@article{BaldKellerKopyra2014, author = {Bald, Ilko and Keller, Adrian and Kopyra, Janina}, title = {On the role of fluoro-substituted nucleosides in DNA radiosensitization for tumor radiation therapy}, series = {RSC Advances : an international journal to further the chemical sciences}, volume = {4}, journal = {RSC Advances : an international journal to further the chemical sciences}, number = {13}, publisher = {Royal Society of Chemistry}, issn = {2046-2069}, doi = {10.1039/C3RA46735J}, pages = {6825 -- 6829}, year = {2014}, abstract = {Gemcitabine (2′,2′-difluorocytidine) is a well-known radiosensitizer routinely applied in concomitant chemoradiotherapy. During irradiation of biological media with high-energy radiation secondary low-energy (<10 eV) electrons are produced that can directly induce chemical bond breakage in DNA by dissociative electron attachment (DEA). Here, we investigate and compare DEA to the three molecules 2′-deoxycytidine, 2′-deoxy-5-fluorocytidine, and gemcitabine. Fluorination at specific molecular sites, i.e., nucleobase or sugar moiety, is found to control electron attachment and subsequent dissociation pathways. The presence of two fluorine atoms at the sugar ring results in more efficient electron attachment to the sugar moiety and subsequent bond cleavage. For the formation of the dehydrogenated nucleobase anion, we obtain an enhancement factor of 2.8 upon fluorination of the sugar, whereas the enhancement factor is 5.5 when the nucleobase is fluorinated. The observed fragmentation reactions suggest enhanced DNA strand breakage induced by secondary electrons when gemcitabine is incorporated into DNA.}, language = {en} } @phdthesis{Secker2014, author = {Secker, Christian}, title = {Polypeptoid block coloymers}, pages = {128}, year = {2014}, language = {en} } @phdthesis{Faber2014, author = {Faber, Michael}, title = {Folding dynamics of RNA secondary structures}, pages = {85}, year = {2014}, language = {en} } @phdthesis{Lindauer2014, author = {Lindauer, T. Marius}, title = {Algorithm selection, scheduling and configuration of Boolean constraint solvers}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-71260}, school = {Universit{\"a}t Potsdam}, pages = {ii, 130}, year = {2014}, abstract = {Boolean constraint solving technology has made tremendous progress over the last decade, leading to industrial-strength solvers, for example, in the areas of answer set programming (ASP), the constraint satisfaction problem (CSP), propositional satisfiability (SAT) and satisfiability of quantified Boolean formulas (QBF). However, in all these areas, there exist multiple solving strategies that work well on different applications; no strategy dominates all other strategies. Therefore, no individual solver shows robust state-of-the-art performance in all kinds of applications. Additionally, the question arises how to choose a well-performing solving strategy for a given application; this is a challenging question even for solver and domain experts. One way to address this issue is the use of portfolio solvers, that is, a set of different solvers or solver configurations. We present three new automatic portfolio methods: (i) automatic construction of parallel portfolio solvers (ACPP) via algorithm configuration,(ii) solving the \$NP\$-hard problem of finding effective algorithm schedules with Answer Set Programming (aspeed), and (iii) a flexible algorithm selection framework (claspfolio2) allowing for fair comparison of different selection approaches. All three methods show improved performance and robustness in comparison to individual solvers on heterogeneous instance sets from many different applications. Since parallel solvers are important to effectively solve hard problems on parallel computation systems (e.g., multi-core processors), we extend all three approaches to be effectively applicable in parallel settings. We conducted extensive experimental studies different instance sets from ASP, CSP, MAXSAT, Operation Research (OR), SAT and QBF that indicate an improvement in the state-of-the-art solving heterogeneous instance sets. Last but not least, from our experimental studies, we deduce practical advice regarding the question when to apply which of our methods.