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Housing in metabolic cages can induce a pronounced stress response. Metabolic cage systems imply housing mice on metal wire mesh for the collection of urine and feces in addition to monitoring food and water intake. Moreover, mice are single-housed, and no nesting, bedding, or enrichment material is provided, which is often argued to have a not negligible impact on animal welfare due to cold stress. We therefore attempted to reduce stress during metabolic cage housing for mice by comparing an innovative metabolic cage (IMC) with a commercially available metabolic cage from Tecniplast GmbH (TMC) and a control cage. Substantial refinement measures were incorporated into the IMC cage design. In the frame of a multifactorial approach for severity assessment, parameters such as body weight, body composition, food intake, cage and body surface temperature (thermal imaging), mRNA expression of uncoupling protein 1 (Ucp1) in brown adipose tissue (BAT), fur score, and fecal corticosterone metabolites (CMs) were included. Female and male C57BL/6J mice were single-housed for 24 h in either conventional Macrolon cages (control), IMC, or TMC for two sessions. Body weight decreased less in the IMC (females—1st restraint: 6.94%; 2nd restraint: 6.89%; males—1st restraint: 8.08%; 2nd restraint: 5.82%) compared to the TMC (females—1st restraint: 13.2%; 2nd restraint: 15.0%; males—1st restraint: 13.1%; 2nd restraint: 14.9%) and the IMC possessed a higher cage temperature (females—1st restraint: 23.7°C; 2nd restraint: 23.5 °C; males—1st restraint: 23.3 °C; 2nd restraint: 23.5 °C) compared with the TMC (females—1st restraint: 22.4 °C; 2nd restraint: 22.5 °C; males—1st restraint: 22.6 °C; 2nd restraint: 22.4 °C). The concentration of fecal corticosterone metabolites in the TMC (females—1st restraint: 1376 ng/g dry weight (DW); 2nd restraint: 2098 ng/g DW; males—1st restraint: 1030 ng/g DW; 2nd restraint: 1163 ng/g DW) was higher compared to control cage housing (females—1st restraint:
640 ng/g DW; 2nd restraint: 941 ng/g DW; males—1st restraint: 504 ng/g DW; 2nd restraint: 537 ng/g DW). Our results show the stress potential induced by metabolic cage restraint that is markedly influenced by the lower housing temperature. The IMC represents a first attempt to target cold stress reduction during metabolic cage application thereby producing more animal welfare friendly data.
Its properties make copper one of the world’s most important functional metals. Numerous megatrends are increasing the demand for copper. This requires the prospection and exploration of new deposits, as well as the monitoring of copper quality in the various production steps. A promising technique to perform these tasks is Laser Induced Breakdown Spectroscopy (LIBS). Its unique feature, among others, is the ability to measure on site without sample collection and preparation. In this work, copper-bearing minerals from two different deposits are studied. The first set of field samples come from a volcanogenic massive sulfide (VMS) deposit, the second part from a stratiform sedimentary copper (SSC) deposit. Different approaches are used to analyze the data. First, univariate regression (UVR) is used. However, due to the strong influence of matrix effects, this is not suitable for the quantitative analysis of copper grades. Second, the multivariate method of partial least squares regression (PLSR) is used, which is more suitable for quantification. In addition, the effects of the surrounding matrices on the LIBS data are characterized by principal component analysis (PCA), alternative regression methods to PLSR are tested and the PLSR calibration is validated using field samples.
Its properties make copper one of the world’s most important functional metals. Numerous megatrends are increasing the demand for copper. This requires the prospection and exploration of new deposits, as well as the monitoring of copper quality in the various production steps. A promising technique to perform these tasks is Laser Induced Breakdown Spectroscopy (LIBS). Its unique feature, among others, is the ability to measure on site without sample collection and preparation. In this work, copper-bearing minerals from two different deposits are studied. The first set of field samples come from a volcanogenic massive sulfide (VMS) deposit, the second part from a stratiform sedimentary copper (SSC) deposit. Different approaches are used to analyze the data. First, univariate regression (UVR) is used. However, due to the strong influence of matrix effects, this is not suitable for the quantitative analysis of copper grades. Second, the multivariate method of partial least squares regression (PLSR) is used, which is more suitable for quantification. In addition, the effects of the surrounding matrices on the LIBS data are characterized by principal component analysis (PCA), alternative regression methods to PLSR are tested and the PLSR calibration is validated using field samples.
Background
The aggregation of a series of N-of-1 trials presents an innovative and efficient study design, as an alternative to traditional randomized clinical trials. Challenges for the statistical analysis arise when there is carry-over or complex dependencies of the treatment effect of interest.
Methods
In this study, we evaluate and compare methods for the analysis of aggregated N-of-1 trials in different scenarios with carry-over and complex dependencies of treatment effects on covariates. For this, we simulate data of a series of N-of-1 trials for Chronic Nonspecific Low Back Pain based on assumed causal relationships parameterized by directed acyclic graphs. In addition to existing statistical methods such as regression models, Bayesian Networks, and G-estimation, we introduce a carry-over adjusted parametric model (COAPM).
Results
The results show that all evaluated existing models have a good performance when there is no carry-over and no treatment dependence. When there is carry-over, COAPM yields unbiased and more efficient estimates while all other methods show some bias in the estimation. When there is known treatment dependence, all approaches that are capable to model it yield unbiased estimates. Finally, the efficiency of all methods decreases slightly when there are missing values, and the bias in the estimates can also increase.
Conclusions
This study presents a systematic evaluation of existing and novel approaches for the statistical analysis of a series of N-of-1 trials. We derive practical recommendations which methods may be best in which scenarios.
The study of subnational and local government systems and reforms has become an increasingly salient topic in comparative public administration. In many European countries, policy implementation, the execution of public tasks and the delivery of services to citizens are largely carried out by local governments, which, at the same time, have been subjected to multiple reforms and sometimes comprehensive institutional re-organizations. This chapter discusses analytical key concepts and outcomes of the comparative study of local governments and local government reforms. It outlines frameworks and analytical tools to capture the variety of institutional settings and developments at the local level of government. It provides an introduction into crucial comparative dimensions, such as functional, territorial and political profiles of local governments, and analyses current reform approaches and outcomes based on recent empirical findings. Finally, the chapter addresses salient issues to be taken up in future comparative studies about local government.
How do social changes, new technologies or new management trends affect communication work? A team of researchers at Leipzig University and the University of Potsdam (Germany) observed new developments in related disciplines. As a result, the five most important trends for corporate communications are identified annually and published in the Communications Trend Radar. Thus, Communications managers can identify challenges and opportunities at an early stage, take a position, address issues and make decisions. For 2023, the Communications Trend Radar identifies five key trends for corporate communications: State Revival, Scarcity Management, Unimagination, Parallel Worlds, Augemented Workflows.
Local laws on urban policy, i.e., ordinances directly affect our daily life in various ways (health, business etc.), yet in practice, for many citizens they remain impervious and complex. This article focuses on an approach to make urban policy more accessible and comprehensible to the general public and to government officials, while also addressing pertinent social media postings. Due to the intricacies of the natural language, ranging from complex legalese in ordinances to informal lingo in tweets, it is practical to harness human judgment here. To this end, we mine ordinances and tweets via reasoning based on commonsense knowledge so as to better account for pragmatics and semantics in the text. Ours is pioneering work in ordinance mining, and thus there is no prior labeled training data available for learning. This gap is filled by commonsense knowledge, a prudent choice in situations involving a lack of adequate training data. The ordinance mining can be beneficial to the public in fathoming policies and to officials in assessing policy effectiveness based on public reactions. This work contributes to smart governance, leveraging transparency in governing processes via public involvement. We focus significantly on ordinances contributing to smart cities, hence an important goal is to assess how well an urban region heads towards a smart city as per its policies mapping with smart city characteristics, and the corresponding public satisfaction.
