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We use panel data from Germany to analyze the effect of population density on urban air pollution (nitrogen oxides, particulate matter and ozone). To address unobserved heterogeneity and omitted variables, we present long difference/fixed effects estimates and instrumental variables estimates, using historical population and soil quality as instruments. Our preferred estimates imply that a one-standard deviation increase in population density increases air pollution by 3-12%.
”Thanks in Advance”
(2019)
This paper studies the effect of the commonly used phrase “thanks in advance” on compliance with a small request. In a controlled laboratory experiment we ask participants to give a detailed answer to an open question. The treatment variable is whether or not they see the phrase “thanks in advance.” Our participants react to the treatment by exerting less effort in answering the request even though they perceive the phrase as polite.
The German start-up subsidy (SUS) program for the unemployed has recently undergone a major make-over, altering its institutional setup, adding an additional layer of selection and leading to ambiguous predictions of the program’s effectiveness. Using propensity score matching (PSM) as our main empirical approach, we provide estimates of long-term effects of the post-reform subsidy on individual employment prospects and labor market earnings up to 40 months after entering the program. Our results suggest large and persistent long-term effects of the subsidy on employment probabilities and net earned income. These effects are larger than what was estimated for the pre-reform program. Extensive sensitivity analyses within the standard PSM framework reveal that the results are robust to different choices regarding the implementation of the weighting procedure and also with respect to deviations from the conditional independence assumption. As a further assessment of the results’ sensitivity, we go beyond the standard selection-on-observables approach and employ an instrumental variable setup using regional variation in the likelihood of receiving treatment. Here, we exploit the fact that the reform increased the discretionary power of local employment agencies in allocating active labor market policy funds, allowing us to obtain a measure of local preferences for SUS as the program of choice. The results based on this approach give rise to similar estimates. Thus, our results indicating that SUS are still an effective active labor market program after the reform do not appear to be driven by “hidden bias”.
We combine ultrafast X-ray diffraction (UXRD) and time-resolved Magneto-Optical Kerr Effect (MOKE) measurements to monitor the strain pulses in laser-excited TbFe2/Nb heterostructures. Spatial separation of the Nb detection layer from the laser excitation region allows for a background-free characterization of the laser-generated strain pulses. We clearly observe symmetric bipolar strain pulses if the excited TbFe2 surface terminates the sample and a decomposition of the strain wavepacket into an asymmetric bipolar and a unipolar pulse, if a SiO2 glass capping layer covers the excited TbFe2 layer. The inverse magnetostriction of the temporally separated unipolar strain pulses in this sample leads to a MOKE signal that linearly depends on the strain pulse amplitude measured through UXRD. Linear chain model simulations accurately predict the timing and shape of UXRD and MOKE signals that are caused by the strain reflections from multiple interfaces in the heterostructure.
We combine ultrafast X-ray diffraction (UXRD) and time-resolved Magneto-Optical Kerr Effect (MOKE) measurements to monitor the strain pulses in laser-excited TbFe2/Nb heterostructures. Spatial separation of the Nb detection layer from the laser excitation region allows for a background-free characterization of the laser-generated strain pulses. We clearly observe symmetric bipolar strain pulses if the excited TbFe2 surface terminates the sample and a decomposition of the strain wavepacket into an asymmetric bipolar and a unipolar pulse, if a SiO2 glass capping layer covers the excited TbFe2 layer. The inverse magnetostriction of the temporally separated unipolar strain pulses in this sample leads to a MOKE signal that linearly depends on the strain pulse amplitude measured through UXRD. Linear chain model simulations accurately predict the timing and shape of UXRD and MOKE signals that are caused by the strain reflections from multiple interfaces in the heterostructure.
This paper presents an experiment on the effect of retroactive price-reduction schemes on buyers’ repeated purchase decisions. Such schemes promise buyers a reduced price for all units that are bought in a certain time frame if the total quantity that is purchased passes a given threshold. This study finds a loyalty-enhancing effect of retroactive price-reduction schemes only if the buyers ex-ante expected that entering into the scheme would maximize their monetary gain, but later learn that they should leave the scheme. Furthermore, the effect crucially hinges on the framing of the price reduction.
A rich literature links knowledge inputs with innovative outputs. However, most of what is known is restricted to manufacturing. This paper analyzes whether the three aspects involving innovative activity - R&D; innovative output; and productivity - hold for knowledge intensive services. Combining the models of Crepon et al. (1998) and of Ackerberg et al. (2015), allows for causal interpretation of the relationship between innovation output and labor productivity. We find that knowledge intensive services benefit from innovation activities in the sense that these activities causally increase their labor productivity. Moreover, the firm size advantage found for manufacturing in previous studies nearly disappears for knowledge intensive services.
The paper extends a static discrete-choice labor supply model by adding participation and hours constraints. We identify restrictions by survey information on the eligibility and search activities of individuals as well as actual and desired hours. This provides for a more robust identification of preferences and constraints. Both, preferences and restrictions are allowed to vary by and are related through observed and unobserved characteristics. We distinguish various restrictions mechanisms: labor demand rationing, working hours norms varying across occupations, and insufficient public childcare on the supply side of the market. The effect of these mechanisms is simulated by relaxing different constraints at a time. We apply the empirical frame- work to evaluate an in-work benefit for low-paid parents in the German institutional context. The benefit is supposed to increase work incentives for secondary earners. Based on the structural model we are able to disentangle behavioral reactions into the pure incentive effect and the limiting impact of constraints at the intensive and extensive margin. We find that the in-work benefit for parents substantially increases working hours of mothers of young children, especially when they have a low education. Simulating the effects of restrictions shows their substantial impact on employment of mothers with young children.
In this work we investigated ultrafast demagnetization in a Heusler-alloy. This material belongs to the halfmetal and exists in a ferromagnetic phase. A special feature of investigated alloy is a structure of electronic bands. The last leads to the specific density of the states. Majority electrons form a metallic like structure while minority electrons form a gap near the Fermi-level, like in semiconductor. This particularity offers a good possibility to use this material as model-like structure and to make some proof of principles concerning demagnetization. Using pump-probe experiments we carried out time-resolved measurements to figure out the times of demagnetization. For the pumping we used ultrashort laser pulses with duration around 100 fs. Simultaneously we used two excitation regimes with two different wavelengths namely 400 nm and 1240 nm. Decreasing the energy of photons to the gap size of the minority electrons we explored the effect of the gap on the demagnetization dynamics. During this work we used for the first time OPA (Optical Parametrical Amplifier) for the generation of the laser irradiation in a long-wave regime. We tested it on the FETOSPEX-beamline in BASSYII electron storage ring. With this new technique we measured wavelength dependent demagnetization dynamics. We estimated that the demagnetization time is in a correlation with photon energy of the excitation pulse. Higher photon energy leads to the faster demagnetization in our material. We associate this result with the existence of the energy-gap for minority electrons and explained it with Elliot-Yaffet-scattering events. Additionally we applied new probe-method for magnetization state in this work and verified their effectivity. It is about the well-known XMCD (X-ray magnetic circular dichroism) which we adopted for the measurements in reflection geometry. Static experiments confirmed that the pure electronic dynamics can be separated from the magnetic one. We used photon energy fixed on the L3 of the corresponding elements with circular polarization. Appropriate incidence angel was estimated from static measurements. Using this probe method in dynamic measurements we explored electronic and magnetic dynamics in this alloy.
The DNA origami technique has great potential for the development of brighter and more sensitive reporters for fluorescence based detection schemes such as a microbead-based assay in diagnostic applications. The nanostructures can be programmed to include multiple dye molecules to enhance the measured signal as well as multiple probe strands to increase the binding strength of the target oligonucleotide to these nanostructures. Here we present a proof-of-concept study to quantify short oligonucleotides by developing a novel DNA origami based reporter system, combined with planar microbead assays. Analysis of the assays using the VideoScan digital imaging platform showed DNA origami to be a more suitable reporter candidate for quantification of the target oligonucleotides at lower concentrations than a conventional reporter that consists of one dye molecule attached to a single stranded DNA. Efforts have been made to conduct multiplexed analysis of different targets as well as to enhance fluorescence signals obtained from the reporters. We therefore believe that the quantification of short oligonucleotides that exist in low copy numbers is achieved in a better way with the DNA origami nanostructures as reporters.
