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Solar cells based on hybrid perovskites materials have become significantly important among the third generation photovoltaics over the last few years. The first solid state solar cell was reported in 2012. Over the years, the power conversion efficiencies of these devices have increased at a tremendous pace and this has made the perovskite solar cell devices a serious competitor in the well-established market of thin-film and wafer technologies. Over time, a large number of articles on this topic has been published in peer-reviewed journals. The presence of lead in the most efficient hybrid perovskite materials have raised questions about the possible toxicity of these devices and the extent of their environmental impact. Therefore, a lot of research has been devoted to finding alternative perovskite materials with similar or even better opto-electronic properties. An alternative strategy to improve the efficiency of thin film solar cells is to build efficient tandem cells by combining two or more perovskite materials with specifically tailored band gaps. The first step towards the development of perovskite-only tandem solar cells is to identify complementary hybrid perovskite materials with specific band gaps that maximize the efficiency of tandem solar cells. The optimal set of optical gaps for a tandem structure made of two materials is 1.9 eV and 1.0 eV. Since the electronic properties of hybrid perovskites are known to be strongly dependent on the composition and distortion of the crystal lattice, strong focus has been made towards the structure optimisation as well as the calculation of the energy band gaps of the materials using density functional theory (DFT). In an attempt to study the structure-property relationship of these perovskite materials and to find novel perovskite materials for future applications, researchers have employed computational screening procedures to study a large range of these materials by systematic replacement of the cations and anions from the prototypical perovskite. Density functional theory in particular is used as a theoretical tool, because of it’s precision to determine the properties of materials and also it’s computational viability in dealing with complex systems. In this thesis, the main focus is to do a systematic screening of the perovskite materials, of the composition ABX3 again by replacing the A-site, B-site and the X-site elements to find novel materials with band gaps suitable for application in tandem solar cells. As a first step towards contributing to this vibrant field of research, a high-throughput computational screening has been performed by replacing the metal and the halogen in the conventional CH3NH3PbI3 perovskites with homovalent metals and halogens to find materials in the desired range of band gaps that has already been mentioned earlier. This is achieved by performing a geometry optimisation on all the simulated structures followed by calculating their energy band gaps at the semilocal and the hybrid levels of theory. However, it is well known that the rotation of the organic cation CH3NH3 hinders the stability of these devices by the formation of hydrogen bonds between the hydrogen atoms of the cation and the halogens. This causes the materials to degrade under normal temperature and pressure conditions. As an attempt to prevent these devices from being unstable, a next step has been taken where the CH3NH3 cation has been replaced by inorganic cations of similar ionic radius. This is followed by another thorough screening, similar to the previous step. The stability of the materials has been determined by using the empirical Goldschmidt tolerance factor. As a last part of the thesis, a small proportion of the inorganic cation is mixed with CH3NH3 in order to form mixed-halide perovskites. These structures are optimised and their band gaps are calculated using density functional theory in order to predict materials suitable for single junction as well as tandem solar cell devices. It is expected that the contribution made through this thesis will be helpful for the progress of perovskite solar cells in terms of efficiencies and will also allow the community to explore the different properties these materials for further progress and development.
Recently crops encounter an increased number of individual and combined abiotic and biotic stress, which severely affect their growth and yield. Plants are associated with a large number of microorganisms including beneficial as well as pathogenic microorganisms. The interaction of plants with beneficial microorganisms can exert a substantial impact on plant growth and health and their potential can be utilized in sustainable plant production systems. Currently, climate change will increase the impact of stress on crops which will more likely be exposed to combined abiotic and biotic stress. At present, knowledge on how abiotic and biotic stress and the combination of both stresses affect the plant performance and the microbiome is limited. Soil-borne pathogens are responsible for relevant economic losses and are difficult to control. The root bacterial endophytes have shown potential in alleviating stress on plants and improving crop yield and quality. This raises the question how individual abiotic stress like salinity (ionic) and drought (osmotic) and the combination with biotic stress (Verticillium dahliae or Fusarium oxysporum) affects the root microbiota and thus the performance of the plant. Therefore, the goal of this thesis was to improve the understanding of the impact of individual and combined biotic and abiotic stress especially the endophytic root microbiota and thus plant performance. The work is focused on the economically important horticultural crop tomato. The bacterial rootendophytes of tomato plants exposed to individual and combined abiotic and biotic stress was studied with culture-independent and culture-dependent methods. Bacterial root endophytes obtained from tomato roots exposed to individual and combined stress were characterized for their traits that are beneficial to plant growth and health in in vitro and in vivo assays. Finally, the efficacy of selected endophytes in alleviating individual and combined abiotic and biotic stress in tomato plants was assessed. Furthermore, stress conditions can alter the composition of root exudates and volatiles, which may in turn affect the root microbiota assembly. Therefore, the volatile profiles of healthy and pathogen (F. oxysporum) infected tomato roots grown in soil was investigated. A soil olfactometer was established to study the impact of root volatiles of healthy and infected tomato on migration of applied beneficial bacteria. The results of tomato characteristics (plant growth, photosynthesis rate) confirmed the negative effect of individual abiotic and biotic stress reported in other studies. However, the response of combined abiotic stress with biotic stress on plant growth varied depending on the type of combined stress.. For instance, a significant higher negative impact on plant growth was observed when tomato plants were cultivated under ionic stress and infected with F. oxysporum. No additional negative effect on plant growth was observed when tomato was infected with V. dahliae. Both culture-dependent and cultureindependent analyses of the root microbiota revealed that individual and combined abiotic and biotic stress alter the root microbiota structure and diversity of tomato. A significantly lower number of cultivable root endophytes was obtained from roots exposed to ionic stress. 