Finger-based representation of numbers is a high-level cognitive strategy to assist numerical and arithmetic processing in children and adults. It is unclear whether this paradigm builds on simple perceptual features or comprises several attributes through embodiment. Here we describe the development and initial testing of an experimental setup to study embodiment during a finger-based numerical task using Virtual Reality (VR) and a low-cost tactile stimulator that is easy to build. Using VR allows us to create new ways to study finger-based numerical representation using a virtual hand that can be manipulated in ways our hand cannot, such as decoupling tactile and visual stimuli. The goal is to present a new methodology that can allow researchers to study embodiment through this new approach, maybe shedding new light on the cognitive strategy behind the finger-based representation of numbers. In this case, a critical methodological requirement is delivering precisely targeted sensory stimuli to specific effectors while simultaneously recording their behavior and engaging the participant in a simulated experience. We tested the device's capability by stimulating users in different experimental configurations. Results indicate that our device delivers reliable tactile stimulation to all fingers of a participant's hand without losing motion tracking quality during an ongoing task. This is reflected by an accuracy of over 95% in participants detecting stimulation of a single finger or multiple fingers in sequential stimulation as indicated by experiments with sixteen participants. We discuss possible application scenarios, explain how to apply our methodology to study the embodiment of finger-based numerical representations and other high-level cognitive functions, and discuss potential further developments of the device based on the data obtained in our testing.
The global climate crisis is significantly contributing to changing ecosystems, loss of biodiversity and is putting numerous species on the verge of extinction. In principle, many species are able to adapt to changing conditions or shift their habitats to more suitable regions. However, change is progressing faster than some species can adjust, or potential adaptation is blocked and disrupted by direct and indirect human action. Unsustainable anthropogenic land use in particular is one of the driving factors, besides global heating, for these ecologically critical developments. Precisely because land use is anthropogenic, it is also a factor that could be quickly and immediately corrected by human action.
In this thesis, I therefore assess the impact of three climate change scenarios of increasing intensity in combination with differently scheduled mowing regimes on the long-term development and dispersal success of insects in Northwest German grasslands. The large marsh grasshopper (LMG, Stethophyma grossum, Linné 1758) is used as a species of reference for the analyses. It inhabits wet meadows and marshes and has a limited, yet fairly good ability to disperse. Mowing and climate conditions affect the development and mortality of the LMG differently depending on its life stage.
The specifically developed simulation model HiLEG (High-resolution Large Environmental
Gradient) serves as a tool for investigating and projecting viability and dispersal success under different climate conditions and land use scenarios. It is a spatially explicit, stage- and cohort-based model that can be individually configured to represent the life cycle and characteristics of terrestrial insect species, as well as high-resolution environmental data and the occurrence of external disturbances. HiLEG is a freely available and adjustable software that can be used to support conservation planning in cultivated grasslands.
In the three case studies of this thesis, I explore various aspects related to the structure of simulation models per se, their importance in conservation planning in general, and insights regarding the LMG in particular. It became apparent that the detailed resolution of model processes and components is crucial to project the long-term effect of spatially and temporally confined events. Taking into account conservation measures at the regional level has further proven relevant, especially in light of the climate crisis. I found that the LMG is benefiting from global warming in principle, but continues to be constrained by harmful mowing regimes. Land use measures could, however, be adapted in such a way that they allow the expansion and establishment of the LMG without overly affecting agricultural yields.
Overall, simulation models like HiLEG can make an important contribution and add value
to conservation planning and policy-making. Properly used, simulation results shed light
on aspects that might be overlooked by subjective judgment and the experience of individual stakeholders. Even though it is in the nature of models that they are subject to limitations and only represent fragments of reality, this should not keep stakeholders from using them, as long as these limitations are clearly communicated. Similar to HiLEG, models could further be designed in such a way that not only the parameterization can be adjusted as required, but also the implementation itself can be improved and changed as desired. This openness and flexibility should become more widespread in the development of simulation models.
Modern datasets often exhibit diverse, feature-rich, unstructured data, and they are massive in size. This is the case of social networks, human genome, and e-commerce databases. As Artificial Intelligence (AI) systems are increasingly used to detect pattern in data and predict future outcome, there are growing concerns on their ability to process large amounts of data. Motivated by these concerns, we study the problem of designing AI systems that are scalable to very large and heterogeneous data-sets.
Many AI systems require to solve combinatorial optimization problems in their course of action. These optimization problems are typically NP-hard, and they may exhibit additional side constraints. However, the underlying objective functions often exhibit additional properties. These properties can be exploited to design suitable optimization algorithms. One of these properties is the well-studied notion of submodularity, which captures diminishing returns. Submodularity is often found in real-world applications. Furthermore, many relevant applications exhibit generalizations of this property.
In this thesis, we propose new scalable optimization algorithms for combinatorial problems with diminishing returns. Specifically, we focus on three problems, the Maximum Entropy Sampling problem, Video Summarization, and Feature Selection. For each problem, we propose new algorithms that work at scale. These algorithms are based on a variety of techniques, such as forward step-wise selection and adaptive sampling. Our proposed algorithms yield strong approximation guarantees, and the perform well experimentally.
We first study the Maximum Entropy Sampling problem. This problem consists of selecting a subset of random variables from a larger set, that maximize the entropy. By using diminishing return properties, we develop a simple forward step-wise selection optimization algorithm for this problem. Then, we study the problem of selecting a subset of frames, that represent a given video. Again, this problem corresponds to a submodular maximization problem. We provide a new adaptive sampling algorithm for this problem, suitable to handle the complex side constraints imposed by the application. We conclude by studying Feature Selection. In this case, the underlying objective functions generalize the notion of submodularity. We provide a new adaptive sequencing algorithm for this problem, based on the Orthogonal Matching Pursuit paradigm.
Overall, we study practically relevant combinatorial problems, and we propose new algorithms to solve them. We demonstrate that these algorithms are suitable to handle massive datasets. However, our analysis is not problem-specific, and our results can be applied to other domains, if diminishing return properties hold. We hope that the flexibility of our framework inspires further research into scalability in AI.
Purpose
This study investigates the communication behavior of public health organizations on Twitter during the COVID-19 vaccination campaign in Brazil. It contributes to the understanding of the organizational framing of health communication by showcasing several instances of framing devices that borrow from (Brazilian) internet culture. The investigation of this case extends the knowledge by providing a rich description of the organizational framing of health communication to combat misinformation in a politically charged environment.
Design/methodology/approach
The authors collected a Twitter dataset of 77,527 tweets and analyzed a purposeful subsample of 536 tweets that contained information provided by Brazilian public health organizations about COVID-19 vaccination campaigns. The data analysis was carried out quantitatively and qualitatively by combining social media analytics techniques and frame analysis.
Findings
The analysis showed that Brazilian health organizations used several framing devices that have been identified by previous literature such as hashtags, links, emojis or images. However, the analysis also unearthed hitherto unknown visual framing devices for misinformation prevention and debunking that borrow from internet culture such as “infographics,” “pop culture references” and “internet-native symbolism.”
Research limitations/implications
First, the identification of framing devices relating to internet culture add to our understanding of the so far little addressed framing of misinformation combat messages. The case of Brazilian health organizations provides a novel perspective to knowledge by offering a notion of internet-native symbols (e.g. humor, memes) and popular culture references for misinformation combat, including misinformation prevention. Second, this study introduces a frontier of political contextualization to misinformation research that does not relate to the partisanship of the spreaders but that relates to the political dilemmas of public organizations with a commitment to provide accurate information to citizens.
Practical implications
The findings inform decision-makers and public health organizations about framing devices that are tailored to internet-native audiences and can guide strategies to carry out information campaigns in misinformation-laden social media environments.
Social implications
The findings of this case study expose the often-overlooked cultural peculiarities of framing information campaigns on social media. The report of this study from a country in the Global South helps to contrast several assumptions and strategies that are prevalent in (health) discourses in Western societies and scholarship.
Originality/value
This study uncovers unconventional and barely addressed framing devices of health organizations operating in Brazil, which provides a novel perspective to the body of research on misinformation. It contributes to existing knowledge about frame analysis and broadens the understanding of frame devices borrowing from internet culture. It is a call for a frontier in misinformation research that deals with internet culture as part of organizational strategies for successful misinformation combat.
Sich mit dem eigenen Denken und Handeln reflexiv auseinanderzusetzen ist ein zentrales Element im Selbstreifungsprozess von Lehrkräften im Studium, über die Ausbildung bis hin zur Lehrer:innentätigkeit im Alltag. Der Workshop ermöglichte Zugänge zur selbstreflexiven Auseinandersetzung mit den eigenen Handlungsmustern mithilfe vom Autor (weiter)entwickelter Coachingtools, die im Rahmen der seminaristischen Lehrer:innenbildung in der zweiten Phase konzipiert und erprobt wurden.
Soil is today considered a non-renewable resource on societal time scale, as the rate of soil loss is higher than the one of soil formation.
