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Electron transfer (ET) reactions play a crucial role in the metabolic pathways of all organisms. In biotechnological approaches, the redox properties of the protein cytochrome c (cyt c), which acts as an electron shuttle in the respiratory chain, was utilized to engineer ET chains on electrode surfaces. With the help of the biopolymer DNA, the redox protein assembles into electro active multilayer (ML) systems, providing a biocompatible matrix for the entrapment of proteins.
In this study the characteristics of the cyt c and DNA interaction were defined on the molecular level for the first time and the binding sites of DNA on cyt c were identified. Persistent cyt c/DNA complexes were formed in solution under the assembly conditions of ML architectures, i.e. pH 5.0 and low ionic strength. At pH 7.0, no agglomerates were formed, permitting the characterization of the NMR spectroscopy. Using transverse relaxation-optimized spectroscopy (TROSY)-heteronuclear single quantum coherence (HSQC) experiments, DNAs’ binding sites on the protein were identified. In particular, negatively charged AA residues, which are known interaction sites in cyt c/protein binding were identified as the main contact points of cyt c and DNA.
Moreover, the sophisticated task of arranging proteins on electrode surfaces to create functional ET chains was addressed. Therefore, two different enzyme types, the flavin dependent fructose dehydrogenase (FDH) and the pyrroloquinoline quinone dependent glucose dehydrogenase (PQQ-GDH), were tested as reaction partners of freely diffusing cyt c and cyt c immobilized on electrodes in mono- and MLs. The characterisation of the ET processes was performed by means of electrochemistry and the protein deposition was monitored by microgravimetric measurements. FDH and PQQ-GDH were found to be generally suitable for combination with the cyt c/DNA ML system, since both enzymes interact with cyt c in solution and in the immobilized state. The immobilization of FDH and cyt c was achieved with the enzyme on top of a cyt c monolayer electrode without the help of a polyelectrolyte. Combining FDH with the cyt c/DNA ML system did not succeed, yet. However, the basic conditions for this protein-protein interaction were defined. PQQ-GDH was successfully coupled with the ML system, demonstrating that that the cyt c/DNA ML system provides a suitable interface for enzymes and that the creation of signal chains, based on the idea of co-immobilized proteins is feasible.
Future work may be directed to the investigation of cyt c/DNA interaction under the precise conditions of ML assembly. Therefore, solid state NMR or X-ray crystallography may be required. Based on the results of this study, the combination of FDH with the ML system should be addressed. Moreover, alternative types of enzymes may be tested as catalytic component of the ML assembly, aiming on the development of innovative biosensor applications.
This PhD thesis is essentially a collection of six sequential articles on dynamics of accountability in the reformed employment and welfare administration in different countries. The first article examines how recent changes in the governance of employment services in three European countries (Denmark, Germany and Norway) have influenced accountability relationships from a very wide-ranging perspective. It starts from the overall assumption in the literature that accountability relationships are becoming more numerous and complex, and that these changes may lead to multiple accountability disorder. The article explores these assumptions by analyzing the different actors involved and the information requested in the new governance arrangements in all three countries. It concludes that the considerable changes in organizational arrangements and more managerial information demanded and provided have led to more shared forms of accountability. Nevertheless, a clear development towards less political or administrative accountability could not be observed.
The second article analyzes how the structure and development of reform processes affect accountability relationships and via what mechanisms. It is distinguished between an instrumental perspective and an institutional perspective and each of these perspectives takes a different view on the link between reforms and concrete action and results. By taking the welfare reforms in Norway and Germany as an example, it is shown that the reform outcomes in both countries are the result of a complex process of powering, puzzling and institutional constraints where different situational interpretations of problems, interests and administrative legacies had to be balanced. Accountability thus results not from a single process of environmental necessity or strategic choice, but from a dynamic interplay between different actors and institutional spheres.
The third article then covers a specific instrument of public sector reforms, i.e. the increasing use of performance management. The article discusses the challenges and ambiguities between performance management and different forms of accountability based on the cases of the reformed welfare administration in Norway and Germany. The findings are that the introduction of performance management creates new accountability structures which influence service delivery, but not necessarily in the direction expected by reform agents. Observed unintended consequences include target fixation, the displacement of political accountability and the predominance of control aspects of accountability.
The fourth article analyzes the accountability implications of the increasingly marketized models of welfare governance. It has often been argued that relocating powers and discretion to private contractors involve a trade-off between democratic accountability and efficiency. However, there is limited empirical evidence of how contracting out shapes accountability or is shaped by alternative democratic or administrative forms of accountability. Along these lines the article examines employment service accountability in the era of contracting out in Germany, Denmark and Great Britain. It is found that market accountability instruments are complementary instruments, not substitutes. The findings highlight the importance of administrative and political instruments in legitimizing marketized service provision and shed light on the processes that lead to the development of a hybrid accountability model.