16S rRNA amplicon analysis revealed a stronger impact on the diversity of root-associated bacteria in comparison to biotic stress. The endophytes were characterized as member of the phyla Proteobacteria, Actinobacteria and Firmicutes, and members of Bacteriodetes were only detected by culture-independent approach. A total of 683 cultivable bacterial endophytes were characterized using various in vitro and in vivo plant growth-promoting (PGP) assays. As expected, the highest number of root endophytes with tolerance to ionic stress were obtained from tomato roots exposed to ionic stress. Comparably, a high percentage of root endophytes isolated from roots exposed to osmotic were tolerant to osmotic stress showing that the environment affects the selection of microorganisms by the plant. Interestingly, endopyhtes obtained from roots exposed to abiotic stress showed no traits related to plant growth promotion. Based on in vivo and in vitro traits, five selected endophytes were able to alleviate abiotic and biotic stress on plants. These endophytes were obtained from tomato roots infected with V. dahliae. The blend of root emitted volatiles also differed between healthy and F. oxysporum infected tomato plants. The olfactometer setup results highlighted that root volatiles were involved in attraction of bacteria to the plant roots and beneficial bacteria were observed to migrate towards both, diseased and healthy plants in comparable density. It is proposed that root volatiles from healthy and pathogen infected plants not only work as signals but are also used as an energy source for the rhizosphere bacteria. Concluding, the results of this study indicate that abiotic and biotic stress altered the bacterial rootendophytes and thus affects plant performance. The treatment of plants with beneficial microorganisms reduced the negative impact of stress conditions on plant performance. However, more studies using the selected isolates must be performed in the field for drawing inferences on the efficacy of the selected bacterial isolates in ameliorating the effect of abiotic and biotic stress in plants. The extensive isolate collection will serve as a basis for conducting investigations of root-associated bacteria on plant performance. This is important for the development of new plant protection strategies.
Bioelectrochemical investigation of E. coli TMAO reductase and R. capsulatus formate dehydrogenase
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Each year, donor countries spend billions of Euros on development cooperation. Not surprisingly, a large strand of research has emerged which examines the impact of development cooperation. A sub-discipline within this strand of the literature deals with the question of whether the impact or effectiveness of development cooperation depends on the quality of the recipient country's policy and institutional environment. Over hundreds of studies have assessed this question at the macro level. In so doing, most of these studies test whether a potential effect of aid on the growth of a recipient country’s gross domestic product (GDP) is conditional on the country's policy and institutional environment. However, even after decades of research and hundreds of studies, no conclusive result has been found. One of the main reasons for the inconclusive state of the literature is that most macro-level studies have to deal with a high risk of endogeneity, treat aid as nothing but a pure income transfer, and rely on low-quality GDP data. To solve these three methodical issues, some authors have started to change the analytical focus from the macro to the micro level. Thus, these authors assess the determinants for the performance of individual development projects instead of the determinants for an effect of aid on GDP. Yet, even though the number of studies focusing on the micro level has increased steadily over the last few years, the state of the literature on the determinants for the performance of development projects still contains multiple highly relevant research gaps. The present thesis seeks to address three of these research gaps. The first research gap addressed by this thesis is related to the specific type of development cooperation. So far, nearly all existing studies focus on projects by Multilateral Development Banks. Research on the determinants for the performance of bilateral development projects is still rare. Thus, even though donors pledge to implement effective development projects, there are hardly any micro-level studies on bilateral projects. So far, only three studies use a sample which includes bilateral projects. Yet, none of the three studies assess the determinants for the performance of bilateral technical development projects. The first paper in the present thesis (GIZ paper) seeks to address this research gap by assessing the determinants for the performance of projects by the Deutsche Gesellschaft für Internationale Zusammenarbeit (GIZ), a bilateral state-owned aid agency active in the area of technical cooperation. The results of the paper indicate that some but not all of the existing theoretical arguments can be extended to bilateral technical projects as well.. For example, the level of market interventions in the recipient county only affects the performance of financial development projects, while the recipient country’s government capacity affects both technical and financial development projects. The paper also indicates that effects of determinants may vary among project sectors. The paper also highlights a dilemma of technical development cooperation. The countries with low government capacity are usually the ones most in need of technical cooperation projects. But, at the same time, they are also the countries in which these projects have the poorest performance The second research gap addressed by this thesis is related to one specific factor in the policy and institutional environment of recipient countries, namely corruption. This determinant is often cited as essential for project performance but has gained surprisingly little coverage in empirical studies. The few existing studies on the effect of corruption on project performance are inconclusive. Some