Soil formation is complex, can take several thousands of years and is influenced by a variety of factors, one of them is time. Oftentimes, there is the assumption of constant and progressive conditions for soil and/or profile development (i.e., steady-state). In reality, for most of the soils, their (co-)evolution leads to a complex and irregular soil development in time and space characterised by “progressive” and “regressive” phases.
Lateral transport of soil material (i.e., soil erosion) is one of the principal processes shaping the land surface and soil profile during “regressive” phases and one of the major environmental problems the world faces.
Anthropogenic activities like agriculture can exacerbate soil erosion. Thus, it is of vital importance to distinguish short-term soil redistribution rates (i.e., within decades) influenced by human activities differ from long-term natural rates. To do so, soil erosion (and denudation) rates can be determined by using a set of isotope methods that cover different time scales at landscape level.
With the aim to unravel the co-evolution of weathering, soil profile development and lateral redistribution on a landscape level, we used Pluthonium-239+240 (239+240Pu), Beryllium-10 (10Be, in situ and meteoric) and Radiocarbon (14C) to calculate short- and long-term erosion rates in two settings, i.e., a natural and an anthropogenic environment in the hummocky ground moraine landscape of the Uckermark, North-eastern Germany. The main research questions were:
1. How do long-term and short-term rates of soil redistributing processes differ?
2. Are rates calculated from in situ 10Be comparable to those of using meteoric 10Be?
3. How do soil redistribution rates (short- and long-term) in an agricultural and in a natural landscape compare to each other?
4. Are the soil patterns observed in northern Germany purely a result of past events (natural and/or anthropogenic) or are they imbedded in ongoing processes?
Erosion and deposition are reflected in a catena of soil profiles with no or almost no erosion on flat positions (hilltop), strong erosion on the mid-slope and accumulation of soil material at the toeslope position. These three characteristic process domains were chosen within the CarboZALF-D experimental site, characterised by intense anthropogenic activities. Likewise, a hydrosequence in an ancient forest was chosen for this study and being regarded as a catena strongly influenced by natural soil transport.
The following main results were obtained using the above-mentioned range of isotope methods available to measure soil redistribution rates depending on the time scale needed (e.g., 239+240Pu, 10Be, 14C):
1. Short-term erosion rates are one order of magnitude higher than long-term rates in agricultural settings.
2. Both meteoric and in situ 10Be are suitable soil tracers to measure the long-term soil redistribution rates giving similar results in an anthropogenic environment for different landscape positions (e.g., hilltop, mid-slope, toeslope)
3. Short-term rates were extremely low/negligible in a natural landscape and very high in an agricultural landscape – -0.01 t ha-1 yr-1 (average value) and -25 t ha-1 yr-1 respectively. On the contrary, long-term rates in the forested landscape are comparable to those calculated in the agricultural area investigated with average values of -1.00 t ha-1 yr-1 and -0.79 t ha-1 yr-1.
4. Soil patterns observed in the forest might be due to human impact and activities started after the first settlements in the region, earlier than previously postulated, between 4.5 and 6.8 kyr BP, and not a result of recent soil erosion.
5. Furthermore, long-term soil redistribution rates are similar independently from the settings, meaning past natural soil mass redistribution processes still overshadow the present anthropogenic erosion processes.
Overall, this study could make important contributions to the deciphering of the co-evolution of weathering, soil profile development and lateral redistribution in North-eastern Germany. The multi-methodological approach used can be challenged by the application in a wider range of landscapes and geographic regions.
Interest rates are central determinants of saving and investment decisions. Costly financial intermediation distorts these price signals by creating a spread between deposit and loan rates. This study investigates how bank spreads affect climate policy in its ambition to redirect capital. We identify various channels through which interest spreads affect carbon emissions in a dynamic general equilibrium model. Interest rate spreads increase abatement costs due to the higher relative price for capital-intensive carbon-free energy, but they also tend to reduce emissions due to lower overall economic growth. For the global average interest rate spread of 5.1 percentage points, global warming increases by 0.2°C compared to the frictionless economy. For a given temperature target to be achieved, interest rate spreads necessitate substantially higher carbon taxes. When spreads arise from imperfect competition in the intermediation sector, the associated welfare costs can be reduced by clean energy subsidies or even eliminated by economy-wide investment subsidies.
The work is designed to investigate the impacts and sensitivity of climate change on water resources, droughts and hydropower production in Malawi, the South-Eastern region which is highly vulnerable to climate change. It is observed that rainfall is decreasing and temperature is increasing which calls for the understanding of what these changes may impact the water resources, drought occurrences and hydropower generation in the region. The study is conducted in the Greater Lake Malawi Basin (Lake Malawi and Shire River Basins) and is divided into three projects. The first study is assessing the variability and trends of both meteorological and hydrological droughts from 1970-2013 in Lake Malawi and Shire River basins using the standardized precipitation index (SPI) and standardized precipitation and evaporation Index (SPEI) for meteorological droughts and the lake level change index (LLCI) for hydrological droughts. And later the relationship of the meteorological and hydrological droughts is established.
While the second study extends the drought analysis into the future by examining the potential future meteorological water balance and associated drought characteristics such as the drought intensity (DI), drought months (DM), and drought events (DE) in the Greater Lake Malawi Basin. The sensitivity of drought to changes of rainfall and temperature is also assessed using the scenario-neutral approach. The climate change projections from 20 Coordinated Regional Climate Downscaling Experiment (CORDEX) models for Africa based on two scenarios (RCP4.5 and RCP8.5) for the periods 2021–2050 and 2071–2100 are used. The study also investigates the effect of bias-correction (i.e., empirical quantile mapping) on the ability of the climate model ensemble in reproducing observed drought characteristics as compared to raw climate projections.
The sensitivity of key hydrologic variables and hydropower generation to climate change in Lake Malawi and Shire River basins is assessed in third study. The study adapts the mesoscale Hydrological Model (mHM) which is applied separately in the Upper Lake Malawi and Shire River basins. A particular Lake Malawi model, which focuses on reservoir routing and lake water balance, has been developed and is interlinked between the two basins. Similar to second study, the scenario-neutral approach is also applied to determine the sensitivity of climate change on water resources more particularly Lake Malawi level and Shire River flow which later helps to estimate the hydropower production susceptibility.
Results suggest that meteorological droughts are increasing due to a decrease in precipitation which is exacerbated by an increase in temperature (potential evapotranspiration). The hydrological system of Lake Malawi seems to have a >24-month memory towards meteorological conditions since the 36-months SPEI can predict hydrological droughts ten-months in advance. The study has found the critical lake level that would trigger hydrological drought to be 474.1 m.a.s.l.
Despite the differences in the internal structures and uncertainties that exist among the climate models, they all agree on an increase of meteorological droughts in the future in terms of higher DI and longer events (DM). DI is projected to increase between +25% and +50% during 2021-2050 and between +131% and +388% during 2071-2100. This translates into +3 to +5, and +7 to +8 more drought months per year during both periods, respectively. With longer lasting drought events, DE is decreasing. Projected droughts based on RCP8.5 are 1.7 times more severe than droughts based on RCP4.5.
It is also found that an annual temperature increase of 1°C decreases mean lake level and outflow by 0.3 m and 17%, respectively, signifying the importance of intensified evaporation for Lake Malawi’s water budget. Meanwhile, a +5% (-5%) deviation in annual rainfall changes mean lake level by +0.7 m (-0.6 m). The combined effects of temperature increase and rainfall decrease result in significantly lower flows on Shire River. The hydrological river regime may change from perennial to seasonal with the combination of annual temperature increase and precipitation decrease beyond 1.5°C (3.5°C) and -20% (-15%). The study further projects a reduction in annual hydropower production between 1% (RCP8.5) and 2.5% (RCP4.5) during 2021–2050 and between 5% (RCP4.5) and 24% (RCP8.5) during 2071–2100.
The findings are later linked to global policies more particularly the United Nations Framework Convention on Climate Change (UNFCCC)’s Paris Agreement and the United Nations (UN)’s Sustainable Development Goals (SDGs), and how the failure to adhere the restriction of temperature increase below the global limit of 1.5°C will affect drought and the water resources in Malawi consequently impact the hydropower production. As a result, the achievement of most of the SDGs will be compromised.
The results show that it is of great importance that a further development of hydro energy on the Shire River should take into account the effects of climate change. The information generation is important for decision making more especially supporting the climate action required to fight against climate change. The frequency of extreme climate events due to climate change has reached the climate emergency as saving lives and livelihoods require urgent action.