The fifth and sixth articles focus on the diagonal accountability relationships between public agencies, supreme audit institutions (SAI) and parental ministry or parliament.
The fifth article examines the evolving role of SAIs in Denmark, Germany and Norway focusing particularly on their contribution to public accountability and their ambivalent relationship with some aspects of public sector reform in the welfare sector. The article analyzes how SAIs assess New Public Management inspired reforms in the welfare sector in the three countries. The analysis shows that all three SAIs have taken on an evaluative role when judging New Public Management instruments. At the same time their emphasis on legality and compliance can be at odds with some of the operating principles introduced by New Public Management reforms.
The sixth article focuses on the auditing activities of the German SAI in the field of labor market administration as a single in-depth case study. The purpose is to analyze how SAIs gain impact in diagonal accountability settings. The results show that the direct relationship between auditor and auditee based on cooperation and trust is of outstanding importance for SAIs to give effect to their recommendations. However, if an SAI has to rely on actors of diagonal accountability, it is in a vulnerable position as it might lose control over the interpretation of its results.
In this thesis, I study ultrafast dynamics in perovskite oxides using time resolved broadband spectroscopy. I focus on the observation of coherent phonon propagation by time resolved Brillouin scattering: following the excition of metal transducer films with a femtosecond infrared pump pulse, coherent phonon dynamics in the GHz frequency range are triggered. Their propagation is monitored using a delayed white light probe pulse. The technique is illustrated on various thin films and multilayered samples. I apply the technique to investigate the linear and nonlinear acoustic response in bulk SrTiO_3, which displays a ferroelastic phase transition from a cubic to a tetragonal structural phase at T_a=105 K. In the linear regime, I observe a coupling of the observed acoustic phonon mode to the softening optic modes describing the phase transition. In the nonlinear regime, I find a giant slowing down of the sound velocity in the low temperature phase that is only observable for a strain amplitude exceeding the tetragonality of the material. It is attributed to a coupling of the high frequency phonons to ferroelastic domain walls in the material. I propose a new mechanism for the coupling of strain waves to the domain walls that is only effective for high amplitude strain. A detailed study of the phonon attenuation across a wide temperature range shows that the phonon attenuation at low temperatures is influenced by the domain configuration, which is determined by interface strain. Preliminary measurements on magnetic-ferroelectric multilayers reveal that the excitation fluence needs to be carefully controlled when dynamics at phase transitions are studied.
The overarching goal of this dissertation is to provide a better understanding of the role of wind and water in shaping Earth’s Cenozoic orogenic plateaus - prominent high-elevation, low relief sectors in the interior of Cenozoic mountain belts. In particular, the feedbacks between surface uplift, the build-up of topography and ensuing changes in precipitation, erosion, and vegetation patterns are addressed in light of past and future climate change. Regionally, the study focuses on the two world’s largest plateaus, the Altiplano-Puna Plateau of the Andes and Tibetan Plateau, both characterized by average elevations of >4 km. Both plateaus feature high, deeply incised flanks with pronounced gradients in rainfall, vegetation, hydrology, and surface processes. These characteristics are rooted in the role of plateaus to act as efficient orographic barriers to rainfall and to force changes in atmospheric flow.
The thesis examines the complex topics of tectonic and climatic forcing of the surface-process regime on three different spatial and temporal scales: (1) bedrock wind-erosion rates are quantified in the arid Qaidam Basin of NW Tibet over millennial timescales using cosmogenic radionuclide dating; (2) present-day stable isotope composition in rainfall is examined across the south-central Andes in three transects between 22° S and 28° S; these data are modeled and assessed with remotely sensed rainfall data of the Tropical Rainfall Measuring Mission and the Moderate Resolution Imaging Spectroradiometer; (3) finally, a 2.5-km-long Mio-Pliocene sedimentary record of the intermontane Angastaco Basin (25°45’ S, 66°00’ W) is presented in the context of hydrogen and carbon compositions of molecular lipid biomarker, and oxygen and carbon isotopes obtained from pedogenic carbonates; these records are compared to other environmental proxies, including hydrated volcanic glass shards from volcanic ashes intercalated in the sedimentary strata.
There are few quantitative estimates of eolian bedrock-removal rates from arid, low relief landscapes. Wind-erosion rates from the western Qaidam Basin based on cosmogenic 10Be measurements document erosion rates between 0.05 to 0.4 mm/yr. This finding indicates that in arid environments with strong winds, hyperaridity, exposure of friable strata, and ongoing rock deformation and uplift, wind erosion can outpace fluvial erosion. Large eroded sediment volumes within the Qaidam Basin and coeval dust deposition on the Chinese Loess plateau, exemplify the importance of dust production within arid plateau environments for marine and terrestrial depositional processes, but also health issues and fertilization of soils.