The DNA origami technique has great potential for the development of brighter and more sensitive reporters for fluorescence based detection schemes such as a microbead-based assay in diagnostic applications. The nanostructures can be programmed to include multiple dye molecules to enhance the measured signal as well as multiple probe strands to increase the binding strength of the target oligonucleotide to these nanostructures. Here we present a proof-of-concept study to quantify short oligonucleotides by developing a novel DNA origami based reporter system, combined with planar microbead assays. Analysis of the assays using the VideoScan digital imaging platform showed DNA origami to be a more suitable reporter candidate for quantification of the target oligonucleotides at lower concentrations than a conventional reporter that consists of one dye molecule attached to a single stranded DNA. Efforts have been made to conduct multiplexed analysis of different targets as well as to enhance fluorescence signals obtained from the reporters. We therefore believe that the quantification of short oligonucleotides that exist in low copy numbers is achieved in a better way with the DNA origami nanostructures as reporters.
According to recent literature sodium bicarbonate (NaHCO3) has been proposed as a performance enhancing aid by reducing acidosis during exercise. The aim of the current review is to investigate if the duration of exercise is an essential factor for the effect
of NaHCO3. To collect the latest studies from electronic database
of PubMed, study publication time was restricted from December 2006 to December 2016. The search was updated in July 2018. The studies were divided into exercise durations of > 4 or ≤ 4 minutes for easier comparability of their effects in different exercises. Only randomized controlled trials were included in this review. Of the 775 studies, 35 met the inclusion criteria. Study design, subjects, effects as well as outcome criteria were inconsistent throughout the studies. Seventeen of these studies reported
performance enhancing effects after supplementing NaHCO3. Eleven of twenty studies with exercise duration of ≤ 4 minutes showed positive and four diverse results after supplementing NaHCO3. On the other hand six of fifteen studies with an exercise duration of >4 minutes showed performance enhancing and two studies showed diverse results. Consequently, the duration of exercise might be influential for inducing a performance enhancing effect when supplementing NaHCO3, but to which extent, remains unclear due to the inconsistencies in the study results.
According to recent literature sodium bicarbonate (NaHCO3) has been proposed as a performance enhancing aid by reducing acidosis during exercise. The aim of the current review is to investigate if the duration of exercise is an essential factor for the effect
of NaHCO3. To collect the latest studies from electronic database
of PubMed, study publication time was restricted from December 2006 to December 2016. The search was updated in July 2018. The studies were divided into exercise durations of > 4 or ≤ 4 minutes for easier comparability of their effects in different exercises. Only randomized controlled trials were included in this review. Of the 775 studies, 35 met the inclusion criteria. Study design, subjects, effects as well as outcome criteria were inconsistent throughout the studies. Seventeen of these studies reported
performance enhancing effects after supplementing NaHCO3. Eleven of twenty studies with exercise duration of ≤ 4 minutes showed positive and four diverse results after supplementing NaHCO3. On the other hand six of fifteen studies with an exercise duration of >4 minutes showed performance enhancing and two studies showed diverse results. Consequently, the duration of exercise might be influential for inducing a performance enhancing effect when supplementing NaHCO3, but to which extent, remains unclear due to the inconsistencies in the study results.
Getting a Yes
(2019)
This paper studies how the request for a favor has to be devised in order to maximize its chance of success. We present results from a mini-dictator game, in which the recipient can send a free-form text message to the dictator before the latter decides. We find that putting effort into the message, writing in a humorous way and mentioning reasons why the money is needed pays off. Additionally, we find differences in the behavior of male and female dictators. Only men react positively to efficiency arguments, while only women react to messages that emphasize the dictator’s power and responsibility.
Presupposition triggers differ with respect to whether their presupposition is easily accommodatable. The presupposition of focus-sensitive additive particles like also or too is often classified as hard to accommodate, i.e., these triggers are infelicitous if their presupposition is not entailed by the immediate linguistic or non-linguistic context. We tested two competing accounts for the German additive particle auch concerning this requirement: First, that it requires a focus alternative to the whole proposition to be salient, and second, that it merely requires an alternative to the focused constituent (e.g., an individual) to be salient. We conducted two experiments involving felicity judgments as well as questions asking for the truth of the presupposition to be accommodated. Our results suggest that the latter account is too weak: mere previous mention of a potential alternative to the focused constituent is not enough to license the use of auch. However, our results also suggest that the former account is too strong: when an alternative of the focused constituent is prementioned and certain other accommodation-enhancing factors are present, the context does not have to entail the presupposed proposition. We tested the following two potentially accommodation-enhancing factors: First, whether the discourse can be construed to be from the perspective of the individual that the presupposition is about, and second, whether the presupposition is needed to establish coherence between the host sentence of the additive particle and the preceding context. The factor coherence was found to play a significant role. Our results thus corroborate the results of other researchers showing that discourse participants go to great lengths in order to identify a potential presupposition to accommodate, and we contribute to these results by showing that coherence is one of the factors that enhance accommodation.
Presupposition triggers differ with respect to whether their presupposition is easily accommodatable. The presupposition of focus-sensitive additive particles like also or too is often classified as hard to accommodate, i.e., these triggers are infelicitous if their presupposition is not entailed by the immediate linguistic or non-linguistic context. We tested two competing accounts for the German additive particle auch concerning this requirement: First, that it requires a focus alternative to the whole proposition to be salient, and second, that it merely requires an alternative to the focused constituent (e.g., an individual) to be salient. We conducted two experiments involving felicity judgments as well as questions asking for the truth of the presupposition to be accommodated. Our results suggest that the latter account is too weak: mere previous mention of a potential alternative to the focused constituent is not enough to license the use of auch. However, our results also suggest that the former account is too strong: when an alternative of the focused constituent is prementioned and certain other accommodation-enhancing factors are present, the context does not have to entail the presupposed proposition. We tested the following two potentially accommodation-enhancing factors: First, whether the discourse can be construed to be from the perspective of the individual that the presupposition is about, and second, whether the presupposition is needed to establish coherence between the host sentence of the additive particle and the preceding context. The factor coherence was found to play a significant role. Our results thus corroborate the results of other researchers showing that discourse participants go to great lengths in order to identify a potential presupposition to accommodate, and we contribute to these results by showing that coherence is one of the factors that enhance accommodation.
The semiarid northeast of Brazil is one of the most densely populated dryland regions in the world and recurrently affected by severe droughts. Thus, reliable seasonal forecasts of streamflow and reservoir storage are of high value for water managers. Such forecasts can be generated by applying either hydrological models representing underlying processes or statistical relationships exploiting correlations among meteorological and hydrological variables. This work evaluates and compares the performances of seasonal reservoir storage forecasts derived by a process-based hydrological model and a statistical approach.
Driven by observations, both models achieve similar simulation accuracies. In a hindcast experiment, however, the accuracy of estimating regional reservoir storages was considerably lower using the process-based hydrological model, whereas the resolution and reliability of drought event predictions were similar by both approaches. Further investigations regarding the deficiencies of the process-based model revealed a significant influence of antecedent wetness conditions and a higher sensitivity of model prediction performance to rainfall forecast quality.
Within the scope of this study, the statistical model proved to be the more straightforward approach for predictions of reservoir level and drought events at regionally and monthly aggregated scales. However, for forecasts at finer scales of space and time or for the investigation of underlying processes, the costly initialisation and application of a process-based model can be worthwhile. Furthermore, the application of innovative data products, such as remote sensing data, and operational model correction methods, like data assimilation, may allow for an enhanced exploitation of the advanced capabilities of process-based hydrological models.
The semiarid northeast of Brazil is one of the most densely populated dryland regions in the world and recurrently affected by severe droughts. Thus, reliable seasonal forecasts of streamflow and reservoir storage are of high value for water managers. Such forecasts can be generated by applying either hydrological models representing underlying processes or statistical relationships exploiting correlations among meteorological and hydrological variables. This work evaluates and compares the performances of seasonal reservoir storage forecasts derived by a process-based hydrological model and a statistical approach.