}, language = {en} } @phdthesis{Loersch2014, author = {Loersch, Christian}, title = {Business start-ups and the effect of coaching programs}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-72605}, school = {Universit{\"a}t Potsdam}, pages = {XII, 282}, year = {2014}, abstract = {Entrepreneurship is known to be a main driver of economic growth. Hence, governments have an interest in supporting and promoting entrepreneurial activities. Start-up subsidies, which have been analyzed extensively, only aim at mitigating the lack of financial capital. However, some entrepreneurs also lack in human, social, and managerial capital. One way to address these shortcomings is by subsidizing coaching programs for entrepreneurs. However, theoretical and empirical evidence about business coaching and programs subsidizing coaching is scarce. This dissertation gives an extensive overview of coaching and is the first empirical study for Germany analyzing the effects of coaching programs on its participants. In the theoretical part of the dissertation the process of a business start-up is described and it is discussed how and in which stage of the company's evolvement coaching can influence entrepreneurial success. The concept of coaching is compared to other non-monetary types of support as training, mentoring, consulting, and counseling. Furthermore, national and international support programs are described. Most programs have either no or small positive effects. However, there is little quantitative evidence in the international literature. In the empirical part of the dissertation the effectiveness of coaching is shown by evaluating two German coaching programs, which support entrepreneurs via publicly subsidized coaching sessions. One of the programs aims at entrepreneurs who have been employed before becoming self-employed, whereas the other program is targeted at former unemployed entrepreneurs. The analysis is based on the evaluation of a quantitative and a qualitative dataset. The qualitative data are gathered by intensive one-on-one interviews with coaches and entrepreneurs. These data give a detailed insight about the coaching topics, duration, process, effectiveness, and the thoughts of coaches and entrepreneurs. The quantitative data include information about 2,936 German-based entrepreneurs. Using propensity score matching, the success of participants of the two coaching programs is compared with adequate groups of non-participants. In contrast to many other studies also personality traits are observed and controlled for in the matching process. The results show that only the program for former unemployed entrepreneurs has small positive effects. Participants have a larger survival probability in self-employment and a larger probability to hire employees than matched non-participants. In contrast, the program for former employed individuals has negative effects. Compared to individuals who did not participate in the coaching program, participants have a lower probability to stay in self-employment, lower earned net income, lower number of employees and lower life satisfaction. There are several reasons for these differing results of the two programs. First, former unemployed individuals have more basic coaching needs than former employed individuals. Coaches can satisfy these basic coaching needs, whereas former employed individuals have more complex business problems, which are not very easy to be solved by a coaching intervention. Second, the analysis reveals that former employed individuals are very successful in general. It is easier to increase the success of former unemployed individuals as they have a lower base level of success than former employed individuals. An effect heterogeneity analysis shows that coaching effectiveness differs by region. Coaching for previously unemployed entrepreneurs is especially useful in regions with bad labor market conditions. In summary, in line with previous literature, it is found that coaching has little effects on the success of entrepreneurs. The previous employment status, the characteristics of the entrepreneur and the regional labor market conditions play a crucial role in the effectiveness of coaching. In conclusion, coaching needs to be well tailored to the individual and applied thoroughly. Therefore, governments should design and provide coaching programs only after due consideration.}, language = {en} } @phdthesis{Munack2014, author = {Munack, Henry}, title = {From phantom blocks to denudational noise}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-72629}, school = {Universit{\"a}t Potsdam}, pages = {xvii, 172}, year = {2014}, abstract = {Knowing the rates and mechanisms of geomorphic process that shape the Earth's surface is crucial to understand landscape evolution. Modern methods for estimating denudation rates enable us to quantitatively express and compare processes of landscape downwearing that can be traced through time and space—from the seemingly intact, though intensely shattered, phantom blocks of the catastrophically fragmented basal facies of giant rockslides up to denudational noise in orogen-wide data sets averaging over several millennia. This great variety of spatiotemporal scales of denudation rates is both boon and bane of geomorphic process rates. Indeed, processes of landscape downwearing can be traced far back in time, helping us to understand the Earth's evolution. Yet, this benefit may turn into a drawback due to scaling issues if these rates are to be