und Abpumpen des Tropfenvolumens bestimmt. Durch Messung des CA von verschiedenen Flüssigkeiten und deren Vergleich werden die freie Oberflächenenergie (surface free energy, SFE) und ihre polaren und dispersiven Bestandteile bestimmt. Die Veränderungen der Barriereeigenschaften werden durch Wasserdampftransmissionstests (water vapor transmission rate, WVTR) überprüft. Die chemische Analyse der Oberfläche erfolgt zum einen durch Fourier-Transformations-Infrarotspektroskopie mit spiegelnder Reflexion und zum anderen durch Synchrotron unterstützte Techniken wie der Nahkanten-Röntgenabsorptionsfeinstruktur und der Röntgen-Photoelektronenspektroskopie. Bei der Analyse der Oberflächen nach der O₂ Behandlung, von der zunächst angenommen wurde, dass sie nur der Reinigung und Aktivierung der Oberfläche für die a-C:H Beschichtung dient, wurde festgestellt, dass die Veränderungen drastischer sind als ursprünglich angenommen. Wird PLA zum Beispiel bei 0° für 10 Minuten behandelt, steigt die Rauheit um das Fünffache. Mit zunehmendem Winkel verringert sich diese wieder, bis sie bei 180° wieder dem Ausgangswert entspricht. Bei PHB hingegen wird durchgehend ein ähnlicher Wert gemessen. Für beide Polymere lässt sich zeigen, dass der polare Anteil der SFE zunimmt. In der WVTR ist bei PLA eine Abnahme der Permeabilität und bei PHB ein Anstieg des Ausgangswertes zu beobachten. Die chemische Oberflächenanalyse zeigt, dass die O₂ Behandlung kaum Auswirkungen auf die Oberflächenbindungen hat. Insgesamt kann in dieser Arbeit gezeigt werden, dass sich die O₂ Behandlung auf die Eigenschaften der Oberfläche auswirkt und nicht ausschließlich als Reinigungs- und Aktivierungsprozess betrachtet werden kann. Bei direkter a-C:H Beschichtung (bei 0°) ist sowohl bei PLA als auch bei PHB ein Schichtversagen bei 10.0 Minuten aufgrund von Eigenspannung zu beobachten. Dies ist bei PHB in geringerem Maße auch bei 30° zu erkennen. Die Durchlässigkeit der Polymere wird bei einer fünf minütigen Beschichtung um 47% reduziert und auch die Schicht bei 10.0 Minuten führt diesen Effekt trotz auftretender Risse weiter. Die Aufbringung von a-C:H Schichten zeigt für beide Polymertypen bei direkter Beschichtung eine Dominanz von sp³-Bindungen. Mit zunehmendem Winkel nimmt diese ab und bei indirekten Beschichtungen werden sp²-Bindungen dominierend. Dieses Ergebnis ist für alle Schichtdicken ähnlich, nur der Winkel, bei dem der Wechsel der dominanten Bindung stattfindet, ist unterschiedlich. Es wird gezeigt, dass es möglich ist, die Oberflächeneigenschaften durch eine winkelabhängige Beschichtung zu steuern und somit das Verhältnis sp²/sp³ zu kontrollieren.