Driven by observations, both models achieve similar simulation accuracies. In a hindcast experiment, however, the accuracy of estimating regional reservoir storages was considerably lower using the process-based hydrological model, whereas the resolution and reliability of drought event predictions were similar by both approaches. Further investigations regarding the deficiencies of the process-based model revealed a significant influence of antecedent wetness conditions and a higher sensitivity of model prediction performance to rainfall forecast quality.
Within the scope of this study, the statistical model proved to be the more straightforward approach for predictions of reservoir level and drought events at regionally and monthly aggregated scales. However, for forecasts at finer scales of space and time or for the investigation of underlying processes, the costly initialisation and application of a process-based model can be worthwhile. Furthermore, the application of innovative data products, such as remote sensing data, and operational model correction methods, like data assimilation, may allow for an enhanced exploitation of the advanced capabilities of process-based hydrological models.
The present dissertation investigates profit-maximizing behavior in different phases of the negotiation process. Over the last decades, research dealt in detail with behavior of negotiation actors with the aim of identifying performance enhancing factors. The majority of those studies focused on behavior within the main negotiation phase. This work, however, considers phases which are, so far, underrepresented in research but show an impact on the negotiation process and outcome. Those phases are the pre-negotiation, the first offer, and the main negotiation phase which is further divided by breaks into several rounds. Within these phases, traits of behavior are analyzed that can be used strategically in order to impact the negotiation outcome. The dissertation contains three papers, each one dealing with a specific strategy within one phase. The first paper investigates communication behavior in the pre-negotiation phase. Content analysis of a negotiation experiment shows that the employment of positive communication elements such as the generation of enthusiasm for an upcoming project results in an increase of agreements on entering a negotiation and also leads to a higher willingness to make concessions. The second paper explores the impact of a semantic first anchor, which does not contain a specific number but only gives a numerical direction, on the opponent’s concession behavior and the final outcome. By means of two scenario-based questionnaires and a negotiation experiment it is demonstrated that semantic offers reveal an anchoring effect and lead to better negotiation outcomes. The third paper deals with the introduction of breaks and their effect on the following negotiation process. Therefore, content and outcome of another negotiation experiment are investigated. The analysis shows that breaks evoke a dominant impression but can negatively impact the atmosphere and thereby also the outcome. Finally, the gathered insights are brought together and discussed. The dissertation closes with implications for practice, limitations of the work, and ideas for future research.
Hepcidin-25 was identified as themain iron regulator in the human body, and it by binds to the sole iron-exporter ferroportin. Studies showed that the N-terminus of hepcidin is responsible for this interaction, the same N-terminus that encompasses a small copper(II) binding site known as the ATCUN (amino-terminal Cu(II)- and Ni(II)-binding) motif. Interestingly, this copper-binding property is largely ignored in most papers dealing with hepcidin-25. In this context, detailed investigations of the complex formed between hepcidin-25 and copper could reveal insight into its biological role. The present work focuses on metal-bound hepcidin-25 that can be considered the biologically active form. The first part is devoted to the reversed-phase chromatographic separation of copper-bound and copper-free hepcidin-25 achieved by applying basic mobile phases containing 0.1% ammonia. Further, mass spectrometry (tandemmass spectrometry (MS/MS), high-resolutionmass spectrometry (HRMS)) and nuclear magnetic resonance (NMR) spectroscopy were employed to characterize the copper-peptide. Lastly, a three-dimensional (3D)model of hepcidin-25with bound copper(II) is presented. The identification of metal complexes and potential isoforms and isomers, from which the latter usually are left undetected by mass spectrometry, led to the conclusion that complementary analytical methods are needed to characterize a peptide calibrant or referencematerial comprehensively. Quantitative nuclear magnetic resonance (qNMR), inductively-coupled plasma mass spectrometry (ICP-MS), ion-mobility spectrometry (IMS) and chiral amino acid analysis (AAA) should be considered among others.
We measure valence-to-core x-ray emission spectra of compressed crystalline GeO₂ up to 56 GPa and of amorphous GeO₂ up to 100 GPa. In a novel approach, we extract the Ge coordination number and mean Ge-O distances from the emission energy and the intensity of the Kβ'' emission line. The spectra of high-pressure polymorphs are calculated using the Bethe-Salpeter equation. Trends observed in the experimental and calculated spectra are found to match only when utilizing an octahedral model. The results reveal persistent octahedral Ge coordination with increasing distortion, similar to the compaction mechanism in the sequence of octahedrally coordinated crystalline GeO₂ high-pressure polymorphs.
We measure valence-to-core x-ray emission spectra of compressed crystalline GeO₂ up to 56 GPa and of amorphous GeO₂ up to 100 GPa. In a novel approach, we extract the Ge coordination number and mean Ge-O distances from the emission energy and the intensity of the Kβ'' emission line. The spectra of high-pressure polymorphs are calculated using the Bethe-Salpeter equation. Trends observed in the experimental and calculated spectra are found to match only when utilizing an octahedral model. The results reveal persistent octahedral Ge coordination with increasing distortion, similar to the compaction mechanism in the sequence of octahedrally coordinated crystalline GeO₂ high-pressure polymorphs.
Multifunctional reprogrammable actuators based on polymer networks with crystallizable segments
(2019)
Soft polymeric materials, which can change their shape reversibly in response to external stimuli, can serve as actuating components in robotic systems. Besides electroactive polymers (EAP), hydrogels and liquid crystalline elastomers (LCE), crosslinked crystallizable shape-memory polymers networks have been introduced recently as reprogrammable thermo-reversible actuators. The integration of additional functions in such materials will lead to multifunctional polymeric actuators, which meet the complex requirements of modern robotic applications.
The primary aim of this thesis was to achieve multifunctional reprogrammable thermo-reversible actuators based on thermoplastic polymers. Here, three different actuators providing additional functionalities such as surface modification capability (i), self-healing capability (ii) or a tailorable non-response function enabling noncontinuous multi-step motions (iii) were realized. At first, it was hypothesized that surface modifiable polymeric actuators (i) can be achieved by crosslinking of crystallizable thermoplastic terpolymers having reactive moieties, where subsequent thermomechanical programming enables reversible actuations while the sustained reactive groups allow post surface modification. For the second actuator type (ii) it was hypothesized that self-healing during reprogramming of polymeric actuators prepared by crosslinking of crystallizable linear homopolymers, can be achieved by adjusting the amount of freely interpenetrating extractable polymer moieties. Finally, it was hypothesized that thermo-reversible actuators providing a non-response function (iii) and thus enable multistep motions upon continuous normal stimulation, can be achieved by a crosslinked blend of two thermoplastic polymers with co-continuous morphology having a well-separated melting and crystallization transitions. In addition, these actuators can be physically reprogrammed by heating above all melting transitions to provide a different actuating shape.
In this study, surface functionalizable actuators were realized from crosslinked poly[(ethylene)-co-(ethyl acrylate)-co-(maleic anhydride)] (cPEEAMA) based networks. Here crystallizable polyethylene (PE) segments should serve as actuation segments, ethyl acrylate (EA) provides elasticity to the system required for deformation, while reactive maleic anhydride (MA) will be used as chemically modifiable entities for post surface modification. Networks with varied crosslink density were prepared and its effect on thermomechanical properties as well as actuation performance was analyzed. Cyclic thermomechanical experiments were employed to investigate the actuation capability, which revealed a reversible actuation (ε׳rev) between 5 and 15%. Fourier-transform infrared spectroscopy (FTIR) measurements confirmed that MA groups were sustained at the sample surface after processing and programming, which could be modified by reaction with ethylene diamine. Such amine functionalization allows the attachment of bioactive molecules to the actuator surface, which might provide a route to actuating substrates for biotechnology.
Self-healable actuating materials were realized by poly(ε-caprolactone) (PCL) polymer networks with extractable linear PCL fractions of 5 to 60 wt%. A detailed evaluation of the actuation capabilities by cyclic experiments revealed the highest reversible change in strain of Δε = 24% for the cPCL network with 30 wt% of linear polymer. The thermal treatment of damaged samples resulted in the healing of the network when heated to 80 °C. Here a linear polymer fraction ≥ 30 wt% was necessary to achieve a self-healing efficiency of ≥ 50%. The application of such high temperatures erases the programmed actuator shape and at the same time allows to reprogram a new actuating shape. Such sustainable actuators with self-healing function are of great interest for future robotic devices.
