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Recent studies show that biofilm substances in contact with nanoplastics play an important role in the aggregation and sedimentation of nanoplastics. Consequences of these processes are changes in biofilm formation and stability and changes in the transport and fate of pollutants in the environment. Having a deeper understanding of the nanoplastics–biofilm interaction would help to evaluate the risks posed by uncontrolled nanoplastic pollution. These interactions are impacted by environmental changes due to climate change, such as, e.g., the acidification of surface waters. We apply fluorescence correlation spectroscopy (FCS) to investigate the pH-dependent aggregation tendency of non-functionalized polystyrene (PS) nanoparticles (NPs) due to intermolecular forces with model extracellular biofilm substances. Our biofilm model consists of bovine serum albumin (BSA), which serves as a representative for globular proteins, and the polysaccharide alginate, which is a main component in many biofilms, in solutions containing Na+ with an ionic strength being realistic for fresh-water conditions. Biomolecule concentrations ranging from 0.5 g/L up to at maximum 21 g/L are considered. We use non-functionalized PS NPs as representative for mostly negatively charged nanoplastics. BSA promotes NP aggregation through adsorption onto the NPs and BSA-mediated bridging. In BSA–alginate mixtures, the alginate hampers this interaction, most likely due to alginate–BSA complex formation. In most BSA–alginate mixtures as in alginate alone, NP aggregation is predominantly driven by weaker, pH-independent depletion forces. The stabilizing effect of alginate is only weakened at high BSA contents, when the electrostatic BSA–BSA attraction is not sufficiently screened by the alginate. This study clearly shows that it is crucial to consider correlative effects between multiple biofilm components to better understand the NP aggregation in the presence of complex biofilm substances. Single-component biofilm model systems based on comparing the total organic carbon (TOC) content of the extracellular biofilm substances, as usually considered, would have led to a misjudgment of the stability towards aggregation.
The goal of this PhD thesis is to investigate possibilities of using symbol elimination for solving problems over complex theories and analyze the applicability of such uniform approaches in different areas of application, such as verification, knowledge representation and graph theory. In the thesis we propose an approach to symbol elimination in complex theories that follows the general idea of combining hierarchical reasoning with symbol elimination in standard theories. We analyze how this general approach can be specialized and used in different areas of application.
In the verification of parametric systems it is important to prove that certain safety properties hold. This can be done by showing that a property is an inductive invariant of the system, i.e. it holds in the initial state of the system and is invariant under updates of the system. Sometimes this is not the case for the condition itself, but for a stronger condition it is. In this thesis we propose a method for goal-directed invariant strengthening.
In knowledge representation we often have to deal with huge ontologies. Combining two ontologies usually leads to new consequences, some of which may be false or undesired. We are interested in finding explanations for such unwanted consequences. For this we propose a method for computing interpolants in the description logics EL and EL⁺, based on a translation to the theory of semilattices with monotone operators and a certain form of interpolation in this theory.
In wireless network theory one often deals with classes of geometric graphs in which the existence or non-existence of an edge between two vertices in a graph relies on properties on their distances to other nodes. One possibility to prove properties of those graphs or to analyze relations between the graph classes is to prove or disprove that one graph class is contained in the other. In this thesis we propose a method for checking inclusions between geometric graph classes.
In Geschäftsbeziehungen, z. B. im internationalen Eisenbahnverkehr, können große Datenmengen zwischen den beteiligten Parteien ausgetauscht werden. Für den Austausch solcher Daten wird erwartet, dass das Risiko betrogen zu werden, z. B. durch den Erhalt gefälschter Daten, marginal ist, als auch angemessene Kosten sowie ein vorhersehbarer Gewinn. Da die ausgetauschten Daten für wichtige Geschäftsentscheidungen verwendet werden können, besteht für eine Partei ein hoher Anreiz, die Daten zu ihren Gunsten zu manipulieren. Um diese Art von Manipulation zu unterbinden existieren Mechanismen zur Sicherstellung der Integrität und Authentizität der Daten. In Kombination mit einem Protokoll für einen fairen Austausch kann sichergestellt werden, dass die Integrität und Authentizität dieser Daten auch über einen Austausch mit einer anderen Partei hinweg erhalten bleibt. Gleichzeitig stellt ein solches Protokoll sicher, dass der Austausch der Daten nur bei gleichzeitigem Austausch mit der vereinbarten Gegenleistung, z. B. einer Bezahlung erfolgt, aber auch, dass die Bezahlung nur erfolgt, wenn die Integrität und Authentizität der Daten wie vorher vereinbart, gegeben ist. Um jedoch Fairness garantieren zu können, muss ein Fair Exchange Protokoll eine vertrauenswürdige dritte Partei einbeziehen. Um Betrug durch eine einzelne zentralisierte Partei zu vermeiden, die als vertrauenswürdige dritte Partei agiert, schlägt die aktuelle Forschung vor, die vertrauenswürdige dritte Partei zu dezentralisieren, indem z. B. ein Distributed Ledger-basiertes Fair-Exchange Protokoll verwendet wird. Bei der Bewertung der Fairness eines solchen Austauschs vernachlässigen die aktuellen Ansätze jedoch die Kosten, die den Parteien entstehen, die den Fair Exchange durchführen. Dies kann zu einer Verletzung der skizzierten Erwartung angemessener Kosten führen, insbesondere wenn Distributed Ledger beteiligt sind, deren Benutzung in der Regel mit nicht-vernachlässigbaren Kosten verbunden ist. Darüber hinaus ist die Geschwindigkeit typischer Distributed-Ledger-basierter Fair Exchange-Protokolle begrenzt, was einer breiten Verwendung im Wege steht.