compared across different observation timescales. This thesis investigates the mechanisms, patterns and rates of landscape downwearing across the Himalaya-Tibet orogen. Accounting for the spatiotemporal variability of denudation processes, this thesis addresses landscape downwearing on three distinctly different spatial scales, starting off at the local scale of individual hillslopes where considerable amounts of debris are generated from rock instantaneously: Rocksliding in active mountains is a major impetus of landscape downwearing. Study I provides a systematic overview of the internal sedimentology of giant rockslide deposits and thus meets the challenge of distinguishing them from macroscopically and microscopically similar glacial deposits, tectonic fault-zone breccias, and impact breccias. This distinction is important to avoid erroneous or misleading deduction of paleoclimatic or tectonic implications. -> Grain size analysis shows that rockslide-derived micro-breccia closely resemble those from meteorite impact or tectonic faults. -> Frictionite may occur more frequently that previously assumed. -> M{\"o}ssbauer-spectroscopy derived results indicate basal rock melting in the absence of water, involving short-term temperatures of >1500°C. Zooming out, Study II tracks the fate of these sediments, using the example of the upper Indus River, NW India. There we use river sand samples from the Indus and its tributaries to estimate basin-averaged denudation rates along a ~320-km reach across the Tibetan Plateau margin, to answer the question whether incision into the western Tibetan Plateau margin is currently active or not. -> We find an about one-order-of-magnitude upstream decay—from 110 to 10 mm kyr^-1—of cosmogenic Be-10-derived basin-wide denudation rates across the morphological knickpoint that marks the transition from the Transhimalayan ranges to the Tibetan Plateau. This trend is corroborated by independent bulk petrographic and heavy mineral analysis of the same samples. -> From the observation that tributary-derived basin-wide denudation rates do not increase markedly until ~150-200 km downstream of the topographic plateau margin we conclude that incision into the Tibetan Plateau is inactive. -> Comparing our postglacial Be-10-derived denudation rates to long-term (>10^6 yr) estimates from low-temperature thermochronometry, ranging from 100 to 750 mm kyr^-1, points to an order- of-magnitude decay of rates of landscape downwearing towards present. We infer that denudation rates must have been higher in the Quaternary, probably promoted by the interplay of glacial and interglacial stages. Our investigation of regional denudation patterns in the upper Indus finally is an integral part of Study III that synthesizes denudation of the Himalaya-Tibet orogen. In order to identify general and time-invariant predictors for Be-10-derived denudation rates we analyze tectonic, climatic and topographic metrics from an inventory of 297 drainage basins from various parts of the orogen. Aiming to get insight to the full response distributions of denudation rate to tectonic, climatic and topographic candidate predictors, we apply quantile regression instead of ordinary least squares regression, which has been standard analysis tool in previous studies that looked for denudation rate predictors. -> We use principal component analysis to reduce our set of 26 candidate predictors, ending up with just three out of these: Aridity Index, topographic steepness index, and precipitation of the coldest quarter of the year. -> Topographic steepness index proves to perform best during additive quantile regression. Our consequent prediction of denudation rates on the basin scale involves prediction errors that remain between 5 and 10 mm kyr^-1. -> We conclude that while topographic metrics such as river-channel steepness and slope gradient—being representative on timescales that our cosmogenic Be-10-derived denudation rates integrate over—generally appear to be more suited as predictors than climatic and tectonic metrics based on decadal records.}, language = {en} } @phdthesis{Schmiedchen2014, author = {Schmiedchen, Bettina}, title = {Vitamin D and its linkage between chronic kidney disease and cardiovascular integrity}, pages = {113}, year = {2014}, language = {en} } @phdthesis{Albrecht2014, author = {Albrecht, Steve}, title = {Generation, recombination and extraction of charges in polymer}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-72285}, school = {Universit{\"a}t Potsdam}, pages = {144}, year = {2014}, abstract = {A dramatic efficiency improvement of bulk heterojunction solar cells based on electron-donating conjugated polymers in combination with soluble fullerene derivatives has been achieved over the past years. Certified and reported power conversion efficiencies now reach over 9\% for single junctions and