This paper applies Monster Theory to the use of Greek mythology in three creator-owned comic series by female writers: InSEXts (2016 – 2017) by American comic writer Marguerite Bennett and Indonesian artist working in America Ariela Kristantina as well as Eros/Psyche (2021) and Porcelain (2021) by Maria Llovet, a comic writer and artist from Barcelona. In the first volume of InSEXts, set in Victorian London, there are allusions to the Furies and Pandora, linked with the discourse of the repression of women. In the second volume, set in the late nineteenth century Paris art world, the representation of classical subjects in art becomes a means to repress women, and a goddess with a Gorgon-like appearance takes revenge on the male repressors. In Eros/Psyche the story of Eros and Psyche and broken statues forms the backdrop and context for a tale of love and deception at a girls’ school, and in Porcelain a girl is faced with a choice of paths towards Eros or Thanatos, like Herakles at the crossroads choosing between the paths of virtue and vice. With reference to Cohen’s seven theses of Monster Culture I examine how Bennett and Lovett subvert the idea of the monster and the hero.
Planets outside our solar system, so-called "exoplanets", can be detected with different methods, and currently more than 5000 exoplanets have been confirmed, according to NASA Exoplanet Archive. One major highlight of the studies on exoplanets in the past twenty years is the characterization of their atmospheres usingtransmission spectroscopy as the exoplanet transits. However, this characterization is a challenging process and sometimes there are reported discrepancies in the literature regarding the atmosphere of the same exoplanet. One potential reason for the observed atmospheric inconsistencies is called impact parameter degeneracy, and it is highly driven by the limb darkening effect of the host star. A brief introductionto those topics in presented in chapter 1, while the motivation and objectives of thiswork are described in chapter 2.The first goal is to clarify the origin of the transmission spectrum, which is anindicator of an exoplanet’s atmosphere; whether it is real or influenced by the impactparameter degeneracy. A second goal is to determine whether photometry from space using the Transiting Exoplanet Survey Satellite (TESS), could improve on the major parameters, which are responsible for the aforementioned degeneracy, of known exoplanetary systems. Three individual projects were conducted in order toaddress those goals. The three manuscripts are presented, in short, in the manuscriptoverview in chapter 3.More specifically, in chapter 4, the first manuscript is presented, which is an ex-tended investigation on the impact parameter degeneracy and its application onsynthetic transmission spectra. Evidently, the limb darkening of the host star isan important driver for this effect. It keeps the degeneracy persisting through different groups of exoplanets, based on the uncertainty of their impact parameter and on the type of their host star. The second goal, was addressed in the second and third manuscripts (chapter 5 and chapter 6 respectively). Using observationsfrom the TESS mission, two samples of exoplanets were studied; 10 transiting inflated hot-Jupiters and 43 transiting grazing systems. Potentially, the refinement or confirmation of their major system parameters’ measurements can assist in solving current or future discrepancies regarding their atmospheric characterization.In chapter 7 the conclusions of this work are discussed, while in chapter 8 itis proposed how TESS’s measurements can be able to discern between erroneousinterpretations of transmission spectra, especially on systems where the impact parameter degeneracy is likely not applicable.
Chronologie der Englandreise
(2023)
Im Sommersemester 2022 wurde erstmalig die Lehrveranstaltung „Chemieunterricht für heterogene Lerngruppen“ angeboten. Diese Lehrveranstaltung ist im Rahmen von PSI-Potsdam im Schwerpunkt „Inklusion und Heterogenität“ entstanden. Die Lehrveranstaltung wurde synchron online durchgeführt. Die Studierenden erhielten viele Möglichkeiten zur Diskussion sowie zur selbstständigen Erstellung von Unterrichtsmaterialien. Zum erfolgreichen Abschluss des Moduls erstellten die Studierenden ein Portfolio zu einem selbst gewählten Thema. Die Lehrveranstaltung wurde von den Studierenden sehr gut bewertet.
Charitable giving
(2023)
We investigate how different levels of information influence the allocation decisions of donors who are entitled to freely distribute a fixed monetary endowment between themselves and a charitable organization in both giving and taking frames. Participants donate significantly higher amounts, when the decision is described as taking rather than giving. This framing effect becomes smaller if more information about the charity is provided.
This thesis discusses heat and charge transport phenomena in single-crystalline Silicon penetrated by nanometer-sized pores, known as mesoporous Silicon (pSi). Despite the extensive attention given to it as a thermoelectric material of interest, studies on microscopic thermal and electronic transport beyond its macroscopic characterizations are rarely reported. In contrast, this work reports the interplay of both.
PSi samples synthesized by electrochemical anodization display a temperature dependence of specific heat 𝐶𝑝 that deviates from the characteristic 𝑇^3 behaviour (at 𝑇<50𝐾). A thorough analysis reveals that both 3D and 2D Einstein and Debye modes contribute to this specific heat. Additional 2D Einstein modes (~3 𝑚𝑒𝑉) agree reasonably well with the boson peak of SiO2 in pSi pore walls. 2D Debye modes are proposed to account for surface acoustic modes causing a significant deviation from the well-known 𝑇^3 dependence of 𝐶𝑝 at 𝑇<50𝐾.
A novel theoretical model gives insights into the thermal conductivity of pSi in terms of porosity and phonon scattering on the nanoscale. The thermal conductivity analysis utilizes the peculiarities of the pSi phonon dispersion probed by the inelastic neutron scattering experiments. A phonon mean-free path of around 10 𝑛𝑚 extracted from the presented model is proposed to cause the reduced thermal conductivity of pSi by two orders of magnitude compared to p-doped bulk Silicon. Detailed analysis indicates that compound averaging may cause a further 10-50% reduction. The percolation threshold of 65% for thermal conductivity of pSi samples is subsequently determined by employing theoretical effective medium models.
Temperature-dependent electrical conductivity measurements reveal a thermally activated transport process. A detailed analysis of the activation energy 𝐸𝐴𝜎 in the thermally activated transport exhibits a Meyer Neldel compensation rule between different samples that originates in multi-phonon absorption upon carrier transport. Activation energies 𝐸𝐴𝑆 obtained from temperature-dependent thermopower measurements provide further evidence for multi-phonon assisted hopping between localized states as a dominant charge transport mechanism in pSi, as they systematically differ from the determined 𝐸𝐴𝜎 values.
Dielektrophorese ist die Manipulation polarisierbarer Partikel durch inhomogene elektrische Wechselfelder. In dieser Arbeit wurden drei verschiedene Enzyme durch Dielektrophorese immobilisiert und anschließend hinsichtlich ihrer katalytischen Aktivität untersucht: Meerrettichperoxidase, Cholinoxidase aus Alcaligenes sp. und Glucoseoxidase aus Aspergillus niger. Die Immobilisierung erfolgte durch Dielektrophorese auf nano-Elektrodenarrays aus Wolfram-Zylindern mit 500 nm Durchmesser oder aus Titannitrid-Ringen mit 20 nm Breite. Die Immobilisierung der Enzyme konnte fluoreszenzmikroskopisch entweder anhand der intrinsischen Fluoreszenz oder aufgrund einer Fluoreszenzmarkierung vor oder nach der Immobilisierung für alle getesteten Enzyme nachgewiesen werden. Die Messung der Enzymaktivität erfolgte quantitativ durch den direkten oder indirekten Nachweis des gebildeten Produktes oder, im Falle der Cholinoxidase, durch Beobachtung der intrinsischen Fluoreszenz des Cofaktors FAD, die vom Oxidationszustand dieses Enzyms abhängt. Für die Meerrettichperoxidase konnte so eine hohe erhaltene Enzymaktivität nach der Immobilisierung nachgewiesen werden. Die Aktivität der permanent immobilisierten Fraktion der Meerrettichperoxidase entsprach bis zu 47 % der höchstmöglichen Aktivität einer Monolage dieses Enzyms auf den Elektroden des Chips. Diese Aktivität kann als aktive, aber zufällig gegenüber der Oberfläche ausgerichtete Enzymschicht interpretiert werden. Für die permanent immobilisierte Glucoseoxidase wurde nur eine Aktivität entsprechend <1,3 % der Aktivität einer solchen Enzymschicht detektiert, während für die immobilisierte Cholinoxidase gar keine Aktivität nachgewiesen werden konnte. Die Aktivität der durch DEP immobilisierten Enzyme konnte somit quantitativ bestimmt werden. Der Anteil an erhaltener Aktivität hängt dabei stark vom verwendeten Enzym ab.
