The 10 most recently published documents
Full-waveform-based characterization of acoustic emission activity in a mine-scale experiment
(2020)
Understanding fracturing processes and the hydromechanical relation to induced seismicity is a key question for enhanced geothermal systems (EGS). Commonly massive fluid injection, predominately causing hydroshearing, are used in large-scale EGS but also hydraulic fracturing approaches were discussed. To evaluate the applicability of hydraulic fracturing techniques in EGS, six in situ, multistage hydraulic fracturing experiments with three different injection schemes were performed under controlled conditions in crystalline rock at the Aspo Hard Rock Laboratory (Sweden). During the experiments the near-field ground motion was continuously recorded by 11 piezoelectric borehole sensors with a sampling rate of 1 MHz. The sensor network covered a volume of 30x30x30 m around a horizontal, 28-m-long injection borehole at a depth of 410 m. To extract and characterize massive, induced, high-frequency acoustic emission (AE) activity from continuous recordings, a semi-automated workflow was developed relying on full waveform based detection, classification and location procedures. The approach extended the AE catalogue from 196 triggered events in previous studies to more than 19600 located AEs. The enhanced catalogue, for the first time, allows a detailed analysis of induced seismicity during single hydraulic fracturing experiments, including the individual fracturing stages and the comparison between injection schemes. Beside the detailed study of the spatio-temporal patterns, event clusters and the growth of seismic clouds, we estimate relative magnitudes and b-values of AEs for conventional, cyclic progressive and dynamic pulse injection schemes, the latter two being fatigue hydraulic fracturing techniques. While the conventional fracturing leads to AE patterns clustered in planar regions, indicating the generation of a single main fracture plane, the cyclic progressive injection scheme results in a more diffuse, cloud-like AE distribution, indicating the activation of a more complex fracture network. For a given amount of hydraulic energy (pressure multiplied by injected volume) pumped into the system, the cyclic progressive scheme is characterized by a lower rate of seismicity, lower maximum magnitudes and significantly larger b-values, implying an increased number of small events relative to the large ones. To our knowledge, this is the first direct comparison of high resolution seismicity in a mine-scale experiment induced by different hydraulic fracturing schemes.
The increasing global population has led to a growing demand for cost-effective and eco-friendly methods of water purification. This demand has reached a peak due to the increasing presence of impurities and pollutants in water and a growing awareness of waterborne diseases. Advanced oxidation processes (AOPs) are effective methods to address these challenges, due to the generation of highly reactive radicals, such as sulfate radical (SO4•-), hydroxyl radical (•OH), and/or superoxide radical (•O2-) in oxidation reactions. Relative to conventional hydrogen peroxide (H2O2)-based AOPs for wastewater treatment, the persulfate-related AOPs are receiving increasing attention over the past decades, due to their stronger oxidizing capability and a wider pH working window. Further deployment of the seemingly plausible technology as an alternative for the well-established one in industry, however, necessitates a careful evaluation of compounding factors, such as water matrix effects, toxicological consequences, costs, and engineering challenges, etc. To this end, rational design of efficient and environmentally friendly catalysts constitutes an indispensable pathway to advance persulfate activation efficacy and to elucidate the mechanisms in AOPs, the combined endeavors are expected to provide insightful understanding and guidelines for future studies in wastewater treatment. A dozens of transition metal-based catalysts have been developed for persulfate-related AOPs, while the undesirable metal leaching and poor stability in acidic conditions have been identified as major obstacles. Comparatively, the carbonaceous materials are emerging as alternative candidates, which are characterized by metal-free nature, wide availability, and exceptional resistance to acid and alkali, as well as tunable physicochemical and electronic properties, the combined merits make them an attractive option to overcome the aforementioned limitations in metal-based catalytic systems. This dissertation aims at developing novel carbonaceous materials to boost the activity in peroxymonosulfate (PMS) activation processes. Functionalized carbon materials with metal particles or heteroatoms were constructed and further evaluated in terms of their ability to activate PMS for AOPs. The main contents of this thesis are summarized as follows: (1) Iron oxide-loaded biochar: improving stability and alleviating metal leakage Metal leaching constitutes one of the main drawbacks in using transition metals as PMS activators, which is accompanied by the generation of metal-containing sludge, potentially leading to secondary pollution. Meanwhile, the metal nanoparticles are prone to aggregate, causing rapid decay of catalytic performance. The use of carbons as supports for transition metals could mitigate these deficiencies, because the interaction between metals and carbons could in turn disperse and stabilize metal nanoparticles, thus suppressing the metal leaching. In this work, the environmentally benign lignin with its abundant