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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 international business relationships, such as international railway operations, large amounts of data can be exchanged among the parties involved. For the exchange of such data, a limited risk of being cheated by another party, e.g., by being provided with fake data, as well as reasonable cost and a foreseeable benefit, is expected. As the exchanged data can be used to make critical business decisions, there is a high incentive for one party to manipulate the data in its favor. To prevent this type of manipulation, mechanisms exist to ensure the integrity and authenticity of the data. In combination with a fair exchange protocol, it can be ensured that the integrity and authenticity of this data is maintained even when it is exchanged with another party. At the same time, such a protocol ensures that the exchange of data only takes place in conjunction with the agreed compensation, such as a payment, and that the payment is only made if the integrity and authenticity of the data is ensured as previously agreed. However, in order to be able to guarantee fairness, a fair exchange protocol must involve a trusted third party. To avoid fraud by a single centralized party acting as a trusted third party, current research proposes decentralizing the trusted third party, e.g., by using a distributed ledger based fair exchange protocol. However, for assessing the fairness of such an exchange, state-of-the-art approaches neglect costs arising for the parties conducting the fair exchange. This can result in a violation of the outlined expectation of reasonable cost, especially when distributed ledgers are involved, which are typically associated with non-negligible costs. Furthermore, the performance of typical distributed ledger-based fair exchange protocols is limited, posing an obstacle to widespread adoption.
To overcome the challenges, in this thesis, we introduce the foundation for a data exchange platform allowing for a fully decentralized fair data exchange with reasonable cost and performance. As a theoretical foundation, we introduce the concept of cost fairness, which considers cost for the fairness assessment by requesting that a party following the fair exchange protocol never suffers any unilateral disadvantages. We prove that cost fairness cannot be achieved using typical public distributed ledgers but requires customized distributed ledger instances, which usually lack complete decentralization. However, we show that the highest unilateral cost are caused by a grieving attack.
To allow fair data exchanges to be conducted with reasonable cost and performance, we introduce FairSCE, a distributed ledger-based fair exchange protocol using distributed ledger state channels and incorporating a mechanism to protect against grieving attacks, reducing the possible unilateral cost that have to be covered to a minimum. Based on our evaluation of FairSCE, the worst-case cost for data exchange, even in the presence of malicious parties, is known, which allows an estimate of the possible benefit and, thus, the preliminary estimate of economic utility. Furthermore, to allow for an unambiguous assessment of the correct data being transferred while still allowing for sensitive parts of the data to be masked, we introduce an approach for the hashing of hierarchically structured data, which can be used to ensure integrity and authenticity of the data being transferred.
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.
The biodegradable polymers polylactic acid (PLA) and polyhydroxybutyrate (PHB) produced from renewable raw materials were coated with hydrogenated amorphous carbon layers (a-C:H) at different deposition angles with various thicknesses as part of this thesis. Similar to conventional polymers, biopolymers often have unsuitable surface properties for industrial purposes, e.g. low hardness. For some applications, it is therefore necessary and advantageous to modify the surface properties of biopolymers while retaining the main properties of the substrate material. A suitable surface modification is the deposition of thin a-C:H layers. Their properties depend essentially on the sp² and sp³ hybridization ratio of the carbon atoms and the content of hydrogen atoms. The sp²/sp³ ratio was to be controlled in the present work by varying the coating geometry. Since coatings at 0°, directly in front of the plasma source, contain a higher percentage of sp³ and indirectly coated (180°) a higher amount of sp², it is shown in this work that it is possible to control the sp²/sp³ ratio. For this purpose, the samples are placed in front of the plasma source at angles of 0, 30, 60, 90, 120, 150 and 180° and coated for 2.5, 5.0, 7.5 and 10.0 minutes. For the angles 0°, the layer thicknesses were 25, 50, 75 and 100 nm. The a-C:H layers were all deposited using radio-frequency plasma-enhanced chemical vapor deposition and acetylene as C and H sources after being pretreated with an oxygen plasma for 10 minutes. Following the O₂ treatment and the a-C:H deposition, the surfaces are examined using macroscopic and microscopic measurement methods and the data is then analyzed. The surface morphology is recorded using scanning electron microscopy and atomic force microscopy. In addition, data on the stability of the layer and the surface roughness can be collected. Contact angle (CA) measurements are used to determine not only the wettability, but also the contact angle hysteresis by pumping the drop volume up and down. By measuring the CA with different liquids and comparing them, the surface free energy (SFE) and its polar and disperse components are determined. The changes in barrier properties are verified by water vapor transmission rate tests (WVTR). The chemical analysis of the surface is carried out on the one hand by Fourier transform infrared spectroscopy with specular reflection and on the other hand by synchrotron-supported techniques such as near-edge X-ray absorption fine structure and X-ray photoelectron spectroscopy. When analyzing the surfaces after the O₂ treatment, which was initially assumed to serve only to clean and activate the surface for the a-C:H coating, it was found that the changes were more drastic than originally assumed. For example, if PLA is treated at 0° for 10 minutes, the roughness increases fivefold. As the angle increases, it decreases again until it returns to the initial value at 180°. This can be recognized to a lesser extent with PHB at 30°. For both polymers, it can be shown that the polar fraction of the SFE increases. In the WVTR, a decrease in permeability can be observed for PLA and an increase in the initial value for PHB. The chemical surface analysis shows that the O₂ treatment has little effect on the surface bonds. Overall, it can be shown in this work that the O₂ treatment has an effect on the properties of the surface and cannot be regarded exclusively as a cleaning and activation process. With direct a-C:H coating (at 0°), a layer failure due to internal stress can be observed for both PLA and PHB. This also occurs with PHB at 30°, but to a lesser extent. Permeability of the polymers is reduced by 47% with a five-minute coating and the layer at 10.0 minutes continues to have this effect despite cracks appearing. The application of a-C:H layers shows a dominance of sp³ bonds for both polymer types with direct coating. This decreases with increasing angle and sp² bonds become dominant for indirect coatings. This result is similar for all coating thicknesses, only the angle at which the change of the dominant bond takes place is different. It is shown that it is possible to control the surface properties by an angle-dependent coating and thus to control the ratio sp²/sp³.
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.