exceed the 10\% benchmark for tandem solar cells. This trend brightens the vision of organic photovoltaics becoming competitive with inorganic solar cells including the realization of low-cost and large-area organic photovoltaics. For the best performing organic materials systems, the yield of charge generation can be very efficient. However, a detailed understanding of the free charge carrier generation mechanisms at the donor acceptor interface and the energy loss associated with it needs to be established. Moreover, organic solar cells are limited by the competition between charge extraction and free charge recombination, accounting for further efficiency losses. A conclusive picture and the development of precise methodologies for investigating the fundamental processes in organic solar cells are crucial for future material design, efficiency optimization, and the implementation of organic solar cells into commercial products. In order to advance the development of organic photovoltaics, my thesis focuses on the comprehensive understanding of charge generation, recombination and extraction in organic bulk heterojunction solar cells summarized in 6 chapters on the cumulative basis of 7 individual publications. The general motivation guiding this work was the realization of an efficient hybrid inorganic/organic tandem solar cell with sub-cells made from amorphous hydrogenated silicon and organic bulk heterojunctions. To realize this project aim, the focus was directed to the low band-gap copolymer PCPDTBT and its derivatives, resulting in the examination of the charge carrier dynamics in PCPDTBT:PC70BM blends in relation to by the blend morphology. The phase separation in this blend can be controlled by the processing additive diiodooctane, enhancing domain purity and size. The quantitative investigation of the free charge formation was realized by utilizing and improving the time delayed collection field technique. Interestingly, a pronounced field dependence of the free carrier generation for all blends is found, with the field dependence being stronger without the additive. Also, the bimolecular recombination coefficient for both blends is rather high and increases with decreasing internal field which we suggest to be caused by a negative field dependence of mobility. The additive speeds up charge extraction which is rationalized by the threefold increase in mobility. By fluorine attachment within the electron deficient subunit of PCPDTBT, a new polymer F-PCPDTBT is designed. This new material is characterized by a stronger tendency to aggregate as compared to non-fluorinated PCPDTBT. Our measurements show that for F-PCPDTBT:PCBM blends the charge carrier generation becomes more efficient and the field-dependence of free charge carrier generation is weakened. The stronger tendency to aggregate induced by the fluorination also leads to increased polymer rich domains, accompanied in a threefold reduction in the non-geminate recombination coefficient at conditions of open circuit. The size of the polymer domains is nicely correlated to the field-dependence of charge generation and the Langevin reduction factor, which highlights the importance of the domain size and domain purity for efficient charge carrier generation. In total, fluorination of PCPDTBT causes the PCE to increase from 3.6 to 6.1\% due to enhanced fill factor, short circuit current and open circuit voltage. Further optimization of the blend ratio, active layer thickness, and polymer molecular weight resulted in 6.6\% efficiency for F-PCPDTBT:PC70BM solar cells. Interestingly, the double fluorinated version 2F-PCPDTBT exhibited poorer FF despite a further reduction of geminate and non-geminate recombination losses. To further analyze this finding, a new technique is developed that measures the effective extraction mobility under charge carrier densities and electrical fields comparable to solar cell operation conditions. This method involves the bias enhanced charge extraction technique. With the knowledge of the carrier density under different electrical field and illumination conditions, a conclusive picture of the changes in charge carrier dynamics leading to differences in the fill factor upon fluorination of PCPDTBT is attained. The more efficient charge generation and reduced recombination with fluorination is counterbalanced by a decreased extraction mobility. Thus, the highest fill factor of 60\% and efficiency of 6.6\% is reached for F-PCPDTBT blends, while 2F-PCPDTBT blends have only moderate fill factors of 54\% caused by the lower effective extraction mobility, limiting the efficiency to 6.5\%. To understand the details of the charge generation mechanism and the related losses, we evaluated the yield and field-dependence of free charge generation using time delayed collection field in combination with sensitive measurements of