phenolic groups, which is well known to serve as carbon source with high yields and flexibility, was utilized to load Fe ions. The facile low-temperature pre-treatment pyrolytic strategy was employed to construct a green catalyst with iron oxides embedded in Kraft-lignin-derived biochar (termed as γ-Fe2O3@KC). The γ-Fe2O3@KC was capable of activating PMS to generate stable non-radical species (1O2 and Fe (V)=O) and to enhance electron transfer efficiency. A surface-bound reactive complex (catalyst-PMS*) was identified by electrochemical characterizations and discussed with primary surface-bound radical pairs to explain the contradictions between quenching and EPR detection results. The system also showed encouraging reusability for at least 5 times and high stability at pH 3-9. The low concentration of iron in γ-Fe2O3@KC/PMS system implied that the carbon scaffold of biochar substantially alleviated metal leakage. (2) MOF-derived nanocarbon: new carbon crystals Traditional carbon materials are of rather moderate performance in activation PMS, due to the poor electron transfer capacity within the amorphous structure and limited active sites for PMS adsorption. Herein, we established crystalline nanocarbon materials via a simple NaCl-templated strategy using the monoclinic zeolitic imidazolate framework-8 (ZIF-8) sealed with NaCl crystals as the precursors. Specifically, NaCl captured dual advantages in serving as structure-directing agent during hydrolysis and protective salt reactor to facilitate phase transformation during carbonization. The structure-directing agent NaCl provided a protective and confined space for the evolution of MOF upon carbonization, which led to high doping amounts of nitrogen (N) and oxygen elements (O) in carbon framework (N: 14.16 wt%, O: 9.6 wt%) after calcination at a high temperature of 950 oC. We found that N-O co-doping can activate the chemically inert carbon network and the nearby sp2-hybridized carbon atoms served as active sites for adsorption and activation. Besides, the highly crystallized structure with well-established carbon channels around activated carbon atoms could significantly accelerate electron transfer process after initial adsorption of PMS. As such, this crystalline nanocarbon exhibited excellent catalytic kinetics for various pollutants. (3) MOF-derived 2D carbon layers: enhanced mass/electron transfer The two-dimensional (2D) configuration of carbon-based nanosheets with inherent nanochannels and abundant active sites residing on the layer edges or in between the layers, allowed the accessible interaction and close contact between the substrates and reactants, as well as the dramatically improved electron- and mass-transfer kinetics. In this regard, we developed dual-templating strategy to afford 2D assembly of the crystalline carbons, which found efficiency in reinforcing the interactions between the catalyst surface and foreign pollutants. Specifically, we found that the ice crystals and NaCl promoted the evolution of MOF in a 2D fashion during the freezing casting stage, while the later further allowed the formation of a graphitic surface at high calcination temperature, by virtue of the templating effect of molten salt. Due to the highly retained co-doping amounts, N and O heteroatoms created abundant active sites for PMS activation, the 2D configuration of carbon-based nanosheets enable efficient interaction of PMS and pollutants on the surface, which further boosted the kinetics of degradation.
Development of electrochemical antibody-based and enzymatic assays for mycotoxin analysis in food
(2023)
Electrochemical methods are promising to meet the demand for easy-to-use devices monitoring key parameters in the food industry. Many companies run own lab procedures for mycotoxin analysis, but it is a major goal to simplify the analysis. The enzyme-linked immunosorbent assay using horseradish peroxidase as enzymatic label, together with 3,3',5,5' tetramethylbenzidine (TMB)/H2O2 as substrates allows sensitive mycotoxin detection with optical detection methods. For the miniaturization of the detection step, an electrochemical system for mycotoxin analysis was developed. To this end, the electrochemical detection of TMB was studied by cyclic voltammetry on different screen-printed electrodes (carbon and gold) and at different pH values (pH 1 and pH 4). A stable electrode reaction, which is the basis for the further construction of the electrochemical detection system, could be achieved at pH 1 on gold electrodes. An amperometric detection method for oxidized TMB, using a custom-made flow cell for screen-printed electrodes, was established and applied for a competitive magnetic bead-based immunoassay for the mycotoxin ochratoxin A. A limit of detection of 150 pM (60 ng/L) could be obtained and the results were verified with optical detection. The applicability of the magnetic bead-based immunoassay was tested in spiked beer using a handheld potentiostat connected via Bluetooth to a smartphone for amperometric detection allowing to quantify ochratoxin A down to 1.2 nM (0.5 µg/L).
Based on the developed electrochemical detection system for TMB, the applicability of the approach was demonstrated with a magnetic bead-based immunoassay for the ergot alkaloid, ergometrine. Under optimized assay conditions a limit of detection of 3 nM (1 µg/L) was achieved and in spiked rye flour samples ergometrine levels in a range from 25 to 250 µg/kg could be quantified. All results were verified with optical detection. The developed electrochemical detection method for TMB gives great promise for the detection of TMB in many other HRP-based assays.