Afore mentioned actuators operate continuously between two shapes and their movements can only be interrupted when the temperature is stopped. To overcome this limitation, noncontinuously responding actuators enabling multi-step actuation were realized from crosslinked blend networks prepared from PCL and poly[(ethylene)-co-(vinyl acetate)] (PEVA). These polymers (PCL and PEVA) were selected due to their immiscible character, where crystallizable PE and PCL segments provide two different actuation units, while vinyl acetate (VA) segment enabled sufficient elasticity of the system. A gap of 20 K in the melting and crystallization temperature of PE and PCL was achieved by selecting PEVA with 5 wt% VA content (cPCL-PEVA5) providing a co-continuous phase morphology. Cyclic thermomechanical investigations were employed to investigate noncontinuous actuation, which revealed a high Δε = 25% with a similar contribution from PCL and PE actuation units with a non-response region in the temperature range from 50 to 71 °C in heating step and 30 to 60 °C in cooling step. The actuation related to PCL part changed from 13 to 2% by altering the heating and cooling rates from 3 to 10 K·min-1. Free-standing reversible noncontinuous actuation was realized by rotating demonstrator which exhibits reversible angle change in a custom-made setup. For this purpose, cPCL-PEVA5 stripe was programmed by twisting and reversible rotational actuation was realized from 0 to 180° while pausing in the 90° position during non-response. These blends can be physically programmed to perform reversible noncontinuous actuations, while the programmed geometry can be erased by heating it to temperature above all melting transitions. By physically reprogramming of the material various different actuation modes can be obtained. Such a noncontinuous actuator would be relevant for designing interruptive actuating soft robots at continuous trigger signals.
Skarn deposits are found on every continents and were formed at different times from Precambrian to Tertiary. Typically, the formation of a skarn is induced by a granitic intrusion in carbonates-rich sedimentary rocks. During contact metamorphism, fluids derived from the granite interact with the sedimentary host rocks, which results in the formation of calc-silicate minerals at the expense of carbonates. Those newly formed minerals generally develop in a metamorphic zoned aureole with garnet in the proximal and pyroxene in the distal zone. Ore elements contained in magmatic fluids are precipitated due to the change in fluid composition. The temperature decrease of the entire system, due to the cooling of magmatic fluids and the entering of meteoric water, allows retrogression of some prograde minerals.
The Hämmerlein skarn deposit has a multi-stage history with a skarn formation during regional metamorphism and a retrogression of primary skarn minerals during the granitic intrusion. Tin was mobilized during both events. The 340 Ma old tin-bearing skarn minerals show that tin was present in sediments before the granite intrusion, and that the first Sn enrichment occurred during the skarn formation by regional metamorphism fluids. In a second step at ca. 320 Ma, tin-bearing fluids were produced with the intrusion of the Eibenstock granite. Tin, which has been added by the granite and remobilized from skarn calc-silicates, precipitated as cassiterite.
Compared to clay or marl, the skarn is enriched in Sn, W, In, Zn, and Cu. These metals have been supplied during both regional metamorphism and granite emplacement. In addition, the several isotopic and chemical data of skarn samples show that the granite selectively added elements such as Sn, and that there was no visible granitic contribution to the sedimentary signature of the skarn
The example of Hämmerlein shows that it is possible to form a tin-rich skarn without associated granite when tin has already been transported from tin-bearing sediments during regional metamorphism by aqueous metamorphic fluids. These skarns are economically not interesting if tin is only contained in the skarn minerals. Later alteration of the skarn (the heat and fluid source is not necessarily a granite), however, can lead to the formation of secondary cassiterite (SnO2), with which the skarn can become economically highly interesting.
Force plays a fundamental role in the regulation of biological processes. Cells can sense the mechanical properties of the extracellular matrix (ECM) by applying forces and transmitting mechanical signals. They further use mechanical information for regulating a wide range of cellular functions, including adhesion, migration, proliferation, as well as differentiation and apoptosis. Even though it is well understood that mechanical signals play a crucial role in directing cell fate, surprisingly little is known about the range of forces that define cell-ECM interactions at the molecular level.
Recently, synthetic molecular force sensor (MFS) designs have been established for measuring the molecular forces acting at the cell-ECM interface. MFSs detect the traction forces generated by cells and convert this mechanical input into an optical readout. They are composed of calibrated mechanoresponsive building blocks and are usually equipped with a fluorescence reporter system. Up to date, many different MFS designs have been introduced and successfully used for measuring forces involved in the adhesion of mammalian cells. These MFSs utilize different molecular building blocks, such as double-stranded deoxyribonucleic acid (dsDNA) molecules, DNA hairpins and synthetic polymers like polyethylene glycol (PEG). These currently available MFS designs lack ECM mimicking properties.
In this work, I introduce a new MFS building block for cell biology applications, derived from the natural ECM. It combines mechanical tunability with the ability to mimic the native cellular microenvironment. Inspired by structural ECM proteins with load bearing function, this new MFS design utilizes coiled coil (CC)-forming peptides. CCs are involved in structural and mechanical tasks in the cellular microenvironment and many of the key protein components of the cytoskeleton and the ECM contain CC structures. The well-known folding motif of CC structures, an easy synthesis via solid phase methods and the many roles CCs play in biological processes have inspired studies to use CCs as tunable model systems for protein design and assembly. All these properties make CCs ideal candidates as building blocks for MFSs. In this work, a series of heterodimeric CCs were designed, characterized and further used as molecular building blocks for establishing a novel, next-generation MFS prototype.
A mechanistic molecular understanding of their structural response to mechanical load is essential for revealing the sequence-structure-mechanics relationships of CCs. Here, synthetic heterodimeric CCs of different length were loaded in shear geometry and their mechanical response was investigated using a combination of atomic force microscope (AFM)-based single-molecule force spectroscopy (SMFS) and steered molecular dynamics (SMD) simulations. SMFS showed that the rupture forces of short heterodimeric CCs (3-5 heptads) lie in the range of 20-50 pN, depending on CC length, pulling geometry and the applied loading rate (dF/dt). Upon shearing, an initial rise in the force, followed by a force plateau and ultimately strand separation was observed in SMD simulations. A detailed structural analysis revealed that CC response to shear load depends on the loading rate and involves helix uncoiling, uncoiling-assisted sliding in the direction of the applied force and uncoiling-assisted dissociation perpendicular to the force axis.
The application potential of these mechanically characterized CCs as building blocks for MFSs has been tested in 2D cell culture applications with the goal of determining the threshold force for cell adhesion. Fully calibrated, 4- to 5-heptad long, CC motifs (CC-A4B4 and CC-A5B5) were used for functionalizing glass surfaces with MFSs. 3T3 fibroblasts and endothelial cells carrying mutations in a signaling pathway linked to cell adhesion and mechanotransduction processes were used as model systems for time-dependent adhesion experiments. A5B5-MFS efficiently supported cell attachment to the functionalized surfaces for both cell types, while A4B4-MFS failed to maintain attachment of 3T3 fibroblasts after the first 2 hours of initial cell adhesion. This difference in cell adhesion behavior demonstrates that the magnitude of cell-ECM forces varies depending on the cell type and further supports the application potential of CCs as mechanoresponsive and tunable molecular building blocks for the development of next-generation protein-based MFSs.This novel CC-based MFS design is expected to provide a powerful new tool for observing cellular mechanosensing processes at the molecular level and to deliver new insights into the mechanisms and forces involved. This MFS design, utilizing mechanically tunable CC building blocks, will not only allow for measuring the molecular forces acting at the cell-ECM interface, but also yield a new platform for the development of mechanically controlled materials for a large number of biological and medical applications.