In the south-central Andes, the analysis of 234 stream-water samples for oxygen and hydrogen reveals that areas experiencing deep convective storms do not show the commonly observed patterns of isotopic fractionation and the expected co-varying relationships between oxygen and hydrogen with increasing elevation. These convective storms are formed over semi-arid intermontane basins in the transition between the broken foreland of the Sierras Pampeanas, the Eastern Cordillera, and the Puna Plateau in the interior of the orogen. Here, convective rainfall dominates the precipitation budget and no systematic stable isotope-elevation relationship exists. Regions to the north, in the transition between the broken foreland and the Subandean foreland fold-and-thrust belt, the impact of convection is subdued, with lower degrees of storminess and a stronger expected isotope-elevation relationship. This finding of present-day fractionation trends of meteoric water is of great importance for paleoenvironmental studies in attempts to use stable isotope relationships in the reconstruction of paleoelevations.
The third part of the thesis focuses on the paleohydrological characteristics of the Mio-Pliocene (10-2 Ma) Angastaco Basin sedimentary record, which reveals far-reaching environmental changes during Andean uplift and orographic barrier formation. A precipitation- evapotranspiration record identifies the onset of a precipitation regime related to the South American Low Level Jet at this latitude after 9 Ma. Humid foreland conditions existed until 7 Ma, followed by orographic barrier uplift to the east of the present-day Angastaco Basin. This was superseded by rapid (~0.5 Myr) aridification in an intermontane basin, highlighting the effects of eastward-directed deformation. A transition in vegetation cover from a humid C3 forest ecosystem to semi-arid C4-dominated vegetation was coeval with continued basin uplift to modern elevations.
Anthropogenic activities have transformed the Earth's environment, not only on local level, but on the planetary-scale causing global change. Besides industrialization, agriculture is a major driver of global change. This change in turn impairs the agriculture sector, reducing crop yields namely due to soil degradation, water scarcity, and climate change. However, this is a more complex issue than it appears. Crop yields can be increased by use of agrochemicals and fertilizers which are mainly produced by fossil energy. This is important to meet the increasing food demand driven by global demographic change, which is further accelerated by changes in regional lifestyles. In this dissertation, we attempt to address this complex problem exploring agricultural potential globally but on a local scale. For this, we considered the influence of lifestyle changes (dietary patterns) as well as technological progress and their effects on climate change, mainly greenhouse gas (GHG) emissions. Furthermore, we examined options for optimizing crop yields in the current cultivated land with the current cropping patterns by closing yield gaps. Using this, we investigated in a five-minute resolution the extent to which food demand can be met locally, and/or by regional and/or global trade. Globally, food consumption habits are shifting towards calorie rich diets. Due to dietary shifts combined with population growth, the global food demand is expected to increase by 60-110% between 2005 and 2050. Hence, one of the challenges to global sustainability is to meet the growing food demand, while at the same time, reducing agricultural inputs and environmental consequences. In order to address the above problem, we used several freely available datasets and applied multiple interconnected analytical approaches that include artificial neural network, scenario analysis, data aggregation and harmonization, downscaling algorithm, and cross-scale analysis.
Globally, we identified sixteen dietary patterns between 1961 and 2007 with food intakes ranging from 1,870 to 3,400 kcal/cap/day. These dietary patterns also reflected changing dietary habits to meat rich diets worldwide. Due to the large share of animal products, very high calorie diets that are common in the developed world, exhibit high total per capita emissions of 3.7-6.1 kg CO2eq./day. This is higher than total per capita emissions of 1.4-4.5 kg CO2eq./day associated with low and moderate calorie diets that are common in developing countries. Currently, 40% of the global crop calories are fed to livestock and the feed calorie use is four times the produced animal calories. However, these values vary from less than 1 kcal to greater 10 kcal around the world. On the local and national scale, we found that the local and national food production could meet demand of 1.9 and 4.4 billion people in 2000, respectively. However, 1 billion people from Asia and Africa require intercontinental agricultural trade to meet their food demand. Nevertheless, these regions can become food self-sufficient by closing yield gaps that require location specific inputs and agricultural management strategies. Such strategies include: fertilizers, pesticides, soil and land improvement, management targeted on mitigating climate induced yield variability, and improving market accessibility. However, closing yield gaps in particular requires global N-fertilizer application to increase by 45-73%, P2O5 by 22-46%, and K2O by 2-3 times compare to 2010. Considering population growth, we found that the global agricultural GHG emissions will approach 7 Gt CO2eq./yr by 2050, while the global livestock feed demand will remain similar to 2000. This changes tremendously when diet shifts are also taken into account, resulting in GHG emissions of 20 Gt CO2eq./yr and an increase of 1.3 times in the crop-based feed demand between 2000 and 2050. However, when population growth, diet shifts, and technological progress by 2050 were considered, GHG emissions can be reduced to 14 Gt CO2eq./yr and the feed demand to nearly 1.8 times compare to that in 2000. Additionally, our findings shows that based on the progress made in closing yield gaps, the number of people depending on international trade can vary between 1.5 and 6 billion by 2050. In medium term, this requires additional fossil energy. Furthermore, climate change, affecting crop yields, will increase the need for international agricultural trade by 4% to 16%.