A new sensing approach, based on an enzymatic electrochemical detection system for the mycotoxin fumonisin B1 was established using an Aspergillus niger fumonisin amine oxidase (AnFAO). AnFAO was produced recombinantly in E. coli as maltose-binding protein fusion protein and catalyzes the oxidative deamination of fumonisins, producing hydrogen peroxide. It was found that AnFAO has a high storage and temperature stability. The enzyme was coupled covalently to magnetic particles, and the enzymatically produced H2O2 in the reaction with fumonisin B1 was detected amperometrically in a flow injection system using Prussian blue/carbon electrodes and the custom-made wall-jet flow cell. Fumonisin B1 could be quantified down to 1.5 µM (≈ 1 mg/L). The developed system represents a new approach to detect mycotoxins using enzymes and electrochemical methods.
The change of the mechanical properties of granular materials with pressure is an important topic associated with many industrial applications. In this paper we investigate the influence of hydrostatic pressure (P-e) on the effective bulk compressibility (C-eff) of a granular material by applying two modified theoretical approaches that are based on contact mechanics and micromechanics, respectively. For a granular material composed of rough grains, an extended contact model is developed to elucidate the effect of roughness of grain surfaces on bulk compressibility. At relatively low pressures, the model predicts that the decrease of bulk compressibility with pressure may be described by a power law with an exponent of -1/2 (i.e., C-eff proportional to P-e(1/2) ), but deviates at intermediate pressures. At elevated pressures beyond full contact, bulk compressibility remains almost unchanged, which may be roughly evaluated by continuum contact mechanics. As an alternative explanation of pressure-dependent bulk compressibility, we suggest a micromechanical model that accounts for effects of different types of pore space present in granular materials. Narrow and compliant inter-granular cracks are approximated by three-dimensional oblate spheroidal cracks with rough surfaces, whereas the equant and stiff pores surrounded by three and four neighboring grains are modeled as tubular pores with cross sections of three and four cusp-like corners, respectively. In this model, bulk compressibility is strongly reduced with increasing pressure by progressive closure of rough-walled cracks. At pressures exceeding crack closure pressure, deformation of the remaining equant pores is largely insensitive to pressure, with almost no further change in bulk compressibility. To validate these models, we performed hydrostatic compression tests on Bentheim sandstone (a granular rock consisting of quartz with high porosity) under a wide range of pressure. The relation between observed microstructures and measured pressure-dependent bulk compressibility is well explained by both suggested models.
This research focuses on empowering leadership, a leadership style that shares autonomy and responsibilities with the followers. Empowering leadership enhances the meaningfulness of work by fostering participation in decision-making, expressing confidence in high performance, and providing autonomy in target setting (Cheong, 2016). I examine how empowering leadership affects followers’ reflection. I used data from 528 individuals across 172 teams and found a positive relationship between empowering leadership and followers’ reflection. Followers’ reflection, in turn, is negatively associated with followers’ withdrawal, which mediates the beneficial effect of empowering leadership on leaders’ emotional exhaustion. As for the leaders, I propose that empowering leadership is negatively related also to leaders’ emotional exhaustion. This research broadens our understanding of empowering leadership's effects on both followers and leaders. Moreover, it integrates empowering leadership, leader emotional exhaustion, and burnout literature. Overall, empowering leadership strengthens members’ reflective attitudes and behaviors, which result in reduced withdrawal (and increased presence and contribution) in teams. Because the members contribute to team effort more, the leaders experience less emotional exhaustion. Hence, my work not only identifies new ways through which empowering leadership positively affects followers but also shows how these positive effects on followers benefit the leaders’ well-being.
In dieser Dissertation konnten erfolgreich mechanisch stabile Hydrogele über eine freie radikalische Polymerisation (FRP) in Wasser synthetisiert werden. Dabei diente vor allem das Sulfobetain SPE als Monomer. Dieses wurde mit dem über eine nukleophile Substitution erster bzw. zweiter Ordnung hergestellten Vernetzer TMBEMPA/Br umgesetzt.
Die entstandenen Netzwerke wurden im Gleichgewichtsquellzustand im Wesentlichen mittels Niederfeld-Kernresonanzspektroskopie, Röntgenkleinwinkelstreuung (SAXS), Rasterelektronenmikroskopie mit Tieftemperaturtechnik (Kryo-REM), dynamisch-mechanische Analyse (DMA), Rheologie, thermogravimetrische Analyse (TGA) und dynamische Differenzkalorimetrie (DSC) analysiert.