In 2015, Germany introduced a statutory hourly minimum wage that was not only universally binding but also set at a relatively high level. We discuss the short-run effects of this new minimum wage on a wide set of socio-economic outcomes, such as employment and working hours, earnings and wage inequality, dependent and self-employment, as well as reservation wages and satisfaction. We also discuss difficulties in the implementation of the minimum wage and the measurement of its effects related to non-compliance and suitability of data sources. Two years after the minimum wage introduction, the following conclusions can be drawn: while hourly wages increased for low-wage earners, some small negative employment effects are also identifiable. The effects on aspired goals, such as poverty and inequality reduction, have not materialized in the short run. Instead, a tendency to reduce working hours is found, which alleviates the desired positive impact on monthly income. Additionally, the level of non-compliance was substantial in the short run, thus drawing attention to problems when implementing such a wide-reaching policy.
Human beings are supposed to possess an approximate number system (ANS) dedicated to extracting and representing approximate numerical magnitude information as well as an object tracking system (OTS) for the rapid and accurate enumeration of small sets. It is assumed that the OTS and the ANS independently contribute to the acquisition of more elaborate numerical concepts. Chinese children have been shown to exhibit more elaborate numerical concepts than their non-Chinese peers, but it is still an open question whether similar cross-national differences exist with regard to the underlying systems, namely the ANS and the OTS. In the present study, we investigated this question by comparing Chinese and German preschool children with regard to their performance in a non-symbolic numerical magnitude comparison task (assessing the ANS) and in an enumeration task (assessing the OTS). In addition, we compared children’s counting skills. To ensure that possible between-group differences could not be explained by differences in more general performance factors, we also assessed children’s reasoning ability and processing speed. Chinese children showed a better counting performance and a more accurate performance in the non-symbolic numerical magnitude comparison task. These differences in performance could not be ascribed to differences in reasoning abilities and processing speed. In contrast, Chinese and German children did not differ significantly in the enumeration of small sets. The superior counting performance of Chinese children was thus found to be reflected in the ANS but not in the OTS.
Regulatory focus is a motivational construct that describes humans’ motivational orientation during goal pursuit. It is conceptualized as a chronic, trait-like, as well as a momentary, state-like orientation. Whereas there is a large number of measures to capture chronic regulatory focus, measures for its momentary assessment are only just emerging. This paper presents the development and validation of a measure of Momentary–Chronic Regulatory Focus. Our development incorporates the distinction between self-guide and reference-point definitions of regulatory focus. Ideals and ought striving are the promotion and prevention dimension in the self-guide system; gain and non-loss regulatory focus are the respective dimensions within the reference-point system. Three-survey-based studies test the structure, psychometric properties, and validity of the measure in its version to assess chronic regulatory focus (two samples of working participants, N = 389, N = 672; one student sample [time 1, N = 105; time 2, n = 91]). In two further studies, an experience sampling study with students (N = 84, k = 1649) and a daily-diary study with working individuals (N = 129, k = 1766), the measure was applied to assess momentary regulatory focus. Multilevel analyses test the momentary measure’s factorial structure, provide support for its sensitivity to capture within-person fluctuations, and provide evidence for concurrent construct validity.
Regulatory focus is a motivational construct that describes humans’ motivational orientation during goal pursuit. It is conceptualized as a chronic, trait-like, as well as a momentary, state-like orientation. Whereas there is a large number of measures to capture chronic regulatory focus, measures for its momentary assessment are only just emerging. This paper presents the development and validation of a measure of Momentary–Chronic Regulatory Focus. Our development incorporates the distinction between self-guide and reference-point definitions of regulatory focus. Ideals and ought striving are the promotion and prevention dimension in the self-guide system; gain and non-loss regulatory focus are the respective dimensions within the reference-point system. Three-survey-based studies test the structure, psychometric properties, and validity of the measure in its version to assess chronic regulatory focus (two samples of working participants, N = 389, N = 672; one student sample [time 1, N = 105; time 2, n = 91]). In two further studies, an experience sampling study with students (N = 84, k = 1649) and a daily-diary study with working individuals (N = 129, k = 1766), the measure was applied to assess momentary regulatory focus. Multilevel analyses test the momentary measure’s factorial structure, provide support for its sensitivity to capture within-person fluctuations, and provide evidence for concurrent construct validity.
While the consequences of cyberbullying victimization have received some attention in the literature, to date, little is known about the multiple types of strains in adolescents’ lives, such as whether cyberbullying victimization and peer rejection increase their vulnerability to depression and anxiety. Even though some research found that adolescents with disabilities show higher risk for cyberbullying victimization, most research has focused on typically developing adolescents. Thus, the present study focused on examining the moderating effect of peer rejection in the relationships between cyberbullying victimization, depression, and anxiety among adolescents with autism spectrum disorder. There were 128 participants (89% male; ages ranging from 11–16 years old) with autism spectrum disorder in the sixth, seventh, or eighth grade at 16 middle schools in the United States. Participants completed questionnaires on cyberbullying victimization, peer rejection, depression, and anxiety. Results revealed that cyberbullying victimization was associated positively with peer rejection, anxiety, and depression among adolescents with autism spectrum disorder. Further, peer rejection was linked positively with depression and anxiety. Peer rejection moderated the positive relationship between cyberbullying victimization and depression, but not anxiety. Implications for prevention programs and future research are discussed.
While the consequences of cyberbullying victimization have received some attention in the literature, to date, little is known about the multiple types of strains in adolescents’ lives, such as whether cyberbullying victimization and peer rejection increase their vulnerability to depression and anxiety. Even though some research found that adolescents with disabilities show higher risk for cyberbullying victimization, most research has focused on typically developing adolescents. Thus, the present study focused on examining the moderating effect of peer rejection in the relationships between cyberbullying victimization, depression, and anxiety among adolescents with autism spectrum disorder. There were 128 participants (89% male; ages ranging from 11–16 years old) with autism spectrum disorder in the sixth, seventh, or eighth grade at 16 middle schools in the United States. Participants completed questionnaires on cyberbullying victimization, peer rejection, depression, and anxiety. Results revealed that cyberbullying victimization was associated positively with peer rejection, anxiety, and depression among adolescents with autism spectrum disorder. Further, peer rejection was linked positively with depression and anxiety. Peer rejection moderated the positive relationship between cyberbullying victimization and depression, but not anxiety. Implications for prevention programs and future research are discussed.
This review summarizes features of professional development programs that aim to prepare in-service teachers to improve students’ academic language proficiency when teaching subject areas. The 38 studies reviewed suggest that all of the profiled interventions were effective to some extent. The programs share many characteristics considered important in successful teacher professional development across different subject areas. They also include some features that appear to be specific to teacher training in this particular domain. This review supports the idea that professional development helps change teachers’ thinking and practice and benefits students, if certain features are taken into consideration in its design and implementation.
This review summarizes features of professional development programs that aim to prepare in-service teachers to improve students’ academic language proficiency when teaching subject areas. The 38 studies reviewed suggest that all of the profiled interventions were effective to some extent. The programs share many characteristics considered important in successful teacher professional development across different subject areas. They also include some features that appear to be specific to teacher training in this particular domain. This review supports the idea that professional development helps change teachers’
thinking and practice and benefits students, if certain features are taken into consideration in its design and implementation.
The importance of plasmonic heating for the plasmondriven photodimerization of 4-nitrothiophenol
(2019)
Metal nanoparticles form potent nanoreactors, driven by the optical generation of energetic electrons and nanoscale heat. The relative influence of these two factors on nanoscale chemistry is strongly debated. This article discusses the temperature dependence of the dimerization of 4-nitrothiophenol (4-NTP) into 4,4′-dimercaptoazobenzene (DMAB) adsorbed on gold nanoflowers by Surface-Enhanced Raman Scattering (SERS). Raman thermometry shows a significant optical heating of the particles. The ratio of the Stokes and the anti-Stokes Raman signal moreover demonstrates that the molecular temperature during the reaction rises beyond the average crystal lattice temperature of the plasmonic particles. The product bands have an even higher temperature than reactant bands, which suggests that the reaction proceeds preferentially at thermal hot spots. In addition, kinetic measurements of the reaction during external heating of the reaction environment yield a considerable rise of the reaction rate with temperature. Despite this significant heating effects, a comparison of SERS spectra recorded after heating the sample by an external heater to spectra recorded after prolonged illumination shows that the reaction is strictly photo-driven. While in both cases the temperature increase is comparable, the dimerization occurs only in the presence of light. Intensity dependent measurements at fixed temperatures confirm this finding.