find a statistically significant correlation, while others do not. Furthermore, so far, all existing studies use corruption perception indices as a measurement for corruption, despite the fact that these indices have well-known deficits when it comes to this research topic. One of these deficits is that such indices do not distinguish between different forms of corruption, even though it is likely that the effect of corruption will vary depending on the type of development project and form of corruption. The second paper in this thesis (Corruption paper) seeks to address this inconclusive state of the research while focusing on one specific form of corruption, namely bribery between private firms and public officials. The paper finds a small but statistically significant correlation between the corruption level and the performance of World Bank projects. The systematic effect of corruption on project performance confirms the need to consider the risk of corruption in the design and during the implementation of projects. Nonetheless, the relatively small effect of corruption and the low pseudo R-squareds advise not to overestimate the relevance of corruption for project performance. At least for the project level, the paper finds no indication that corruption is a primary obstacle to aid effectiveness. The third research gap addressed by this thesis is related to one specific sample, namely recipient countries of the International Development Association (IDA). The question of whether the policy and institutional environment affects project performance is of particular relevance for these countries, given that the World Bank's ratings on a country's policy and institutional environment decide how much IDA resources it receives. One core justification of such an allocation system is that it helps to steer more resources to places where they are most effective. However, so far, there is no conclusive empirical evidence for this statement. The only study specifically focusing on this topic, a study by the Independent Evaluation Group of the World Bank from 2010, has essential methodological limitations. The third paper of this thesis (CPR paper) seeks to address this research gap by testing whether a more refined analysis confirms the assumption of previous studies that the policy and institutional environment of IDA-recipient countries, measured by the Country Policy and Institutional Assessment ratings, has an effect on the performance of World Bank projects. Overall, neither the main regression models nor any of the robustness tests indicate a substantial correlation between the policy and institutional environment and project performance. Only for Investments Loans is the coefficient large enough to assume some effect. The overall results not only contradict the results of previous studies, but also raise strong doubts around one of the core justifications for the allocation system of the IDA. All three papers rely on a statistical large-N analysis of the performance ratings of individual development projects. These ratings are usually assigned based on the final evaluation of a project and indicate the merit or worth of an activity. The merit or worth of an activity itself is measured by criteria like relevance, effectiveness, and efficiency. In the case of the two papers on World Bank projects, the needed data stem from different databases of the World Bank. The relevant data for the GIZ paper are gathered from internal evaluation reports of the GIZ. Logistic regressions are applied as the main analytical tool. Overall, the three papers show that the policy and institutional environment of recipient countries matters for project performance, but only to a small degree and under certain circumstances. This result highlights that many researchers and practitioners tend to overestimate the role that the policy and institutional environment of recipient countries plays in project performance. Furthermore, the thesis shows that authors of future studies should consider possible interactions between project- and country-level determinants whenever possible, both in their theoretical arguments and statistical models. Otherwise, the debate on the determinants for project performance is at risk of degenerating into a statistics tournament without any connection to reality.
The European fire-bellied toad (Bombina bombina) is regarded as one of the most threatened species of amphibians in central Europe and is particularly affected by environmental perturbations. During the last decades population numbers in Germany have declined drastically due to pollution, eutrophication and habitat fragmentation. Illegal translocations resulted in an introgression from southern genotypes (probably Austrian) into three local Bombina populations (Northern Germany and Southern Sweden) belonging to the northern lineage of the species. Interestingly, these populations show high frequencies of allochthonous (non-local) alleles at multiple loci and outperform the autochthonous populations in terms of their body condition. Over a time period of ten years, I could show that the Southern lineage haplo- and genotypes are still present in the North and that frequencies of introgressed haplotypes in allochthonous populations did not increase over time. However, the introgression itself expanded towards adjacent populations while the overall haplotype diversity has decreased. In contrast, southern lineage genotypes for two candidate genes under selection, the (immunity) MHC class II gene, as well as the (temperature) stress response HSP70 kDa gene, either do not occur at all or only at low frequencies in northern populations. Furthermore, these alleles do not seem to follow the introgression pattern, as they are also present in non-introgressed populations. This thesis tested two possible outcomes of introgressive hybridization in Northern B. bombina populations: (1) local populations (autochthonous) of Bombina bombina are highly adapted to their environments so that introgression of alien genes causes outbreeding depression or (2) local populations of Bombina bombina potentially lack adaptive variation so that introgression of alien genes causes genetic rescue and promotes adaptive change. I found that this unintentional experiment, as a result of illegal translocations imitating introgression of alien genes coming from a southern population (potentially adapted to warmer climate) into a northern lineage (potentially adapted to local pathogens), has increased the genetic diversity and improved fitness in introgressed northern populations, without disrupting local adaptation in the threatened amphibian species B. bombina, favouring the genetic rescue hypothesis. These results and conclusions represent relevant information for future conservation plans, including supportive breeding programmes for fire-bellied toads in Northern Germany and Southern Sweden.