Das hierarchisch aufgebaute Netzwerk wurde anschließend für die matrixgesteuerten Mineralisation von Calciumphosphat und –carbonat genutzt. Über das alternierende Eintauchverfahren (engl. „alternate soaking method“) und der Variation von Mineralisationsparametern, wie pH-Wert, Konzentration c und Temperatur T konnten dann verschiedene Modifikationen des Calciumphosphats generiert werden. Das entstandene Hybridmaterial wurde qualitativ mittels Röntgenpulverdiffraktometrie (XRD), abgeschwächte Totalreflexion–fouriertransformierte Infrarot Spektroskopie (ATR-FTIR), Raman-Spektroskopie, Rasterelektronenmikroskopie (REM) mit energiedispersiver Röntgenspektroskopie (EDXS) und optischer Mikroskopie (OM) als auch quantitative mittels Gravimetrie und TGA analysiert.
Für die potentielle Verwendung in der Medizintechnik, z.B. als Implantatmaterial, ist die grundlegende Einschätzung der Wechselwirkung zwischen Hydrogel bzw. Hybridmaterial und verschiedener Zelltypen unerlässlich. Dazu wurden verschiedene Zelltypen, wie Einzeller, Bakterien und adulte Stammzellen verwendet. Die Wechselwirkung mit Peptidsequenzen von Phagen komplettiert das biologische Unterkapitel.
Hydrogele sind mannigfaltig einsetzbar. Diese Arbeit fasst daher weitere Projektperspektiven, auch außerhalb des biomedizinischem Anwendungsspektrums, auf. So konnten erste Ansätze zur serienmäßige bzw. maßgeschneiderte Produktion über das „Inkjet“ Verfahren erreicht werden. Um dies ermöglichen zu können wurden erfolgreich weitere Synthesestrategien, wie die Photopolymerisation und die redoxinitiierte Polymerisation, ausgenutzt. Auch die Eignung als Filtermaterial oder Superabsorber wurde analysiert.
Establishment of final leaf size in plants represents a complex mechanism that relies on the precise regulation of two interconnected cellular processes, cell division and cell expansion. In previous work, the barley protein BROAD LEAF1 (BLF1) was identified as a novel negative regulator of cell proliferation, that mainly limits leaf growth in the width direction. Here I identified a novel RING/U-box protein that interacts with BLF1 through a yeast two hybrid screen. Using BiFC, Co-IP and FRET I confirmed the interaction of the two proteins in planta. Enrichment of the BLF1-mEGFP fusion protein and the increase of the FRET signal upon MG132 treatment of tobacco plants, together with an in vivo ubiquitylation assay in bacteria, confirmed that the RING/U-box E3 interacts with BLF1 to mediate its ubiquitylation and degradation by the 26S proteasome system. Consistent with regulation of endogenous BLF1 in barley by proteasomal degradation, inhibition of the proteasome by bortezomib treatment on BLF1-vYFP transgenic barley plants also resulted in an enrichment of the BLF1 protein. I thus demonstrated that RING/U-box E3 is colocalized with BLF1 in nuclei and negatively regulates BLF1 protein levels. Analysis of ring-e3_1 knock-out mutants suggested the involvement of the RING/U-box E3 gene in leaf growth control, although the effect was mainly on leaf length. Together, my results suggest that proteasomal degradation, possibly mediated by RING/U-box E3, contributes to fine-tuning BLF1 protein-level in barley.
Deutsche Blauhelme in Afrika
(2023)
Warum trat die Bundesregierung ab Ende der 1980er Jahre weltweit als sicherheitspolitischer Akteur in Erscheinung? Warum engagierte sie sich in multinationalen Missionen der Vereinten Nationen etwa in Somalia, Namibia und Ruanda mit Soldaten oder Polizisten - und in anderen Missionen in Afrika im gleichen Zeitraum nicht? Gestützt auf ministerielle Archivquellen untersucht Torsten Konopka die Prozesse der nationalen Entscheidungsfindung, die zu einer Beteiligung oder Nichtbeteiligung an VN-Missionen in Afrika führten. Das Buch leistet einen politik- sowie militärgeschichtlichen Beitrag zur Genese der frühen Auslandsverwendungen der Bundeswehr.
In two eye-tracking experiments, we investigated the processing of information about phonological consistency of Chinese phonograms during sentence reading. In Experiment 1, we adopted the error disruption paradigm in silent reading and found significant effects of phonological consistency and homophony in the foveal vision, but only in a late processing stage. Adding oral reading to Experiment 2, we found both effects shifted to earlier indices of parafoveal processing. Specifically, low-consistency characters led to a better homophonic foveal recovery effect in Experiment 1 and stronger homophonic preview benefits in Experiment 2. These findings suggest that phonological consistency information can be obtained during sentence reading, and compared to the low-consistency previews the high-consistency previews are processed faster, which leads to greater interference to the recognition of target characters.