Predator-prey interactions provide central links in food webs. These interaction are directly or indirectly impacted by a number of factors. These factors range from physiological characteristics of individual organisms, over specifics of their interaction to impacts of the environment. They may generate the potential for the application of different strategies by predators and prey. Within this thesis, I modelled predator-prey interactions and investigated a broad range of different factors driving the application of certain strategies, that affect the individuals or their populations. In doing so, I focused on phytoplankton-zooplankton systems as established model systems of predator-prey interactions.
At the level of predator physiology I proposed, and partly confirmed, adaptations to fluctuating availability of co-limiting nutrients as beneficial strategies. These may allow to store ingested nutrients or to regulate the effort put into nutrient assimilation. We found that these two strategies are beneficial at different fluctuation frequencies of the nutrients, but may positively interact at intermediate frequencies. The corresponding experiments supported our model results. We found that the temporal structure of nutrient fluctuations indeed has strong effects on the juvenile somatic growth rate of {\itshape Daphnia}.
Predator colimitation by energy and essential biochemical nutrients gave rise to another physiological strategy. High-quality prey species may render themselves indispensable in a scenario of predator-mediated coexistence by being the only source of essential biochemical nutrients, such as cholesterol. Thereby, the high-quality prey may even compensate for a lacking defense and ensure its persistence in competition with other more defended prey species.
We found a similar effect in a model where algae and bacteria compete for nutrients. Now, being the only source of a compound that is required by the competitor (bacteria) prevented the competitive exclusion of the algae. In this case, the essential compounds were the organic carbon provided by the algae. Here again, being indispensable served as a prey strategy that ensured its coexistence.
The latter scenario also gave rise to the application of the two metabolic strategies of autotrophy and heterotrophy by algae and bacteria, respectively. We found that their coexistence allowed the recycling of resources in a microbial loop that would otherwise be lost. Instead, these resources were made available to higher trophic levels, increasing the trophic transfer efficiency in food webs.
The predation process comprises the next higher level of factors shaping the predator-prey interaction, besides these factors that originated from the functioning or composition of individuals. Here, I focused on defensive mechanisms and investigated multiple scenarios of static or adaptive combinations of prey defense and predator offense. I confirmed and extended earlier reports on the coexistence-promoting effects of partially lower palatability of the prey community. When bacteria and algae are coexisting, a higher palatability of bacteria may increase the average predator biomass, with the side effect of making the population dynamics more regular. This may facilitate experimental investigations and interpretations. If defense and offense are adaptive, this allows organisms to maximize their growth rate. Besides this fitness-enhancing effect, I found that co-adaptation may provide the predator-prey system with the flexibility to buffer external perturbations.
On top of these rather internal factors, environmental drivers also affect predator-prey interactions. I showed that environmental nutrient fluctuations may create a spatio-temporal resource heterogeneity that selects for different predator strategies. I hypothesized that this might favour either storage or acclimation specialists, depending on the frequency of the environmental fluctuations.
We found that many of these factors promote the coexistence of different strategies and may therefore support and sustain biodiversity. Thus, they might be relevant for the maintenance of crucial ecosystem functions that also affect us humans. Besides this, the richness of factors that impact predator-prey interactions might explain why so many species, especially in the planktonic regime, are able to coexist.
A reliable inference of networks from data is of key interest in many scientific fields. Several methods have been suggested in the literature to reliably determine links in a network. These techniques rely on statistical methods, typically controlling the number of false positive links, but not considering false negative links. In this thesis new methodologies to improve network inference are suggested. Initial analyses demonstrate the impact of falsepositive and false negative conclusions about the presence or absence of links on the resulting inferred network. Consequently, revealing the importance of making well-considered choices leads to suggest new approaches to enhance existing network reconstruction methods.
A simulation study, presented in Chapter 3, shows that different values to balance false positive and false negative conclusions about links should be used in order to reliably estimate network characteristics. The existence of type I and type II errors in the reconstructed network, also called biased network, is accepted. Consequently, an analytic method that describes the influence of these two errors on the network structure is explored. As a result of this analysis, an analytic formula of the density of the biased vertex degree distribution is found (Chapter 4).
In the inverse problem, the vertex degree distribution of the true underlying network is analytically reconstructed, assuming the probabilities of type I and type II errors. Chapters 4-5 show that the method is robust to incorrect estimates of α and β within reasonable limits. In Chapter 6, an iterative procedure to enhance this method is presented in the case of large errors on the estimates of α and β.
The investigations presented so far focus on the influence of false positive and false negative links on the network characteristics. In Chapter 7, the analysis is reversed - the study focuses on the influence of network characteristics on the probability of type I and type II errors, in the case of networks of coupled oscillators. The probabilities of α and β are influenced by the shortest path length and the detour degree, respectively. These results have been used to improve the network reconstruction, when the true underlying network is not known a priori, introducing a novel and advanced concept of threshold.
The worldwide populist wave has contributed to a perception that international law is currently in a state of crisis. This article examines in how far populist governments have challenged prevailing interpretations of international law. The article links structural features of populism with an analysis of populist governmental strategies and argumentative practices. It demonstrates that, in their rhetoric, populist governments promote an understanding of international law as a mere law of coordination. This is, however, not entirely reflected in their legal practices where an instrumental, cherry-picking approach prevails. The article concludes that policies of populist governments affect the current state of international law on two different levels: In the political sphere their practices alter the general environment in which legal rules are interpreted. In the legal sphere populist governments push for changes in the interpretation of established international legal rules. The article substantiates these propositions by focusing on the principle of nonintervention and foreign funding for NGOs.
International adjudication is currently under assault, encouraging a number of States to withdraw, or to consider withdrawing, from treaties providing for international dispute settlement. This Working Paper argues that the act of treaty withdrawal is not merely as the unilateral executive exercise of the individual sovereign prerogative of a State. International law places checks upon the exercise of withdrawal, recognising that it is an act that of its nature affects the interests of other States parties, which have a collective interest in constraining withdrawal. National courts have a complementary function in restraining unilateral withdrawal in order to support the domestic constitution. The arguments advanced against international adjudication in the name of popular democracy at the national level can serve as a cloak for the exercise of executive power unrestrained by law. The submission by States of their disputes to peaceful settlement through international adjudication is central, not incidental, to the successful operation of the international legal system.
The identification of vulnerabilities in IT infrastructures is a crucial problem in enhancing the security, because many incidents resulted from already known vulnerabilities, which could have been resolved. Thus, the initial identification of vulnerabilities has to be used to directly resolve the related weaknesses and mitigate attack possibilities. The nature of vulnerability information requires a collection and normalization of the information prior to any utilization, because the information is widely distributed in different sources with their unique formats. Therefore, the comprehensive vulnerability model was defined and different sources have been integrated into one database. Furthermore, different analytic approaches have been designed and implemented into the HPI-VDB, which directly benefit from the comprehensive vulnerability model and especially from the logical preconditions and postconditions.
Firstly, different approaches to detect vulnerabilities in both IT systems of average users and corporate networks of large companies are presented. Therefore, the approaches mainly focus on the identification of all installed applications, since it is a fundamental step in the detection. This detection is realized differently depending on the target use-case. Thus, the experience of the user, as well as the layout and possibilities of the target infrastructure are considered. Furthermore, a passive lightweight detection approach was invented that utilizes existing information on corporate networks to identify applications.
In addition, two different approaches to represent the results using attack graphs are illustrated in the comparison between traditional attack graphs and a simplistic graph version, which was integrated into the database as well. The implementation of those use-cases for vulnerability information especially considers the usability. Beside the analytic approaches, the high data quality of the vulnerability information had to be achieved and guaranteed. The different problems of receiving incomplete or unreliable information for the vulnerabilities are addressed with different correction mechanisms. The corrections can be carried out with correlation or lookup mechanisms in reliable sources or identifier dictionaries. Furthermore, a machine learning based verification procedure was presented that allows an automatic derivation of important characteristics from the textual description of the vulnerabilities.