Heat stress (HS) is one of the major abiotic stresses which adversely affects the survival and growth of plants due to their sessile nature. To combat the detrimental effects of HS and develop thermotolerance, plants have evolved several defense mechanisms. Thermomemory is one such molecular mechanism whereby plants that have been acclimated (or primed/P) by a moderate HS can respond more efficiently and continue their growth after exposure to a severe or lethal HS (called triggering/T), while unprimed plants cannot survive. Thermomemory is known to be regulated by several transcription factors (TFs), epigenetic changes, chromatin remodellers, post-transcriptional changes and it also involves protein stability control and primary metabolism adjustment. Recent research has suggested that the shoot apical meristem (SAM) in Arabidopsis thaliana has a distinct transcriptional thermomemory which is possibly regulated by eight TFs called HEAT SHOCK FACTORS (HSFs). The main objective of this PhD thesis is to investigate the role of HSFA7b (one of the eight HSFs), in regulating thermomemory at the SAM by identifying the molecular networks it regulates. HSFA7a, a close homolog of HSFA7b, is also one of the eight HSFs that are involved in regulating thermomemory at the SAM. Thermomemory was found to be defective in the hsfa7b and hsfa7a hsfa7b mutants; the percentage survival of these seedlings was significantly lower than in wild-type (WT) seedlings after the priming and triggering (PT) treatment. Transcriptome and ChIP analyses were performed to identify the molecular networks controlled by HSFA7b and its close homolog HSFA7a, in regulating thermomemory at the SAM. The chromatin regulator SPLAYED (SYD) was found to be regulated by both HSFA7a and HSFA7b at the SAM during thermomemory. SYD is directly involved in SAM maintenance by directly regulating WUSCHEL (WUS), a master regulator of stem cell maintenance. WUS expression was down-regulated at the SAM of PT treated hsfa7a/b mutants compared to WT-Col-0 seedlings. HSFA7a and HSFA7b also jointly regulate the expression of orphan gene QUA QUINE STARCH (QQS) during thermomemory. Starch accumulation negatively correlates with QQS expression and this trend was observed in WT plants in response to thermopriming. The remobilization of starch was affected in the hsfa7a/b mutants compared to WT plants during the recovery period after T treatment. These findings indicate that defects in SAM maintenance and starch remobilization could possibly contribute to the reduced thermomemory in the hsfa7a/b mutants. Moreover, transcriptome and ChIP analysis indicate that ethylene signaling genes are directly regulated by HSFA7b during thermomemory. Transcriptome analysis of the HSFA7b-IOE line indicates that HSFA7b positively regulates the expression of HEAT STRESS ASSOCIATED 32 (HSA32), an important thermomemory gene, and HSFA7b strongly suppresses the expression of the reactive oxygen species (ROS) responsive REDOX RESPONSIVE TRANSCRIPTION FACTOR 1 (RRTF1) gene, which is also a repressed target of SYD. In Arabidopsis, the HSFA7b transcript undergoes alternative splicing at high temperatures to form two splice variants: one correctly/constitutively spliced variant which is functional and codes for the HSFA7b protein and one intron retained splice variant. Higher accumulation of the functional HSFA7b splice variant was found at the SAM compared to other tissues. Moreover, accumulation of the functional splice variant was higher in P and PT plants compared to control plants, whereas higher levels of the intron retained splice variant is found in plants subjected directly to the T treatment. The intron retained HSFA7b splice variant is degraded by the non-sense mediated decay (NMD) pathway as a means of regulating transcript level essential for protein synthesis at high temperatures. Importantly, HSFA7b protein accumulation was observed in plants subjected to PT treatment that survive and continue growth, but not in plants subjected directly to T treatment that do not survive, indicating that constitutive/ correct splicing of the HSFA7b transcript is a component of thermomemory. Taken together, these findings suggest that HSFA7a and HSFA7b jointly regulate SAM maintenance via the chromatin remodeller SYD and starch remobilization via QQS. In addition to them, HSFA7b also regulates the expression of ethylene signaling genes, heat responsive genes and the ROS responsive RRTF1. Furthermore, constitutive/correct splicing in the HSFA7b transcript is also an essential component of thermomemory.
The trace elements, selenium (Se) and copper (Cu) play an important role in maintaining normal brain function. Since they have essential functions as cofactors of enzymes or structural components of proteins, an optimal supply as well as a well-defined homeostatic regulation are crucial. Disturbances in trace element homeostasis affect the health status and contribute to the incidence and severity of various diseases. The brain in particular is vulnerable to oxidative stress due to its extensive oxygen consumption and high energy turnover, among other factors. As components of a number of antioxidant enzymes, both elements are involved in redox homeostasis. However, high concentrations are also associated with the occurrence of oxidative stress, which can induce cellular damage. Especially high Cu concentrations in some brain areas are associated with the development and progression of neurodegenerative diseases such as Alzheimer's disease (AD). In contrast, reduced Se levels were measured in brains of AD patients. The opposing behavior of Cu and Se renders the study of these two trace elements as well as the interactions between them being particularly relevant and addressed in this work.
In this work, binding interactions between biomolecules were analyzed by a technique that is based on electrically controllable DNA nanolevers. The technique was applied to virus-receptor interactions for the first time. As receptors, primarily peptides on DNA nanostructures and antibodies were utilized. The DNA nanostructures were integrated into the measurement technique and enabled the presentation of the peptides in a controllable geometrical order. The number of peptides could be varied to be compatible to the binding sites of the viral surface proteins.
Influenza A virus served as a model system, on which the general measurability was demonstrated. Variations of the receptor peptide, the surface ligand density, the measurement temperature and the virus subtypes showed the sensitivity and applicability of the technology. Additionally, the immobilization of virus particles enabled the measurement of differences in oligovalent binding of DNA-peptide nanostructures to the viral proteins in their native environment.
When the coronavirus pandemic broke out in 2020, work on binding interactions of a peptide from the hACE2 receptor and the spike protein of the SARS-CoV-2 virus revealed that oligovalent binding can be quantified in the switchSENSE technology. It could also be shown that small changes in the amino acid sequence of the spike protein resulted in complete loss of binding. Interactions of the peptide and inactivated virus material as well as pseudo virus particles could be measured. Additionally, the switchSENSE technology was utilized to rank six antibodies for their binding affinity towards the nucleocapsid protein of SARS-CoV-2 for the development of a rapid antigen test device.
The technique was furthermore employed to show binding of a non-enveloped virus (adenovirus) and a virus-like particle (norovirus-like particle) to antibodies. Apart from binding interactions, the use of DNA origami levers with a length of around 50 nm enabled the switching of virus material. This proved that the technology is also able to size objects with a hydrodynamic diameter larger than 14 nm.
A theoretical work on diffusion and reaction-limited binding interactions revealed that the technique and the chosen parameters enable the determination of binding rate constants in the reaction-limited regime.
Overall, the applicability of the switchSENSE technique to virus-receptor binding interactions could be demonstrated on multiple examples. While there are challenges that remain, the setup enables the determination of affinities between viruses and receptors in their native environment. Especially the possibilities regarding the quantification of oligo- and multivalent binding interactions could be presented.
Challenges and proposals for introducing digital certificates in higher education infrastructures
(2023)
Questions about the recognition of MOOCs within and outside higher education were already being raised in the early 2010s. Today, recognition decisions are still made more or less on a case-by-case basis. However, digital certification approaches are now emerging that could automate recognition processes. The technical development of the required machinereadable documents and infrastructures is already well advanced in some cases. The DigiCerts consortium has developed a solution based on a collective blockchain. There are ongoing and open discussions regarding the particular technology, but the institutional implementation of digital certificates raises further questions. A number of workshops have been held at the Institute for Interactive Systems at Technische Hochschule Lübeck, which have identified the need for new responsibilities for issuing certificates. It has also become clear that all members of higher education institutions need to develop skills in the use of digital certificates.
The analysis of event time series is in general challenging. Most time series analysis tools are limited for the analysis of this kind of data. Recurrence analysis, a powerful concept from nonlinear time series analysis, provides several opportunities to work with event data and even for the most challenging task of comparing event time series with continuous time series. Here, the basic concept is introduced, the challenges are discussed, and the future perspectives are summarized.