the external quantum efficiency and absorption coefficients for a variety of blends. Importantly, both the yield and field-dependence of free charge generation is found to be unaffected by excitation energy, including direct charge transfer excitation below the optical band gap. To access the non-detectable absorption at energies of the relaxed charge transfer emission, the absorption was reconstructed from the CT emission, induced via the recombination of thermalized charges in electroluminescence. For a variety of blends, the quantum yield at energies of charge transfer emission was identical to excitations with energies well above the optical band-gap. Thus, the generation proceeds via the split-up of the thermalized charge transfer states in working solar cells. Further measurements were conducted on blends with fine-tuned energy levels and similar blend morphologies by using different fullerene derivatives. A direct correlation between the efficiency of free carrier generation and the energy difference of the relaxed charge transfer state relative to the energy of the charge separated state is found. These findings open up new guidelines for future material design as new high efficiency materials require a minimum energetic offset between charge transfer and the charge separated state while keeping the HOMO level (and LUMO level) difference between donor and acceptor as small as possible.}, language = {en} } @phdthesis{Supaporn2014, author = {Supaporn, Worakrit}, title = {Categorical equivalence of clones}, pages = {89}, year = {2014}, language = {en} } @phdthesis{Mauri2014, author = {Mauri, Marco}, title = {A model for sigma factor competition in bacterial cells}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-72098}, school = {Universit{\"a}t Potsdam}, pages = {167}, year = {2014}, abstract = {Bacteria respond to changing environmental conditions by switching the global pattern of expressed genes. In response to specific environmental stresses the cell activates several stress-specific molecules such as sigma factors. They reversibly bind the RNA polymerase to form the so-called holoenzyme and direct it towards the appropriate stress response genes. In exponentially growing E. coli cells, the majority of the transcriptional activity is carried out by the housekeeping sigma factor, while stress responses are often under the control of alternative sigma factors. Different sigma factors compete for binding to a limited pool of RNA polymerase (RNAP) core enzymes, providing a mechanism for cross talk between genes or gene classes via the sharing of expression machinery. To quantitatively analyze the contribution of sigma factor competition to global changes in gene expression, we develop a thermodynamic model that describes binding between sigma factors and core RNAP at equilibrium, transcription, non-specific binding to DNA and the modulation of the availability of the molecular components. Association of housekeeping sigma factor to RNAP is generally favored by its abundance and higher binding affinity to the core. In order to promote transcription by alternative sigma subunits, the bacterial cell modulates the transcriptional efficiency in a reversible manner through several strategies such as anti-sigma factors, 6S RNA and generally any kind of transcriptional regulators (e.g. activators or inhibitors). By shifting the outcome of sigma factor competition for the core, these modulators bias the transcriptional program of the cell. The model is validated by comparison with in vitro competition experiments, with which excellent agreement is found. We observe that transcription is affected via the modulation of the concentrations of the different types of holoenzymes, so saturated promoters are only weakly affected by sigma factor competition. However, in case of overlapping promoters or promoters recognized by two types of sigma factors, we find that even saturated promoters are strongly affected. Active transcription effectively lowers the affinity between the sigma factor driving it and the core RNAP, resulting in complex cross talk effects and raising the question of how their in vitro measure is relevant in the cell. We also estimate that sigma factor competition is not strongly affected by non-specific binding of core RNAPs, sigma factors, and holoenzymes to DNA. Finally, we analyze the role of increased core RNAP availability upon the shut-down of ribosomal RNA transcription during stringent response. We find that passive up-regulation of alternative sigma-dependent transcription is not only possible, but also displays hypersensitivity based on the sigma factor competition. Our theoretical analysis thus provides support for a significant role of passive control during that global switch of the gene expression program and gives new insights into RNAP partitioning in the cell.}, language = {en} }