Advancing charge selective contacts for efficient monolithic perovskite-silicon tandem solar cells
(2019)
Hybrid organic-inorganic perovskites are one of the most promising material classes for photovoltaic energy conversion. In solar cells, the perovskite absorber is sandwiched between n- and p-type contact layers which selectively transport electrons and holes to the cell’s cathode and anode, respectively. This thesis aims to advance contact layers in perovskite solar cells and unravel the impact of interface and contact properties on the device performance. Further, the contact materials are applied in monolithic perovskite-silicon heterojunction (SHJ) tandem solar cells, which can overcome the single junction efficiency limits and attract increasing attention. Therefore, all contact layers must be highly transparent to foster light harvesting in the tandem solar cell design. Besides, the SHJ device restricts processing temperatures for the selective contacts to below 200°C.
A comparative study of various electron selective contact materials, all processed below 180°C, in n-i-p type perovskite solar cells highlights that selective contacts and their interfaces to the absorber govern the overall device performance. Combining fullerenes and metal-oxides in a TiO2/PC60BM (phenyl-C60-butyric acid methyl ester) double-layer contact allows to merge good charge extraction with minimized interface recombination. The layer sequence thereby achieved high stabilized solar cell performances up to 18.0% and negligible current-voltage hysteresis, an otherwise pronounced phenomenon in this device design. Double-layer structures are therefore emphasized as a general concept to establish efficient and highly selective contacts.
Based on this success, the concept to combine desired properties of different materials is transferred to the p-type contact. Here, a mixture of the small molecule Spiro-OMeTAD [2,2’,7,7’-tetrakis(N,N-di-p-methoxyphenylamine)-9,9’-spirobifluoren] and the doped polymer PEDOT [poly(3,4-ethylenedioxythiophene)] is presented as a novel hole selective contact. PEDOT thereby remarkably suppresses charge recombination at the perovskite surface, allowing an increase of quasi-Fermi level splitting in the absorber. Further, the addition of Spiro-OMeTAD into the PEDOT layer is shown to enhance charge extraction at the interface and allow high efficiencies up to 16.8%.
Finally, the knowledge on contact properties is applied to monolithic perovskite-SHJ tandem solar cells. The main goal is to optimize the top contact stack of doped Spiro-OMeTAD/molybdenum oxide(MoOx)/ITO towards higher transparency by two different routes. First, fine-tuning of the ITO deposition to mitigate chemical reduction of MoOx and increase the transmittance of MoOx/ITO stacks by 25%. Second, replacing Spiro-OMeTAD with the alternative hole transport materials PEDOT/Spiro-OMeTAD mixtures, CuSCN or PTAA [poly(triaryl amine)]. Experimental results determine layer thickness constrains and validate optical simulations, which subsequently allow to realistically estimate the respective tandem device performances. As a result, PTAA represents the most promising replacement for Spiro-OMeTAD, with a projected increase of the optimum tandem device efficiency for the herein used architecture by 2.9% relative to 26.5% absolute. The results also reveal general guidelines for further performance gains of the technology.
Hyperspectral remote sensing of the spatial and temporal heterogeneity of low Arctic vegetation
(2019)
Arctic tundra ecosystems are experiencing warming twice the global average and Arctic vegetation is responding in complex and heterogeneous ways. Shifting productivity, growth, species composition, and phenology at local and regional scales have implications for ecosystem functioning as well as the global carbon and energy balance. Optical remote sensing is an effective tool for monitoring ecosystem functioning in this remote biome. However, limited field-based spectral characterization of the spatial and temporal heterogeneity limits the accuracy of quantitative optical remote sensing at landscape scales. To address this research gap and support current and future satellite missions, three central research questions were posed:
• Does canopy-level spectral variability differ between dominant low Arctic vegetation communities and does this variability change between major phenological phases?
• How does canopy-level vegetation colour images recorded with high and low spectral resolution devices relate to phenological changes in leaf-level photosynthetic pigment concentrations?
• How does spatial aggregation of high spectral resolution data from the ground to satellite scale influence low Arctic tundra vegetation signatures and thereby what is the potential of upcoming hyperspectral spaceborne systems for low Arctic vegetation characterization?
To answer these questions a unique and detailed database was assembled. Field-based canopy-level spectral reflectance measurements, nadir digital photographs, and photosynthetic pigment concentrations of dominant low Arctic vegetation communities were acquired at three major phenological phases representing early, peak and late season. Data were collected in 2015 and 2016 in the Toolik Lake Research Natural Area located in north central Alaska on the North Slope of the Brooks Range. In addition to field data an aerial AISA hyperspectral image was acquired in the late season of 2016. Simulations of broadband Sentinel-2 and hyperspectral Environmental and Mapping Analysis Program (EnMAP) satellite reflectance spectra from ground-based reflectance spectra as well as simulations of EnMAP imagery from aerial hyperspectral imagery were also obtained.
Results showed that canopy-level spectral variability within and between vegetation communities differed by phenological phase. The late season was identified as the most discriminative for identifying many dominant vegetation communities using both ground-based and simulated hyperspectral reflectance spectra. This was due to an overall reduction in spectral variability and comparable or greater differences in spectral reflectance between vegetation communities in the visible near infrared spectrum.
Red, green, and blue (RGB) indices extracted from nadir digital photographs and pigment-driven vegetation indices extracted from ground-based spectral measurements showed strong significant relationships. RGB indices also showed moderate relationships with chlorophyll and carotenoid pigment concentrations. The observed relationships with the broadband RGB channels of the digital camera indicate that vegetation colour strongly influences the response of pigment-driven spectral indices and digital cameras can track the seasonal development and degradation of photosynthetic pigments.
Spatial aggregation of hyperspectral data from the ground to airborne, to simulated satel-lite scale was influenced by non-photosynthetic components as demonstrated by the distinct shift of the red edge to shorter wavelengths. Correspondence between spectral reflectance at the three scales was highest in the red spectrum and lowest in the near infra-red. By artificially mixing litter spectra at different proportions to ground-based spectra, correspondence with aerial and satellite spectra increased. Greater proportions of litter were required to achieve correspondence at the satellite scale.
Overall this thesis found that integrating multiple temporal, spectral, and spatial data is necessary to monitor the complexity and heterogeneity of Arctic tundra ecosystems. The identification of spectrally similar vegetation communities can be optimized using non-peak season hyperspectral data leading to more detailed identification of vegetation communities. The results also highlight the power of vegetation colour to link ground-based and satellite data. Finally, a detailed characterization non-photosynthetic ecosystem components is crucial for accurate interpretation of vegetation signals at landscape scales.
The size structure of autotroph communities – the relative abundance of small vs. large individuals – shapes the functioning of ecosystems. Whether common mechanisms underpin the size structure of unicellular and multicellular autotrophs is, however, unknown. Using a global data compilation, we show that individual body masses in tree and phytoplankton communities follow power-law distributions and that the average exponents of these individual size distributions (ISD) differ. Phytoplankton communities are characterized by an average ISD exponent consistent with three-quarter-power scaling of metabolism with body
mass and equivalence in energy use among mass classes. Tree communities deviate from this pattern in a manner consistent with equivalence in energy use among diameter size classes. Our findings suggest that whilst universal metabolic constraints ultimately underlie the emergent size structure of autotroph communities, divergent aspects of body size (volumetric vs. linear dimensions) shape the ecological outcome of metabolic scaling in forest vs. pelagic ecosystems.
Carbonate-rich silicate and carbonate melts play a crucial role in deep Earth magmatic processes and their melt structure is a key parameter, as it controls physical and chemical properties. Carbonate-rich melts can be strongly enriched in geochemically important trace elements. The structural incorporation mechanisms of these elements are difficult to study because such melts generally cannot be quenched to glasses, which are usually employed for structural investigations. This thesis investigates the influence of CO2 on the local environments of trace elements contained in silicate glasses with variable CO2 concentrations as well as in silicate and carbonate melts. The compositions studied include sodium-rich peralkaline silicate melts and glasses and carbonate melts similar to those occurring naturally at Oldoinyo Lengai volcano, Tanzania.