In summary, three general conclusions are drawn from this dissertation. First, changing dietary patterns will significantly increase crop demand, agricultural GHG emissions, and international food trade in the future when compared to population growth only. Second, such increments can be reduced by technology transfer and technological progress that will enhance crop yields, decrease agricultural emission intensities, and increase livestock feed conversion efficiencies. Moreover, international trade dependency can be lowered by consuming local and regional food products, by producing diverse types of food, and by closing yield gaps. Third, location specific inputs and management options are required to close yield gaps. Sustainability of such inputs and management largely depends on which options are chosen and how they are implemented. However, while every cultivated land may not need to attain its potential yields to enable food security, closing yield gaps only may not be enough to achieve food self-sufficiency in some regions. Hence, a combination of sustainable implementations of agricultural intensification, expansion, and trade as well as shifting dietary habits towards a lower share of animal products is required to feed the growing population.
Plant cell walls are complex structures that underpin plant growth and are widely exploited in diverse human activities thus placing them with a central importance in biology. Cell walls have been a prominent area of research for a long time, but the chemical complexity and diversity of cell walls not just between species, but also within plants, between cell-types, and between cell wall micro-domains pose several challenges. Progress accelerated several-fold in cell wall biology owing to advances in sequencing technology, aided soon thereafter by advances in omics and imaging technologies. This development provides additional perspectives of cell walls across a rapidly growing number of species, highlighting a myriad of architectures, compositions, and functions.
Furthermore, rather than the component centric view, integrative analysis of the different cell wall components across system-levels help to gain a more in-depth understanding of the structure and biosynthesis of the cell envelope and its interactions with the environment.
To this end, in this work three case studies are detailed, all pertaining to the integrative analysis of heterogeneous cell wall related data arising from different system-levels and analytical techniques. A detailed account of multiblock methods is provided and in particular canonical correlation and regression methods of data integration are discussed. In the first integrative analysis, by employing canonical correlation analysis - a multivariate statistical technique to study the association between two datasets - novel insight to the relationship between glycans and phenotypic traits is gained. In addition, sparse partial least squares regression approach that adapts Lasso penalization and allows for the selection of a subset of variables was employed. The second case study focuses on an integrative analysis of images obtained from different spectroscopic techniques. By employing yet another multiblock approach - multiple co-inertia analysis, insitu biochemical composition of cell walls from different cell-types is studied thereby highlighting the common and complementary parts of the two hyperspectral imaging techniques. Finally, the third integrative analysis facilitates gene expression analysis of the Arabidopsis root transcriptome and translatome for the identification of cell wall related genes and compare expression patterns of cell wall synthesis genes. The computational analysis considered correlation and variation of expression across cell-types at both system-levels, and also provides insight into the degree of co-regulatory relationships that are preserved between the two processes.
The integrative analysis of glycan data and phenotypic traits in cotton fibers using canonical methods led to the identification of specific polysaccharides which may play a major role during fiber development for the final fiber characteristics. Furthermore, this analysis provides a base for future studies on glycan arrays in case of developing cotton fibers. The integrative analysis of images from infrared and Raman spectroscopic approaches allowed the coupling of different analytical techniques to characterize complex biological material, thereby, representing various facets of their chemical properties. Moreover, the results from the co-inertia analysis demonstrated that the study was well adapted as it is relevant for coupling data tables in a symmetric way. Several indicators are proposed to investigate how the global and block scores are related. In addition, studying the root cells of \textit{Arabidopsis thaliana} allowed positing a novel pipeline to systematically investigate and integrate the different levels of information available at the global and single-cell level. The conducted analysis also confirms that previously identified key transcriptional activators of secondary cell wall development display highly conserved patterns of transcription and translation across the investigated cell-types. Moreover, the biological processes that display conserved and divergent patterns based on the cell-type-specific expression and translation levels are identified.