To implement OERs at HEIs sustainably, not just technical infrastructure is required, but also well-trained staff. The University of Graz is in charge of an OER training program for university staff as part of the collaborative project Open Education Austria Advanced (OEAA) with the aim of ensuring long-term competence growth in the use and creation of OERs. The program consists of a MOOC and a guided blended learning format that was evaluated to find out which accompanying teaching and learning concepts can best facilitate targeted competence development. The evaluation of the program shows that learning videos, self-study assignments and synchronous sessions are most useful for the learning process. The results indicate that the creation of OERs is a complex process that can be undergone more effectively in the guided program.
Continental rifts are key geodynamic regions where the complex interplay of magmatism and faulting activity can be studied to understand the driving forces of extension and the formation of new divergent plate boundaries. Well-preserved rift morphology can provide a wealth of information on the growth, interaction, and linkage of normal-fault systems through time. If rift basins are preserved over longer geologic time periods, sedimentary archives generated during extensional processes may mirror tectonic and climatic influences on erosional and sedimentary processes that have varied over time. Rift basins are furthermore strategic areas for hydrocarbon and geothermal energy exploration, and they play a central role in species dispersal and evolution as well as providing or inhibiting hydrologic connectivity along basins at emerging plate boundaries.
The Cenozoic East African rift system (EARS) is one of the most important continental extension zones, reflecting a range of evolutionary stages from an early rift stage with isolated basins in Malawi to an advanced stage of continental extension in southern Afar. Consequently, the EARS is an ideal natural laboratory that lends itself to the study of different stages in the breakup of a continent. The volcanically and seismically active eastern branch of the EARS is characterized by multiple, laterally offset tectonic and magmatic segments where adjacent extensional basins facilitate crustal extension either across a broad deformation zone or via major transfer faulting. The Broadly Rifted Zone (BRZ) in southern Ethiopia is an integral part of the eastern branch of the EARS; in this region, rift segments of the southern Ethiopian Rift (sMER) and northern Kenyan Rift (nKR) propagate in opposite directions in a region with one of the earliest manifestations of volcanism and extensional tectonism in East Africa. The basin margins of the Chew-Bahir Basin and the Gofa Province, characterized by a semi-arid climate and largely uniform lithology, provide ideal conditions for studying the tectonic and geomorphologic features of this complex kinematic transfer zone, but more importantly, this area is suitable for characterizing and quantifying the overlap between the propagating structures of the sMER and nKR and the resulting deformation patterns of the BRZ transfer zones.
In this study, I have combined data from thermochronology, thermal modeling, morphometry, paleomagnetic analysis, geochronology, and geomorphological field observations with information from published studies to reconstruct the spatiotemporal relationship between volcanism and fault activity in the BRZ and quantify the deformation patterns of the overlapping rift segments. I present the following results: (1) new thermochronological data from the en-échelon basin margins and footwall blocks of the rift flanks and morphometric results verified in the field to link different phases of magmatism and faulting during extension and infer geomorphological landscape features related to the current tectonic interaction between the nKR and the sMER; (2) temporally constrained paleomagnetic data from the BRZ overlap zone between the Ethiopian and Kenyan rifts to quantitatively determine block rotation between the two segments. Combining the collected data, time-temperature histories of thermal modeling results from representative samples show well-defined deformation phases between 25–20 Ma, 15–9Ma, and ~5 Ma to the present. Each deformation phase is characterized by the onset of rapid cooling (>2°C/Ma) of the crust associated with uplift or exhumation of the rift shoulder. After an initial, spatially very diffuse phase of extension, the rift has gradually evolved into a system of connected structures formed in an increasingly focused rift zone during the last 5 Ma. Regarding the morphometric analysis of the rift structures, it can be shown that normalized slope indices of the river courses, spatial arrangement of knickpoints in the river longitudinal profiles of the footwall blocks, local relief values, and the average maximum values of the slope of the river profiles indicate a gradual increase in the extension rate from north (Sawula basin: mature) to south (Chew Bahir: young). The complexity of the structural evolution of the BRZ overlap zone between nKR and sMER is further emphasized by the documentation of crustal blocks around a vertical axis. A comparison of the mean directions obtained for the Eo-Oligocene (Ds=352.6°, Is=-17.0°, N=18, α95=5.5°) and Miocene (Ds=2.9°, Is=0.9°, N=9, α95=12.4°) volcanics relative to the pole for stable South Africa and with respect to the corresponding ages of the analyzed units record a significant counterclockwise rotation of ~11.1°± 6.4° and insignificant CCW rotation of ~3.2° ± 11.5°, respectively.
Cell-level systems biology model to study inflammatory bowel diseases and their treatment options
(2023)
To help understand the complex and therapeutically challenging inflammatory bowel diseases (IBDs), we developed a systems biology model of the intestinal immune system that is able to describe main aspects of IBD and different treatment modalities thereof. The model, including key cell types and processes of the mucosal immune response, compiles a large amount of isolated experimental findings from literature into a larger context and allows for simulations of different inflammation scenarios based on the underlying data and assumptions. In the context of a large and diverse virtual IBD population, we characterized the patients based on their phenotype (in contrast to healthy individuals, they developed persistent inflammation after a trigger event) rather than on a priori assumptions on parameter differences to a healthy individual. This allowed to reproduce the enormous diversity of predispositions known to lead to IBD. Analyzing different treatment effects, the model provides insight into characteristics of individual drug therapy. We illustrate for anti-TNF-alpha therapy, how the model can be used (i) to decide for alternative treatments with best prospects in the case of nonresponse, and (ii) to identify promising combination therapies with other available treatment options.
Case report
(2023)
The increasing prevalence of Long COVID is an imminent public health disaster, and established approaches have not provided adequate diagnostics or treatments. Recently, anesthetic blockade of the stellate ganglion was reported to improve Long COVID symptoms in a small case series, purportedly by "rebooting" the autonomic nervous system. Here, we present a novel diagnostic approach based on the Adaptive Force (AF), and report sustained positive outcome for one severely affected Long COVID patient using individualized pulsed electromagnetic field (PEMF) at the area C7/T1. AF reflects the capacity of the neuromuscular system to adapt adequately to external forces in an isometric holding manner. In case, maximal isometric AF (AFiso(max)) is exceeded, the muscle merges into eccentric muscle action. Thereby, the force usually increases further until maximal AF (AFmax) is reached. In case adaptation is optimal, AFiso(max) is similar to 99-100% of AFmax. This holding capacity (AFiso(max)) was found to be vulnerable to disruption by unpleasant stimulus and, hence, was regarded as functional parameter. AF was assessed by an objectified manual muscle test using a handheld device. Prior to treatment, AFiso(max) was considerably lower than AFmax for hip flexors (62 N = similar to 28% AFmax) and elbow flexors (71 N = similar to 44% AFmax); i.e., maximal holding capacity was significantly reduced, indicating dysfunctional motor control. We tested PEMF at C7/T1, identified a frequency that improved neuromuscular function, and applied it for similar to 15 min. Immediately post-treatment, AFiso(max) increased to similar to 210 N (similar to 100% AFmax) at hip and 184 N (similar to 100% AFmax) at elbow. Subjective Long COVID symptoms resolved the following day. At 4 weeks post-treatment, maximal holding capacity was still on a similarly high level as for immediately post-treatment (similar to 100% AFmax) and patient was symptom-free. At 6 months the patient's Long COVID symptoms have not returned. This case report suggests (1) AF could be a promising diagnostic for post-infectious illness, (2) AF can be used to test effective treatments for post-infectious illness, and (3) individualized PEMF may resolve post-infectious symptoms.
Solar photocatalysis is the one of leading concepts of research in the current paradigm of sustainable chemical industry. For actual practical implementation of sunlight-driven catalytic processes in organic synthesis, a cheap, efficient, versatile and robust heterogeneous catalyst is necessary. Carbon nitrides are a class of organic semiconductors who are known to fulfill these requirements.
First, current state of solar photocatalysis in economy, industry and lab research is overviewed, outlining EU project funding, prospective synthetic and reforming bulk processes, small scale solar organic chemistry, and existing reactor designs and prototypes, concluding feasibility of the approach.
Then, the photocatalytic aerobic cleavage of oximes to corresponding aldehydes and ketones by anionic poly(heptazine imide) carbon nitride is discussed. The reaction provides a feasible method of deprotection and formation of carbonyl compounds from nitrosation products and serves as a convenient model to study chromoselectivity and photophysics of energy transfer in heterogeneous photocatalysis.