The local environments of the three elements yttrium (Y), lanthanum (La) and strontium (Sr) were investigated in synthesized glasses and melts using X-ray absorption fine structure (XAFS) spectroscopy. Especially extended X-ray absorption fine structure spectroscopy (EXAFS) provides element specific information on local structure, such as bond lengths, coordination numbers and the degree of disorder. To cope with the enhanced structural disorder present in glasses and melts, EXAFS analysis was based on fitting approaches using an asymmetric distribution function as well as a correlation model according to bond valence theory. Firstly, silicate glasses quenched from high pressure/temperature melts with up to 7.6 wt % CO2 were investigated. In strongly and extremely peralkaline glasses the local structure of Y is unaffected by the CO2 content (with oxygen bond lengths of ~ 2.29 Å). Contrary, the bond lengths for Sr-O and La-O increase with increasing CO2 content in the strongly peralkaline glasses from ~ 2.53 to ~ 2.57 Å and from ~ 2.52 to ~ 2.54 Å, respectively, while they remain constant in extremely peralkaline glasses (at ~ 2.55 Å and 2.54 Å, respectively). Furthermore, silicate and unquenchable carbonate melts were investigated in-situ at high pressure/temperature conditions (2.2 to 2.6 GPa, 1200 to 1500 °C) using a Paris-Edinburgh press. A novel design of the pressure medium assembly for this press was developed, which features increased mechanical stability as well as enhanced transmittance at relevant energies to allow for low content element EXAFS in transmission. Compared to glasses the bond lengths of Y-O, La-O and Sr-O are elongated by up to + 3 % in the melt and exhibit higher asymmetric pair distributions. For all investigated silicate melt compositions Y-O bond lengths were found constant at ~ 2.37 Å, while in the carbonate melt the Y-O length increases slightly to 2.41 Å. The La-O bond lengths in turn, increase systematically over the whole silicate – carbonate melt joint from 2.55 to 2.60 Å. Sr-O bond lengths in melts increase from ~ 2.60 to 2.64 Å from pure silicate to silicate-bearing carbonate composition with constant elevated bond length within the carbonate region.
For comparison and deeper insight, glass and melt structures of Y and Sr bearing sodium-rich silicate to carbonate compositions were simulated in an explorative ab initio molecular dynamics (MD) study. The simulations confirm observed patterns of CO2-dependent local changes around Y and Sr and additionally provide further insights into detailed incorporation mechanisms of the trace elements and CO2. Principle findings include that in sodium-rich silicate compositions carbon either is mainly incorporated as a free carbonate-group or shares one oxygen with a network former (Si or [4]Al) to form a non-bridging carbonate. Of minor importance are bridging carbonates between two network formers. Here, a clear preference for two [4]Al as adjacent network formers occurs, compared to what a statistical distribution would suggest. In C-bearing silicate melts minor amounts of molecular CO2 are present, which is almost totally dissolved as carbonate in the quenched glasses.
The combination of experiment and simulation provides extraordinary insights into glass and melt structures. The new data is interpreted on the basis of bond valence theory and is used to deduce potential mechanisms for structural incorporation of investigated elements, which allow for prediction on their partitioning behavior in natural melts. Furthermore, it provides unique insights into the dissolution mechanisms of CO2 in silicate melts and into the carbonate melt structure. For the latter, a structural model is suggested, which is based on planar CO3-groups linking 7- to 9-fold cation polyhedra, in accordance to structural units as found in the Na-Ca carbonate nyerereite. Ultimately, the outcome of this study contributes to rationalize the unique physical properties and geological phenomena related to carbonated silicate-carbonate melts.
The paper aims to lay out a framework for evaluating value shifts in the international legal order for the purposes of a forthcoming book. In view of current contestations it asks whether we are observing yet another period of norm change (Wandel) or even a more fundamental transformation of international law – a metamorphosis (Verwandlung). For this purpose it suggests to look into the mechanisms of how norms change from the perspective of legal and political science and also to approximate a reference point where change turns into metamorphosis. It submits that such a point may be reached where specific legally protected values are indeed changing (change of legal values) or where the very idea of protecting certain values through law is renounced (delegalizing of values). The paper discusses the benefits of such an interdisciplinary exchange and tries to identify differences and commonalities among both disciplinary perspectives.
Over the past decade, society has witnessed an increasing expansion of service economies as manufacturing (i.e., product-oriented) companies break free from their product-based business model and move toward more service-oriented value creation as a result of several economic, technological, and social changes. As they shift from products to (service) solutions, manufacturing companies pursue new strategic direction, inter alia, by extensively employing service business development activities.
The objective of this dissertation is to investigate the considerable (re-)emerging stream of service business development by providing vital insights for academia and management into important focus areas that have hardly, if at all, been (empirically) investigated in the existing literature before. Therefore, these findings can be vital to informing a differentiation in current and future marketing strategies in business practice.
First of all, this dissertation focuses on the extent to which service business development is transposed into business practice. Because scarce empirical-quantitative research has studied the current state of service business development across various industry and market sectors, this study analyzes a unique, manually collected dataset of 266 (product and service) business development activities. In so doing, this investigation contributes to literature by presenting a comprehensive, industry-wide status quo and trend report of service business development in practice.
Furthermore, given the surprisingly limited scientific attention paid to the question of how service business development is strategically configured and further applied to different environmental circumstances, this dissertation provides comprehensive theoretical and practical implications by analyzing in detail a sample of 137 service business developments of 66 product-oriented companies.
Lastly, manufacturers are recognizing that service-oriented value creation is moving toward a more collaborative process of co-creation as a promising measure to achieve competitive advantage, and even more as an appropriate response to complex business environments. Thus, an increasing number of companies around the world have recently introduced business models related to access-based services such as car-, scooter-, and bike-sharing systems. But despite the considerable advantages of access-based services as an alternative to ownership, these companies are now seeing that consumer adoption and (re-)usage rates remain insufficient. Owing to the lack of general and cross-national scientific knowledge, the purpose of this dissertation continues to explore which factors impede diffusion of related service business development activities from a consumer perspective and what kind of differences can be established between countries. Consequently, with a total of 1,443 participants, a cross-national survey was carried out in three countries, i.e., the United States, Germany, and China, to measure a vast number of different adoption barriers derived from a developed integrated framework that combines established theories within innovation and adoption behavior research.
We develop an amplitude spectral ratio method for event couples from clustered earthquakes to estimate seismic wave attenuation (Q-1) in the source volume. The method allows to study attenuation within the source region of earthquake swarms or aftershocks at depth, independent of wave path and attenuation between source region and surface station. We exploit the high-frequency slope of phase spectra using multitaper spectral estimates. The method is tested using simulated full wave-field seismograms affected by recorded noise and finite source rupture. The synthetic tests verify the approach and show that solutions are independent of focal mechanisms but also show that seismic noise may broaden the scatter of results. We apply the event couple spectral ratio method to northwest Bohemia, Czech Republic, a region characterized by the persistent occurrence of earthquake swarms in a confined source region at mid-crustal depth. Our method indicates a strong anomaly of high attenuation in the source region of the swarm with an averaged attenuation factor of Qp < 100. The application to S phases fails due to scattered P-phase energy interfering with S phases. The Qp anomaly supports the common hypothesis of highly fractured and fluid saturated rocks in the source region of the swarms in northwest Bohemia. However, high temperatures in a small volume around the swarms cannot be excluded to explain our observations.
Unfolding the history of one of the oldest human val-ues, the freedom of expression, while defining its limits, is a complicated task. Does freedom stop where hate starts? This very old dilemma is -now more than ever before- revealing new dimensions. Politicians and new laws aim at regulating free expression, while disagree-ments over such regulation gradually become a source of endless conflict in newly formed multicultural, inter-connected, and digitized societies. The example of the Network Enforcement Act is used to understand the idea of restrictive legal practices in Germany, but also to enlighten the fact that law is a human construction which was created in order to regulate communication among individuals. Alternative practices, to straight legal ones, are summarized to show other dimensions of regulating hate speech without involving top-down approaches. The article proposes the approach of re-storative justice as a combination of legal and medita-tive practices in cases of hate speech. One advantage of the restorative justice approach elaborated in this arti-cle is the potential to remedy the inner hate and the pain, both of the victim and perpetrator. Finally, reveal-ing parts of history and new aspects of the ‘hate speech-puzzle’, leads to a questioning of contemporary social structures that possibly generate hate itself.