Um diese Herausforderungen zu überwinden, stellen wir in dieser Arbeit die Grundlage für eine Datenaustauschplattform vor, die einen vollständig dezentralisierten Fair Exchange mit angemessenen Kosten und Geschwindigkeit ermöglicht. Als theoretische Grundlage führen wir das Konzept der cost fairness ein, die die Kosten für die Fairnessbewertung berücksichtigt, indem verlangt wird, dass eine Partei, die dem Fair Exchange-Protokoll folgt, niemals einseitige Nachteile erleidet. Wir weisen nach, dass cost fairness nicht mit typischen öffentlichen Distributed Ledgers erreicht werden kann, sondern maßgeschneiderte Distributed Ledger-Instanzen erfordert, die in der Regel nicht vollständig dezentralisiert sind. Wir zeigen jedoch, dass die meisten einseitigen Kosten durch Angriffe einer unehrlichen Partei im Rahmen einer Grieving Attack verursacht werden können. Um einen Fair Exchange zu angemessenen Kosten und Geschwindigkeit zu ermöglichen, stellen wir FairSCE vor, ein Distributed Ledger-basiertes Fair Exchange-Protokoll, welches Distributed Ledger State Channels verwendet und einen Mechanismus zum Schutz vor Grieving Attacks enthält, wodurch die möglichen einseitigen Kosten auf ein Minimum reduziert werden. Auf der Grundlage unserer Evaluation von FairSCE sind die Worst Case-Kosten für den Datenaustausch selbst bei Vorhandensein von böswilligen Parteien bekannt, was eine Abschätzung des möglichen Nutzens und damit eine vorläufige Schätzung des wirtschaftlichen Nutzens ermöglicht. Um eine eindeutige Bewertung der korrekten übertragenen Daten zu ermöglichen und gleichzeitig sensible Teile der Daten zu maskieren, stellen wir außerdem einen Ansatz für das Hashing hierarchisch strukturierter Daten vor, mit dem die Integrität und Authentizität der übertragenen Daten sichergestellt werden kann.
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.
Examining the role of post-event processing in test anxiety—Pilot testing in three student samples
(2024)
This work investigates the occurrence of post-event processing (PEP) in the context of test anxiety; PEP involves rumination and self-critical thinking following an event and commonly observed in social anxiety. Three short-term longitudinal studies in student samples examined whether PEP occurs after exams and how it is associated with test anxiety. University students (N =35 in Study 1, N =146 in Study 2, and N =37 in Study 3) completed measures of trait and state test anxiety before an actual exam; PEP related to the exam was assessed at various time points afterward. Results revealed that PEP occurred to a meaningful extent after exam situations. Overall, it was positively associated with trait and state test anxiety, although some variations in the relations were found across the three studies. These findings underscore the relevance of PEP in the context of test anxiety, as PEP might contribute to maintaining test anxiety in the long term. Implications for future studies are discussed.
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.
Reducing gender bias in STEM is key to generating more equality and contributing to a more balanced workforce in this field. Spatial ability and its components are cognitive processes crucial to success in STEM education and careers. Significant gender differences have consistently been found in mental rotation (MR), the ability to mentally transform two- and three-dimensional objects. The aim of this pilot study is to examine factors in psychological assessment which may contribute to gender differences in MR performance. Moreover, findings will inform the development of the new approaches to assessment using computer adaptive testing (CAT). (1) Background: The study examines the impact of emotional regulation on MR performance in primary school children whose mean age was 9.28 years old. (2) Methods: Skin conductance was measured to assess the impact of emotional reactivity (ER) on performance during an MR task. (3) Results: Patterns of ER influence response time (RT) on specific items in the task. (4) Conclusions: Identifying the effects of emotional arousal and issues of test construction such as stereotyped stimuli and item difficulty in tests of spatial ability warrants ongoing investigation. It is vital to ensure that these factors do not compromise the accurate measurement of performance and inadvertently contribute to the gender gap in STEM.
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.
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.
How to begin? This short question addresses a problem that is anything but simple, especially when regarding something as sophisticated and multilayered as musical theatre. However, scholars of this vast research area have mostly neglected this question so far. This study analyses and compares the initial sections of late Victorian popular musical theatre and is therefore a contribution to several fields of research: the analysis of initial sections of musical theatre in general, the analysis of the music of popular musical theatre in particular, and therefore operetta studies. The 1890s are especially interesting times for popular musical theatre in London: The premiered works include the last collaborations of Gilbert and Sullivan as well as offshoots of Savoy opera; but the so-called ‘naughty nineties’ also saw the emergence of a new genre, musical comedy, which captured the late Victorian zeitgeist like no other. This new form of theatrical entertainment was carefully and consciously constructed and promoted as modern and fashionable, walking a fine line between respectability and mildly risqué excitement.
Because a deep understanding of the developments and new tendencies concerning popular musical theatre in the 1890s is crucial in order to interpret differences as well as similarities, the analyses of the opening numbers are preceded by a detailed discussion of the relevant genres: comic opera, musical comedy, musical play and operetta. Since the producers of the analysed works wanted to distance themselves from former and supposedly old-fashioned traditions, this book also considers influences from their British predecessors, but also from Viennese operetta and French opéra bouffe.