Afterwards, the ability of mesoporous graphitic carbon nitride to conduct proton-coupled electron transfer was utilized for the direct oxygenation of 1,3-oxazolidin-2-ones to corresponding 1,3-oxazlidine-2,4-diones. This reaction provides an easier access to a key scaffold of diverse types of drugs and agrochemicals.
Finally, a series of novel carbon nitrides based on poly(triazine imide) and poly(heptazine imide) structure was synthesized from cyanamide and potassium rhodizonate. These catalysts demonstrated a good performance in a set of photocatalytic benchmark reactions, including aerobic oxidation, dual nickel photoredox catalysis, hydrogen peroxide evolution and chromoselective transformation of organosulfur precursors.
Concluding, the scope of carbon nitride utilization for net-oxidative and net-neutral photocatalytic processes was expanded, and a new tunable platform for catalyst synthesis was discovered.
Carbon nitride semiconductors: properties and application as photocatalysts in organic synthesis
(2023)
Graphitic carbon nitrides (g-CNs) are represented by melon-type g-CN, poly(heptazine imides) (PHIs), triazine-based g-CN and poly(triazine imide) with intercalated LiCl (PTI/Li+Cl‒). These materials are composed of sp2-hybridized carbon and nitrogen atoms; C:N ratio is close to 3:4; the building unit is 1,3,5-triazine or tri-s-triazine; the building units are interconnected covalently via sp2-hybridized nitrogen atoms or NH-moieties; the layers are assembled into a stack via weak van der Waals forces as in graphite. Due to medium band gap (~2.7 eV) g-CNs, such as melon-type g-CN and PHIs, are excited by photons with wavelength ≤ 460 nm. Since 2009 g-CNs have been actively studied as photocatalysts in evolution of hydrogen and oxygen – two half-reactions of full water splitting, by employing corresponding sacrificial agents. At the same time application of g-CNs as photocatalysts in organic synthesis has been remaining limited to few reactions only. Cumulative Habilitation summarizes research work conducted by the group ‘Innovative Heterogeneous Photocatalysis’ between 2017-2023 in the field of carbon nitride organic photocatalysis, which is led by Dr. Oleksandr Savatieiev.
g-CN photocatalysts activate molecules, i.e. generate their more reactive open-shell intermediates, via three modes: i) Photoinduced electron transfer (PET); ii) Excited state proton-coupled electron transfer (ES-PCET) or direct hydrogen atom transfer (dHAT); iii) Energy transfer (EnT). The scope of reactions that proceed via oxidative PET, i.e. one-electron oxidation of a substrate to the corresponding radical cation, are represented by synthesis of sulfonylchlorides from S-acetylthiophenols. The scope of reactions that proceed via reductive PET, i.e. one-electron reduction of a substrate to the corresponding radical anion, are represented by synthesis of γ,γ-dichloroketones from the enones and chloroform.
Due to abundance of sp2-hybridized nitrogen atoms in the structure of g-CN materials, they are able to cleave X-H bonds in organic molecules and store temporary hydrogen atom. ES-PCET or dHAT mode of organic molecules activation to the corresponding radicals is implemented for substrates featuring relatively acidic X-H bonds and those that are characterized by low bond dissociation energy, such as C-H bond next to the heteroelements. On the other hand, reductively quenched g-CN carrying hydrogen atom reduces a carbonyl compound to the ketyl radical via PCET that is thermodynamically more favorable pathway compared to the electron transfer. The scope of these reactions is represented by cyclodimerization of α,β-unsaturated ketones to cyclopentanoles.
g-CN excited state demonstrates complex dynamics with the initial formation of singlet excited state, which upon intersystem crossing produces triplet excited state that is characterized by the lifetime > 2 μs. Due to long lifetime, g-CN activate organic molecules via EnT. For example, g-CN sensitizes singlet oxygen, which is the key intermediate in the dehydrogenation of aldoximes to nitrileoxides. The transient nitrileoxide undergoes [3+2]-cycloaddition to nitriles and gives oxadiazoles-1,2,4.
PET, ES-PCET and EnT are fundamental phenomena that are applied beyond organic photocatalysis. Hybrid composite is formed by combining conductive polymers, such as poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) with potassium poly(heptazine imide) (K-PHI). Upon PET, K-PHI modulated population of polarons and therefore conductivity of PEDOT:PSS. The initial state of PEDOT:PSS is recovered upon material exposure to O2. K-PHI:PEDOT:PSS may be applied in O2 sensing.
In the presence of electron donors, such as tertiary amines and alcohols, and irradiation with light, K-PHI undergoes photocharging – the g-CN material accumulates electrons and charge-compensating cations. Such photocharged state is stable under anaerobic conditions for weeks, but at the same time it is a strong reductant. This feature allows decoupling in time light harvesting and energy storage in the form of electron-proton couples from utilization in organic synthesis. The photocharged state of K-PHI reduces nitrobenzene to aniline, and enables dimerization of α,β-unsaturated ketones to hexadienones in dark.
The urge of light utilization in fabrication of materials is as encouraging as challenging. Steadily increasing energy consumption in accordance with rapid population growth, is requiring a corresponding solution within the same rate of occurrence speed. Therefore, creating, designing and manufacturing materials that can interact with light and in further be applicable as well as disposable in photo-based applications are very much under attention of researchers. In the era of sustainability for renewable energy systems, semiconductor-based photoactive materials have received great attention not only based on solar and/or hydrocarbon fuels generation from solar energy, but also successful stimulation of photocatalytic reactions such as water splitting, pollutant degradation and organic molecule synthesisThe turning point had been reached for water splitting with an electrochemical cell consisting of TiO2-Pt electrode illuminated by UV light as energy source rather than an external voltage, that successfully pursued water photolysis by Fujishima and Honda in 1972. Ever since, there has been a great deal of interest in research of semiconductors (e.g. metal oxide, metal-free organic, noble-metal complex) exhibiting effective band gap for photochemical reactions. In the case of environmental friendliness, toxicity of metal-based semiconductors brings some restrictions in possible applications. Regarding this, very robust and ‘earth-abundant’ organic semiconductor, graphitic carbon nitride has been synthesized and successfully applied in photoinduced applications as novel photocatalyst. Properties such as suitable band gap, low charge carrier recombination and feasibility for scaling up, pave the way of advance combination with other catalysts to gather higher photoactivity based on compatible heterojunction.
This dissertation aims to demonstrate a series of combinations between organic semiconductor g-CN and polymer materials that are forged through photochemistry, either in synthesis or in application. Fabrication and design processes as well as applications performed in accordance to the scope of thesis will be elucidated in detail. In addition to UV light, more attention is placed on visible light as energy source with a vision of more sustainability and better scalability in creation of novel materials and solar energy based applications.
Focusing on the passive use of Instagram, we apply the affordance perspective to deeply explore its use and use-related outcomes. In the qualitative study, we uncover the affordances of focal social media features. Two distinct groups of affordances (self- and others-oriented) emerge. Following the grounded theory methodology, we develop the affordances-actualizations-outcomes model, explaining how immediate goals associated with features translate into outcomes. In the quantitative study, we test the model by applying structural equation modeling. Our findings confirm that actualizations of self- and others-oriented affordances are associated with distinct outcomes: social connectedness, positive affect, and overall satisfaction with Instagram experience.
Brasilien in den BRICS
(2023)
Art. 1 Abs. 2 Buchst. b der RL 93/83/EWG des Rates vom 27. September 1993 zur Koordinierung bestimmter urheber- und leistungsschutzrechtlicher Vorschriften betreffend Satellitenrundfunk und Kabelweiterverbreitung ist dahin auszulegen, dass ein Satellitenbouquet-Anbieter, der verpflichtet ist, für eine Handlung in Form der öffentlichen Wiedergabe über Satellit, an der er mitwirkt, die Zustimmung der Inhaber der betreffenden Urheberrechte und verwandten Schutzrechte einzuholen, diese Zustimmung – entsprechend der dem betreffenden Sendeunternehmen erteilten Zustimmung – nur in dem Mitgliedstaat einholen muss, in dem die programmtragenden Signale in die zum Satelliten führende Kommunikationskette eingegeben werden.
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.
Biostimulant SuperFifty based molecular priming to increase plant strength and stress tolerance
(2023)
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.
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.
Biogeochemical analyses of lacustrine environments are well-established methods that allow exploring and understanding complex systems in the lake ecosystem. However, most were conducted in temperate lakes controlled by entirely different physical conditions than in tropical climates. The most important difference between the temperate and tropical lakes is lacking seasonal temperature fluctuations in the latter, which leads to a stable temperature gradient in the water column. Thus, the water column in tropical latitudes generally is void of perturbations that can be seen in their temperate counterparts. Permanent stratification in the water column provides optimal conditions for intact sedimentation. The geochemical processes in the water column and the weathering process in the distinct lithology in the catchment leads to the different biogeochemical characteristic in the sediment. Conducting a biogeochemical study in this lake sediment, especially in the Sediment Water Interface (SWI) helps reveal the sedimentation and diagenetic process records influenced by the internal or external loading. Lake Sentani, the study area, is one of the thousands of lakes in Indonesia and located in the Papua province. This tropical lake has a unique feature, as it consists of four interconnected sub-basins with different water depths. More importantly, its catchment is comprised of various different lithologies. Hence, its lithological characteristics are highly diverse, and range from mafic and ultramafic rocks to clastic sediment and carbonates. Each sub-basin receives a distinct sediment input. Equally important, besides the natural loading, Lake Sentani is also influenced by anthropogenic input. Previous studies have elaborated that there is an increase in population growth rate around the lake which has direct consequences on eutrophication. Considering these factors, the government of The Republic of Indonesia put Lake Sentani on the list of national priority lakes for restoration. This thesis aims to develop a fundamental understanding of Lake Sentani's sedimentary geochemistry and geomicrobiology with a special focus on the effects of different lithologies and anthropogenic pressures in the catchment area. We conducted geochemical and geomicrobiology research on Lake Sentani to meet this objective. We investigated geochemical characteristics in the water column, porewater, and sediment core of the four sub-basins. Additional to direct investigations of the lake itself, we also studied the sediments in the tributary rivers, of which some are ephemeral, as well as the river mouths, as connections between riverine and the lacustrine habitat. The thesis is composed of three main publications about Lake Sentani and supported by several publications that focus on other tropical lakes in Indonesia. The first main publication investigates the geochemical characterization of the water column, porewater, and surface sediment (upper 40-50 cm) from the center of the four sub-basins. It reveals that besides catchment lithology, the water column heavily influences the geochemical characteristics in the lake sediments and their porewater. The findings indicate that water column stratification has a strong influence on overall chemistry. The four sub-basins are very different with regard to their water column chemistry. Based on the physicochemical profiles, especially dissolved oxygen, one sub-basin is oxygenated, one intermediate i.e. just reaches oxygen depletion at the sediment-water interface, and two sub-basins are fully meromictic. However, all four sub-basins share the same surface water chemistry. The structure of the water column creates differences on the patterns of anions and cations in the porewater. Likewise, the distinct differences in geochemical composition between the sub-basins show that the lithology in the catchment affects the geochemical characteristic in the sediment. Overall, water column stratification and particularly bottom water oxygenation strongly influence the overall elemental composition of the sediment and porewater composition. The second publication reveals differences in surface sediment composition between habitats, influenced by lithological variations in the catchment area. The macro-element distribution shows that the geochemical characteristics between habitats are different. Furthermore, the geochemical composition also indicates a distinct distribution between the sub-basins. The geochemical composition of the eastern sub-basin suggests that lithogenic elements are more dominant than authigenic elements. This is also supported by sulfide speciation, particle distribution, and smear slide data. The third publication is a geomicrobiological study of the surface sediment. We compare the geochemical composition of the surface sediment and its microbiological composition and compare the different signals. Next Generation Sequencing (NGS) of the 16S rRNA gene was applied to determine the microbial community composition of the surface sediment from a great number of locations. We use a large number of sampling sites in all four sub-basins as well as in the rivers and river mouths to illustrate the links between the river, the river mouth, and the lake. Rigorous assessment of microbial communities across the diverse Lake Sentani habitats allowed us to study some of these links and report novel findings on microbial patterns in such ecosystems. The main result of the Principal Coordinates Analysis (PCoA) based on microbial community composition highlighted some commonalities but also differences between the microbial community analysis and the geochemical data. The microbial community in rivers, river mouths and sub-basins is strongly influenced by anthropogenic input from the catchment area. Generally, Bacteroidetes and Firmicutes could be an indicator for river sediments. The microbial community in the river is directly influenced by anthropogenic pressure and is markedly different from the lake sediment. Meanwhile, the microbial community in the lake sediment reflects the anoxic environment, which is prevalent across the lake in all sediments below a few mm burial depth. The lake sediments harbour abundant sulfate reducers and methanogens. The microbial communities in sediments from river mouths are influenced by both rivers and lake ecosystems. This study provides valuable information to understand the basic processes that control biogeochemical cycling in Lake Sentani. Our findings are critical for lake managers to accurately assess the uncertainties of the changing environmental conditions related to the anthropogenic pressure in the catchment area. Lake Sentani is a unique study site directly influenced by the different geology across the watershed and morphometry of the four studied basins. As a result of these factors, there are distinct geochemical differences between the habitats (river, river mouth, lake) and the four sub-basins. In addition to geochemistry, microbial community composition also shows differences between habitats, although there are no obvious differences between the four sub-basins. However, unlike sediment geochemistry, microbial community composition is impacted by human activities. Therefore, this thesis will provide crucial baseline data for future lake management.
Controlling bioenergy-induced land-use-change emissions is key to exploiting bioenergy for climate change mitigation. However, the effect of different land-use and energy sector policies on specific bioenergy emissions has not been studied so far. Using the global integrated assessment model REMIND-MAgPIE, we derive a biofuel emission factor (EF) for different policy frameworks. We find that a uniform price on emissions from both sectors keeps biofuel emissions at 12 kg CO2 GJ−1. However, without land-use regulation, the EF increases substantially (64 kg CO2 GJ−1 over 80 years, 92 kg CO2 GJ−1 over 30 years). We also find that comprehensive coverage (>90%) of carbon-rich land areas worldwide is key to containing land-use emissions. Pricing emissions indirectly on the level of bioenergy consumption reduces total emissions by cutting bioenergy demand but fails to reduce the average EF. In the absence of comprehensive and timely land-use regulation, bioenergy thus may contribute less to climate change mitigation than assumed previously.
Climate change of anthropogenic origin is affecting Earth’s biodiversity and therefore ecosystems and their services. High latitude ecosystems are even more impacted than the rest of Northern Hemisphere because of the amplified polar warming. Still, it is challenging to predict the dynamics of high latitude ecosystems because of complex interaction between abiotic and biotic components. As the past is the key to the future, the interpretation of past ecological changes to better understand ongoing processes is possible. In the Quaternary, the Pleistocene experienced several glacial and interglacial stages that affected past ecosystems. During the last Glacial, the Pleistocene steppe-tundra was covering most of unglaciated northern hemisphere and disappeared in parallel to the megafauna’s extinction at the transition to the Holocene (~11,700 years ago). The origin of the steppe-tundra decline is not well understood and knowledge on the mechanisms, which caused shifts in past communities and ecosystems, is of high priority as they are likely comparable to those affecting modern ecosystems. Lake or permafrost core sediments can be retrieved to investigate past biodiversity at transitions between glacial and interglacial stages. Siberia and Beringia were the origin of dispersal of the steppe-tundra, which make investigation this area of high priority. Until recently, macrofossils and pollen were the most common approaches. They are designed to reconstruct past composition changes but have limit and biases. Since the end of the 20th century, sedimentary ancient DNA (sedaDNA) can also be investigated. My main objectives were, by using sedaDNA approaches to provide scientific evidence of compositional and diversity changes in the Northern Hemisphere ecosystems at the transition between Quaternary glacial and interglacial stages.
In this thesis, I provide snapshots of entire ancient ecosystems and describe compositional changes between Quaternary glacial and interglacial stages, and confirm the vegetation composition and the spatial and temporal boundaries of the Pleistocene steppe-tundra. I identify a general loss of plant diversity with extinction events happening in parallel of megafauna’ extinction. I demonstrate how loss of biotic resilience led to the collapse of a previously well-established system and discuss my results in regards to the ongoing climate change. With further work to constrain biases and limits, sedaDNA can be used in parallel or even replace the more established macrofossils and pollen approaches as my results support the robustness and potential of sedaDNA to answer new palaeoecological questions such as plant diversity changes, loss and provide snapshots of entire ancient biota.